compendium of the european cluster on catalysis · (water splitting, co 2 reduction, pollutant...

Catalysis Cluster - Compendium 2015

1

Compendium of the European Cluster on Catalysis

Edition 2015

Editor: Fotis Katsaros

N.C.S.R. Demokritos


2

Contents

A. Projects ....................................................................................................................... 3

CARINHYPH ..................................................................................................................... 4

CAPITA ............................................................................................................................ 9

CASCATBEL .................................................................................................................... 14

CEOPS ........................................................................................................................... 21

CyclicCO2R ..................................................................................................................... 26

DECORE ......................................................................................................................... 32

DEMCAMER .................................................................................................................. 39

eCAMM ........................................................................................................................ 46

FREECATS ...................................................................................................................... 49

INCAS ............................................................................................................................ 56

LIMPID .......................................................................................................................... 60

MEMERE ....................................................................................................................... 67

NEXT-GEN-CAT .............................................................................................................. 74

NEXT-GTL ...................................................................................................................... 80

NOVACAM .................................................................................................................... 84

OCMOL ......................................................................................................................... 90

PCATDES ....................................................................................................................... 96

4G-PHOTOCAT ............................................................................................................ 101

SCOT ........................................................................................................................... 107

SusFuelCat .................................................................................................................. 110

TERRA ......................................................................................................................... 115

B. Institutions .............................................................................................................. 119

CEFIC ........................................................................................................................... 120

CNR ............................................................................................................................. 122

E-MRS ......................................................................................................................... 124

ERIC ............................................................................................................................ 126

INSTM ......................................................................................................................... 129


3

A. Projects


4

CARINHYPH Bottom-up fabrication of nano carbon-

inorganic hybrid materials for photocatalytic hydrogen production

Proposal full Name: Bottom-up fabrication of nano carbon-inorganic hybrid materials for photocatalytic hydrogen production

Acronym: CARINHYPH Call Identifier: FP7-NMP-2012-SMALL-6 Duration: 01/01/2013 – 31/12/2015 Grant Agreement No: 310184 Total Budget: 3,879,770.08 € Coordinator: Dr. Juan José Vilatela Website: www.carinhyph.eu

Consortium List

No Beneficiary Name Short name

Country

1 Fundación IMDEA Materiales IMDEA Spain 2 Westfaelische Wilhelms-Universitaet Muenster WWU Germany 3 Thomas Swan & CO Limited TSwan United Kingdom 4 The chancellor, Masters and Scholars of the University

of Cambridge UCAM United Kingdom

5 Friedrich-Alexander-Universitat Erlangen Nurnberg FAU Germany 6 Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia

dei Materiali INSTM Italy

7 INAEL Electrical Systems S.A. INAEL Spain 8 Eidgenoessische Materialpruefungs-Und Forschungsanstalt EMPA Switzerland 9 Université de Fribourg AMI Switzerland

Contents 1. Summary .................................................................................................................................................... 5 2. Keywords ................................................................................................................................................... 5 3. Background – Current state of the art ....................................................................................................... 5 4. Scientific and technological challenges ..................................................................................................... 5 5. Objectives .................................................................................................................................................. 6 6. Significant results / exploitable results ..................................................................................................... 7 7. Expected impact ........................................................................................................................................ 7 8. People involved in the project ................................................................................................................... 7 9. References ................................................................................................................................................. 8 10. Copyright statement ................................................................................................................................ 8

http://en.wikipedia.org/wiki/Switzerland

http://en.wikipedia.org/wiki/Switzerland


5

1. Summary

CARINHYPH projects deals with the hierarchical assembly of functional nanomaterials into novel nanocarbon-inorganic hybrid structures for energy generation by photocatalyic hydrogen production, with Carbon NanoTubes (CNTs) and graphene the choice of nanocarbons. The scientific activities include the development of new functionalisation strategies targeted at improving charge transfer in hybrids and therefore their photocatalytic activity, and in transferring these synergistic effects by assembling the hybrid units into macroscopic structures.

Three different types of hybrid architectures will be explored: Hybrid 1 – consisting of inorganic gyroids impregnated with the nanocarbon; Hybrid 2 – consisting of nanocarbon membranes coated with the inorganic compound by atomic layer deposition; and Hybrid 3 - electrospun hybrid fibres.

CARINHYPH specifically aims to tailor interfacial charge and energy transfer processes by means of chemical functionalisation and evaluate them with photochemical and transient spectroscopy, as well as explore the effect of the nanocarbon as a substrate and heat sink, which stabilises smaller semiconductor particles and reduces agglomeration that will result in larger accessible surface areas.

Two industrial partners in the consortium, a (TSwan) nanocarbon supplier and a potential end user (INAEL), guarantee that both ends of the production line are taken into account for the development of new technologies and the production of a roadmap for industrial deployment. This roadmap will also measure sustainability of processes and materials developed in this project in terms of environmental and economic impact as compared to state-of-the-art techniques for the production of hydrogen by the use of adequate Life Cycle Costing (LCC) and Life Cycle Assessment (LCA) approaches.

2. Keywords

Energy generation, photocatalytic hydrogen production, hybrid materials, nanohybrids, graphene, carbon nanotubes.

3. Background – Current state of the art

Activated carbon has been considered for decades as an ideal material for photocatalytic application due to its high surface area and electrical conductivity, yet the availability of new 1D and 2D forms of nanostructured carbon which can be tailored at the nanoscale has opened a completely new range of engineering possibilities

1. The interface between nanocarbon and the

photoactive material, for example, has emerged as a powerful parameter that could potentially increase charge lifetime and therefore photocatalytic efficiency; yet current knowledge of interfacial charge transfer processes is very limited

2. Of particular interest is also

the role of defects and edges in nanocarbons3,

particularly in graphene samples, and which can result in higher chemical activity

4. Defects and edges are difficult

to control in graphene samples, especially when produced by high pressure exfoliation or oxidative treatments, unlike the liquid exfoliation route (used in this project) which can preserve the high crystallinity of graphene layers.

The bases of this project are molecular engineering, production of hybrids and hierarchical assembly of nanoscale building blocks, in the context of photocatalytic hydrogen generation. This project proposes strategies that will contribute to these three areas beyond the state-of-the-art.

Additionally, in contrast to other projects in the field of photochemical energy applications, it will focus on the materials challenge rather than on the application per se. Materials science holds the key to elevate semiconductor photocatalysis to its next level.

4. Scientific and technological challenges

There is an ever growing need to protect our environment by increasing energy efficiency and developing “clean” energy sources. These are global challenges, and their resolution is vital to our energy security. Using the energy of sunlight to split water into its constituent elements, oxygen and hydrogen, is the key requirement to realise the successful use of hydrogen as a clean energy source and was recently identified by the European Science Foundation as one of the world’s emerging key research fields. Many conventional materials, such as metals, ceramics, and plastics, cannot fulfil all requirements for these new technologies. It appears that these frontiers will not be realised solely by developing new materials, but by optimising material combinations on different length scales, taking advantage of their synergistic functions.

The aim of this project is to hierarchically assemble functional nanomaterials into novel nanocarbon-inorganic hybrid structures for energy generation by means of photocatalytic hydrogen production, the nanocarbons being CNTs and graphene. The key challenges include the optimisation of the interface between the nanocarbon and the inorganic semiconductor

5, e.g. by means of chemical

functionalisation6; the evaluation of synergistic effects

based on interfacial charge and energy transfer


6

processes, e.g. through photochemical and transient spectroscopy; and the development of novel hybrid architectures with controlled morphologies and pore structures. This development will be carried out in the context of energy generation through hydrogen production, but by its own nature, the project will contribute to current understanding of nanomaterials, hybrids and their assembly into larger structures.

The appeal of nanomaterials lies in their ability to downscale conventional technologies by at least an order of magnitude, offering a potentially cheaper and more environmentally friendly production route due to a drastic reduction in raw materials. Scaling down the particle size to nanometre dimensions also increases the specific surface area of the material; thus, applications with reactions at the gas-solid or liquid-solid interface will benefit most from this “striving to the smaller”. When two or more nanomaterials are combined together, their large surface areas also results in a large interfacial area, with the effect that the properties of the material become dominated by those of the interface rather than those of the individual bulk components. As a consequence, interfacial engineering has established itself as a powerful route to alter the properties and create advanced functional materials.

Figure 1: Scheme for interfacial charge transfer processes in nanocarbon-inorganic hybrid materials

One of the most promising examples of such materials is nanocarbon-inorganic hybrids, which have recently been introduced as a new class of multifunctional composite materials

7. In these hybrids, the nanocarbon is coated by

the inorganic material in the form of a thin amorphous, polycrystalline or single-crystalline film. In contrast to nanocomposites, in which the volume fraction of the nanocarbon is normally less than a few percent, hybrids are formed by both components with similar volume fractions. Typically, the inorganic compound is deposited from molecular precursors directly onto the surface of the nanocarbon, although the attachment of presynthesised building blocks via anchor molecules is also possible. The close proximity and similar size domains of the two phases introduce the interface as a powerful new parameter. Interfacial processes such as charge and energy transfer create synergistic effects beyond the properties of the individual components and have resulted in nanocarbon-inorganic hybrids with tremendous potential as supercapacitors, batteries, fuel

cells, photovoltaics and in field emission devices8;. These

hybrids also have great potential in photocatalytic applications, such as hydrogen production, solar energy conversion by dyesensitized solar cells, i.e. “Grätzel cell”, water and air purification, and self-cleaning surfaces

9. As

an example, the hybridisation of a photoactive zeolite (titanosilicate, TS-1) with graphene has enhanced its photocatalytic activity for the degradation of organic dyes by more than 25 times

10; which can be considered a

milestone in photocatalysis research.

Besides these interfacial effects, photocatalytic activity is also affected by the morphology and microstructure of the hybrid material, as these determine its specific surface area and pore size distribution, both being of paramount importance in photocatalytic reaction.

5. Objectives

The overall aim of this project is to exploit these synergistic effects to create new macroscopic materials with improved photocatalytic performance for the production of hydrogen. This will be accomplished through the following objectives:

Industrially produced nanocarbons with a very high purity (<5wt.% non-carbon) and degree of graphitisation (<1wt.% amorphous C) will be used. The nanocarbons will be chemically functionalised with specially designed groups.

These nanocarbons will be hybridised with inorganic semiconductors and assemble them into macroscopic materials with different morphologies and three different hybrid architectures: o Hybrid 1 - involving porous membranes and

vertical arrays o Hybrid 2 - nanocarbon-impregnated

inorganic gyroids. o Hybrid 3 - in-situ synthesis of nanocarbon-

inorganic hybrids via electrospinning.

The origin of interfacial processes and their effect on photocatalytic performance will be investigated. A key part of this project will be detailed studies of the nature of charge and energy transfer processes at the interface, which will be probed systematically by steady-state and timeresolved physicochemical means including transient absorption, Electron Spin Resonance (ESR), photoluminescence and Raman spectroscopy

5. The overriding challenge is to gain

control over the structural and electronic defect states and electronic coupling between the organic and inorganic constituents.Combining band-gap tuning with self-assembly features will lead to a toolbox for constructing materials that are accessible by straightforward fabrication methods and have exciting transport properties.


7

Assess the sustainability and safety of processes and materials developed in this project, in terms of environmental impacts and cost compared to today’s means for the production of hydrogen by the use of adequate Life Cycle Costing (LCC) and Life Cycle Assessment (LCA) approaches, and through an Environmental Health and Safety (EHS) assessment.

Development and testing of a demonstrator consisting of a photoreactor for solar photochemical hydrogen production with integrated nanocarbon-inorganic hybrid materials, and the preparation of a roadmap for industrial deployment based on an exhaustive study of component costs, feasibility of industrial scale up, viability of the process compared to today´s means of hydrogen production, and an analysis of potential impact of the new hybrid technology.

6. Significant results / exploitable results

At the moment (may 2015), and due to the low TRL of the project, an enhancer for multi-redox catalysis

(water splitting, CO2 reduction, pollutant degradation, valorization of methanol, etc) has been identified potential exploitable result of the project (short term). In the long term (out of the scope of the project), a catalyst itself could be developed. This enhancer is versatile (can be applied to many photocatalytic processes), efficient (high surface area and unique nanostructure allow for increased lifetime and stability of the photocatalysts), and possesses a hybrid structure (electronic hybridisation upon addition to photocatalyst). Additionally, CARINHYPH is developing knowledge in areas where there is currently a lack of information (inventory for LCA).

7. Expected impact

Understanding of nucleation, templating and “heat sink” effects at nanoscale and implications for bulk device properties.

Lab-scale production of nanohybrids engineered for charge transfer processes through interfacial tailoring.

8. People involved in the project

First Name Last Name Affiliation Address email

Juan José Vilatela IMDEA C/ Eric Kandel 2, Tecnogetafe, 28906, Getafe (Madrid), Spain

[email protected]

Dominik Eder WWU Corrensstr. 28/30. D-48149, Münster, Germany

[email protected]

Simon Grant TSwan Rotary Way, Consett, County Durham, DH8 7ND, United Kingdom

[email protected]

Ulrich Steiner AMI Chemin des Verdiers 4, CH-1700 Fribourg, Switzerland

[email protected]

Murizio Prato INSTM Piazzale Europa, 1, 34128 Trieste TS, Italy

[email protected]

Daniel Fernández INAEL C/ Jarama, 5, Polígono Industrial, 45007, Toledo, Spain

[email protected]

Roland Hischier EMPA Lerchenfeldstrasse 5, CH-9014, St. Gallen, Switzerland

[email protected]

mailto:[email protected]








8

9. References

1. Su DS, 2012, “Catalysis on nano-carbon materials: Going where to?”, Catalysis Today, vol 186, p1.

2. Su DS, Chen X, Weinberg G, Klein-Hofmann, Timpe O, Bee S, Hamid A, Schlogl R, 2005 “Hierarchically structured carbon: Synthesis of carbon nanofibers nested inside or immobilized onto modified activated carbon”, Ang. Chem., vol 44, p5488

3. Liang C, Xie V, Howe J, Dai S, Overbury SH, 2009, “Open-cage fullerene-like 4. Biddinger EJ, Ozkan US, 2010, “Role of graphitic edge plane exposure in carbon nanostructures for oxygen reduction

reaction”, J. Phys. Chem. C, vol 114, p15306. 5. Eder, D 2010, “Carbon nanotube - inorganic hybrid materials”, Chem. Rev., vol 110, pp. 1348 - 1385. 6. Rojas, GD, van der Pol, C, Brinkhaus, L, Katsukis, G, Bryce, MR, Clark, T & Guldi, DM 2010, “Control over Charge

Transfer through Molecular Wires by Temperature and Chemical Structure Modifications“, ACS Nano, vol 4, p. 6449.

7. Eder, D 2010, “Carbon nanotube - inorganic hybrid materials”, Chem. Rev., vol 110, pp. 1348 - 1385. 8. Vilatela, JJ & Eder, D 2012, “Nanocarbon composites and hybrids in sustainability: a review”, Chem. Sus. Chem., vol

3. 9. Eder, D 2010, “Carbon nanotube - inorganic hybrid materials”, Chem. Rev., vol 110, pp. 1348 - 1385. 10. Ren, Z, Kim, E, Pattinson, SW, Subrahmanyam, KS, Rao, CN, Cheetham, AK & Eder, D 2012, “Hybridizing

photoactive zeolites with graphene: a powerful strategy towards superior photocatalytic properties”, Chem. Sci., p. DOI: 10.1039/C1SC00511A.

10. Copyright statement

© 2015, IMDEA, C/ Eric Kandel 2, Tecnogetafe, 28906, Getafe (Madrid), Spain on behalf of the CARINHYPH consortium. CARINHYPH is a Small Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:

to Share — to copy, distribute and transmit the work

to Remix — to adapt the work

to make commercial use of the work; Under the following conditions: Attribution.

CARINHYPH and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;

For any reuse or distribution, you must make clear to others the license terms of this work. The best way to do this is with a link to this web page: http://creativecommons.org/licenses/by/3.0.

Statutory fair use and other rights are in no way affected by the above.


9

Catalytic Processes for Innovative

Technology Applications

Proposal full Name: Catalytic processes for innovative technology applications Acronym: CAPITA Call Identifier: NMP.3-ER-2011-266543 Duration: 01/01/2012 – 31/051/2014 Grant Agreement No: 266543 Total Budget: € 468,141.43 Coordinator: Dr. Nico Kos Website: www.era-capita.eu

Consortium List

No Beneficiary Name Short name Country

1 Netherlands Organisation for Scientific Research NWO Netherlands 2 Ministerio de Economia y Competitividad MICINN Spain 3 Centre National de la Recherche Scientifique CNRS France 4 Geniki Grammatia Erevnas Kai Technologias, Ypourgio

Paidias, Dia Viou Mathisis & Thriskevmaton GSRT Greece

5 Ministero dell’Istruzione, dell’Universita’ e della Ricerca MIUR Italy 6 Centre for Research and Technology Hellas CERTH Greece 7 Agentschap voor Innovatie door Wetenschap en Technologie IWT Belgium 8 Fundacao para a Ciencia e a Tecnologia FCT Portugal 9 Irish Research Council IRC Ireland 10 Rijksdienst voor Ondernemend Nederland RVO Netherlands 11 European Research Institute of Catalysis ERIC Belgium 12 Gesellschaft für Chemische Technik und Biotechnologie e.V. DECHEMA Germany 13 European Technology Platform for Sustainable Chemistry SUSCHEM Belgium

Contents

1. Summary .................................................................................................................................................... 9 2. Keywords ................................................................................................................................................. 10 3. Background – Current state of the art ..................................................................................................... 10 4. Scientific and technological challenges ................................................................................................... 10 5. Objectives ................................................................................................................................................ 10 6. Significant results / exploitable results ................................................................................................... 11 7. Expected impact ...................................................................................................................................... 12 8. People involved in the project ................................................................................................................. 12 9. Copyright statement ................................................................................................................................ 13

1. Summary

CAPITA ERA-NET has the ambition to better structure and enhance the coordination and cooperation between all innovation-driven research programmes in the ERA of Applied Catalysis and related sustainable chemical research. It aims to build on the achievements and network of the previous initiative

ACENET. It will work closely with the ETP SusChem and the European Research Institute of Catalysis (ERIC). To achieve a more sustainable industrial society in the next decades requires the development of new clean and affordable catalytic technologies for the production of liquid fuels, chemicals, pharmaceuticals and materials. Indeed, ETP SusChem has identified catalysis as the most important technology for process

http://www.era-capita.eu/


10

design. A strong science and engineering base in applied catalysis is thus essential to maintain Europe’s strength in this critical industrial sector and CAPITA aims to contribute to this.

2. Keywords

Catalytic processes, process technologies, innovative exploitation, low value carbon.


Applied Catalysis is an interdisciplinary research field which combines exciting, high-quality science and engineering with a unique potential to contribute to economically and environmentally sustainable technologies.

At present there is little coordination between the catalysis and the closely related sustainable chemistry research programmes of the EU member states, although many of them, acting individually and recognising the importance of the topic, have made catalysis a strong feature in their chemistry, bioscience, and materials and engineering research programmes.

The structured work programme includes development of dedicated procedures and systems for the coordination and integration of national programmatic applied research activities, identification of programmes and topics most relevant with respect to innovative potential for Europe, the creation of new, jointly managed, transnational programmes amongst others focussed on innovation, encouraging co-operation and the co-ordination of cross-border facilitative activities, e.g. education and training, and research infrastructure development.

The set goals are:

Initiation of joint transnational research activities and funding initiatives in Applied Catalysis

Establishment of a joint European framework for education and training in Applied Catalysis

Development of the necessary tools and activities for communication and information exchange

Through its links with end-users the CAPITA ERA-NET creates an effective system for encouraging commercial exploitation of research output, since it builds on a pan-European scale from the experience of successful national initiatives in The Netherlands, Germany and the United Kingdom. These initiatives have combined the knowledge and experience of academics, industrial end-users and funding bodies to

create successful innovation-driven strategic research programmes.


Applied Catalysis is an interdisciplinary research field which combines exciting, high-quality science and engineering with a unique potential to contribute to economically and environmentally sustainable technologies. At present there is little coordination between the catalysis and the closely related sustainable chemistry research programmes of the EU member states, although many of them, acting individually and recognising the importance of the topic, have made catalysis a strong feature in their chemistry, bioscience, and materials and engineering research programmes

The structured work programme includes development of dedicated procedures and systems for the coordination and integration of national programmatic applied research activities, identification of programmes and topics most relevant with respect to innovative potential for Europe, the creation of new, jointly managed, transnational programmes amongst others focussed on innovation, encouraging co-operation and the co-ordination of cross-border facilitative activities, e.g. education and training, and research infrastructure development.

The set goals are:

Initiation of joint transnational research activities and funding initiatives in Applied Catalysis

Establishment of a joint European framework for education and training in Applied Catalysis

Development of the necessary tools and activities for communication and information exchange

Through its links with end-users the CAPITA ERA-NET creates an effective system for encouraging commercial exploitation of research output, since it builds on a pan-European scale from the experience of successful national initiatives in The Netherlands, Germany and the United Kingdom. These initiatives have combined the knowledge and experience of academics, industrial end-users and funding bodies to create successful innovation-driven strategic research programmes.

5. Objectives

CAPITA ERA-NET has the ambition to better structure and enhance the coordination and cooperation between all innovation-driven research programmes in the ERA of Applied Catalysis and related sustainable


11

chemical research. This ambition is realised by pursuing the following objectives:

SYSTEMATIC EXCHANGE OF INFORMATION AND GOOD

PRACTICES on existing research programmes in the field of Applied Catalysis concerning their content and objectives, used selection and monitoring processes, dissemination of knowledge, utilisation of research results and cooperation mechanisms between universities, research organisations, industries and SMEs involved in these programmes;

COMMON AGREEMENT ON AND JOINT

IMPLEMENTATION OF EFFICIENT AND EFFECTIVE JOINT

PROCESSES, MECHANISMS AND PROCEDURES to manage the whole “chain of knowledge” covered by applied catalysis research programmes (i.e. from identifying relevant research priorities to stimulate the translation of the research results into (industrial) innovations);

COORDINATION, COOPERATION AND JOINT

PROGRAMME MANAGEMENT OF EXISTING RESEARCH

PROGRAMMES, amongst others by case studies in which programme managers of different organisations cooperate, focussed on the establishment of complete, joint management procedures, improved dissemination of generated knowledge between programmes and industrial users and implementation of the solutions obtained by the case studies for possible barriers to co-operation;

FORMULATION AND ESTABLISHMENT OF NEW

TRANSNATIONAL PAN-EUROPEAN RESEARCH

PROGRAMMES OR INITIATIVES, the content of which is based on the European Strategic Research Agenda (SRA) developed in the European Technology Platform (ETP) on Sustainable Chemistry; the management is performed according to procedures jointly defined by the ERA-NET partners and the funding is by consortia of stakeholders which were involved in the development of the SRA;

DEVELOPMENT OF THE NECESSARY TOOLS AND

ACTIVITIES FOR COMMUNICATION AND INFORMATION

EXCHANGE to reach the above-mentioned objectives;

DEVELOPMENT OF A FRAMEWORK FOR A EUROPEAN

EDUCATION AND TRAINING PROGRAMME that addresses strategic needs on all academic levels, to boost the standards of professionals

in this area, to improve the fit between employer demand and job-market supply and to enhance student, researcher and job market mobility. The European education and training programme will address both students and researchers with an interest in an academic career or an industrial or entrepreneurial career.


For achieving its ambition and objectives the CAPITA ERA-NET partners divided the work in five different work packages:

Main examples of successful activities carried out within these work packages include:

Mapping and coordinating the research priorities of national agencies

Developing a roadmap for Applied Catalysis in Europe

Launch of the a jointly coordinated, transnational call for project proposals in Applied Catalysis

Developing a coherent European training and education programme ready for implementation

WORKPACKAGE 1 Strategic development of

he CAPITA ERA-NET, its

programme and its

consortium

WORKPACKAGE2 Implementation of regular

transnational calls for

projects

WORKPACKAGE 3 Training & education and

interaction with European

industry, initiatives and

stakeholders

WORKPACKAGE 4 Information management,

communication and

dissemination

WORKPACKAGE 5 CAPITA ERA-NET project

coordination and

management


12

As a result of the first Capita call for proposals "Innovative catalysis for the monetization of low value carbon" five research projects have been Main examples of successful activities carried out within these work packages include:

Mapping and coordinating the research priorities of national agencies

Developing a roadmap for Applied Catalysis in Europe

Launch of the a jointly coordinated, transnational call for project proposals in Applied Catalysis

Developing a coherent European training and education programme ready for implementation

In June 2013, CAPITA launched its first transnational call for project proposals in Applied Catalysis, entitled: ‘Innovative catalysis for the monetization of low value carbon’. , CAPITA utilized M€ 2.2 of the call budget and another k€ 120 of private funding.

Funding was awarded to three projects:

WAste bio-feedstocks hydro-Valorisation processES (WAVES) A collaboration between Greece, the Netherlands, Italy, Belgium and Spain

Valorization of CARbon DIOxide containing industrial streams via non-conventional catalytic systems and SOLarized processes (CARDIOSOL) A collaboration between Greece and Italy

CO2 Conversion to Chemicals using Regenerable and Reusable Multifunctional Heterogeneous Catalysts

(CO2-HETCAT) A collaboration between Italy, The Netherlands and Spain

7. Expected impact

The impact of CAPITA, as expressed by the 1st

CAPITA Joint Call, the Joint Education activities and other dissemination actions, reveals desire for a European catalysis network.

The CAPITA partners have developed strong links amongst each other, and have focused their future plans in teaming up with Euro-chemistry, creating a pan-European Programme on Catalysis, based on the framework that CAPITA developed, with the aim of strengthening their links with industry and multiple R&D funding agencies.

Within Euro-chemistry CAPITA will utilize the European synergy for research in chemistry, to express the potential of bringing together national research organisations and funding agencies to establish joint strategies for collaborative research and improves funding mechanisms for European research in chemistry.

Core partners of the CAPITA ERANET, together with new partners will explore options for continuing the CAPITA activities, such as joint transnational calls and an advanced framework for training of PhD students, Post-Docs and industrial staff in innovative applied catalysis for the implementation of the principles of sustainable chemistry.



Alexandros Prosmitis CERTH Centre for Research & Technology Hellas, Mesogeion 357-359, 15231, Athens

[email protected]

Antonio Monzón Mineco C/ Albacete, 5. 28027˗Madrid, Spain

[email protected]

Pascale Massiani CNRS 3 rue Michel-Ange - 75794 Paris cedex 16, France

[email protected]

Guillermo Morales-Rodrigues

MINECO C/ Albacete, 5. 28027˗Madrid, Spain

[email protected]

Nico Kos NWO Laan van Nieuw Oost-Indië 300, 2593 CE The Hague, Netherlands

[email protected]

Michele Aresta MIUR Piazza Kennedy, 20 00144 ROMA, Italy

[email protected]

Axel Löfberg CNRS 3 rue Michel-Ange - 75794 Paris cedex 16, France

[email protected]

George Skevis CERTH Centre for Research & Technology Hellas, Mesogeion 357-359, 15231, Athens

[email protected]

Angel Lappas CERTH Centre for Research & Technology Hellas, Mesogeion

[email protected]



13

357-359, 15231, Athens

Fernando Dorado UCLM Facultad de Químicas. Campus Universitario s/n, 13004 Ciudad Real. Spain

[email protected]


© 2015, NWO, Laan van Nieuw Oost-Indië 300, 2593 CE The Hague, Netherlands, on behalf of the CAPITA consortium. CAPITA is a NMP under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




CAPITA and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




14

CASCATBEL CAScade deoxygenation process using tailored

nanoCATalysts for the production of BiofuELs from lignocellullosic biomass

Proposal full Name: CAScade deoxygenation process using tailored nanoCATalysts for the

production of BiofuELs from lignocellullosic biomass

Acronym: CASCATBEL Call Identifier: NMP-2013-LARGE-7 Duration: 01/11/2013 – 30/10/2017 Grant Agreement No: 604307 Total Budget: 9.301.176,53 € Coordinator: Prof. Dr. David Serrano Website: www.cascatbel.eu

Consortium List


1 Fundación IMDEA Energía IMDEA Energy Spain 2 ENCE Investigación y Desarrollo SAU ENCE Spain 3 Universita Karlova v Praze CUNI Czech Republic 4 Universitá degli Studi di Milano-Bicocca UNIMIB Italy 5 Ustav Fyzikalni Chemie J. Heirovskeho Av. CR, v.v.i. HIPC Czech Republic 6 Universiteit Utrecht UU Netherlands 7 Aston University AU U. Kingdom 8 Abengoa Research, S.L. ABR Spain 9 Eidgenoessische Tecnische Hochschule Zürich ETH Switzerland 10 Max Planck Institut Fuer Kohlenforschung MPIK Germany 11 Mast Carbon International Ltd. MASTCARBON U. Kingdom 12 SILKEM Proizvodnja Zeolitov Doo SILKEM Slovenia 13 NANOLOGICA AB NANOLOGICA Sweden 14 Centre for Research and Technology Hellas CERTH/CPERI Greece 15 ENI S.p.A ENI Italy 16 Technische Universitaet Hamburg TUHH Germany 17 OUTOTEC GmbH OUTOTEC Germany

Contents 1. Summary .......................................................................................................................................... 15 2. Keywords ......................................................................................................................................... 15 3. Background – Current state of the art ............................................................................................. 15 4. Scientific and technological challenges ........................................................................................... 16 5. Objectives ........................................................................................................................................ 16 6. Significant results / exploitable results ........................................................................................... 17 7. Expected impact .............................................................................................................................. 18 8. People involved in the project ......................................................................................................... 19 9. Copyright statement ........................................................................................................................ 19

http://www.cascatbel.eu/


15

1. Summary

CASCATBEL is aimed to the development of a multi-step process for the production of second-generation biofuels from lignocellulosic biomass in a cost-efficient way through the use of tailored nanostructured catalysts.

The proposed process is based on the cascade combination of three catalytic transformations: catalytic pyrolysis, intermediate deoxygenation and hydrodeoxygenation. The sequential coupling of catalytic steps is an essential factor for achieving a progressive and controlled biomass deoxygenation, which is expected to lead to liquid biofuels with a chemical composition and properties similar to those of oil-derived fuels. According to this strategy, the best nanocatalytic system in each step will be selected to deal with the remarkable chemical complexity of lignocellulose pyrolysis products, as well as to optimize the bio-oil yield and properties. Since hydrodeoxygenation (HDO) is outlined in this scheme as the ultimate deoxygenation treatment, the overall hydrogen consumption should be strongly minimized, resulting in a significant improvement of the process economic profitability. The use of nanostructured catalysts will be the key tool for obtaining in each chemical step of the cascade process, the optimum deoxygenation degree, as well as high efficiency, in terms both of matter and energy, minimizing at the same time the possible environmental impacts. The project involves experiments at laboratory, bench and pilot plant scales, as well as a viability study of its possible commercial application. Thereby, the integrated process will be assessed according to technical, economic, social, safety, toxicological and environmental criteria. The consortium is formed by 17 partners, including 4 research institutions, 6 universities, 5 large industries and 2 SME.

2. Keywords

Advanced biofuels, lignocellulose residues, catalytic pyrolysis, hydrodeoxygenation, aldol condensation, ketonization, esterification, hierarchical zeolites, functionalized mesoporous materials.


First generation biofuels (bioethanol and biodiesel) have shown important limitations to achieve targets for oil-derived product substitution, climate change mitigation, and economic growth, mainly due to the high water and energy consumption during their production, and the biofuel versus food controversy. The cumulative impacts of these concerns have increased the interest in developing biofuels produced from non-food biomass.

Lignocellulosic biomass, either from forestry or agriculture, offers such potential.

Lignocellulose materials consist of polysaccharide-containing biomass formed by three main components: cellulose, hemicellulose and lignin. Lignocellulose is the most abundant source of continental biomass and it is usually a low-cost raw material. Accordingly, the use of non-edible lignocellulosic biomass from agriculture and forestry represents a very interesting alternative resource for the production of second-generation biofuels with reduced environmental impact. Additionally, lignocellulosic biomass can be supplied on a large-scale basis from different low-cost raw materials such as municipal and industrial wastes, wood and agricultural residues. Lignocellulosic biomass holds the key for the sustainable production of liquid transportation fuels without impacting the food supply.

Figure 1. Raw Lignocellulose, Bio-oil and Advanced

Biofuel

The total energy potential of forestry by-products considering only the EU Western countries is estimated at 17.5 Mtoe/year, while agricultural wastes in the EU could reach 39.9 Mtoe/year by 20202. Therefore, lignocellulose resources could provide a significant amount of the energy consumed in the transportation sector, playing an important role in reducing the external European fossil fuel dependency and decreasing the overall CO2 emissions, in line with Europe 2020 Strategy3 and related SET Plan. Furthermore, their use not only allows the production of a valuable biofuel, but the utilization of a wide range of residues of domestic, agricultural and industrial activities. However, lignocellulose is a very complex material that requires an intensive labour and high capital cost for its processing. Although conversion of lignocellulose into transportation fuels has been attempted by a number of different routes, it is not a trivial goal due to its chemical complexity, elevated stability and high oxygen content. Three main pathways can be considered for the conversion of lignocellulose into fuels and chemicals based on hydrolytic, biochemical and thermochemical transformations, respectively. Among the various thermochemical transformation processes, biomass pyrolysis has shown to be a very promising option for the conversion of large volumes of solid biomass to liquids. In this route, biomass is treated under inert atmosphere to yield gases, liquids (bio-oil) and a solid residue (char). The use of high heating rates


16

(fast pyrolysis), combined with moderate temperatures (around 500 ºC) and short residence times, leads to an enhanced production of bio-oil.

Bio-oil presents a high potential as liquid fuel since it retains up to 70% of the energy stored in the raw biomass and contains less N and S than petroleum fractions. However, bio-oil possesses 15 - 25 wt% water, more than 40 wt% of oxygen and shows a dark red-brown colour. It has a very complex composition (up to 400 different components have been identified) and several shortcomings, such as relatively low heating value (16-19 MJ/Kg; less than half that of petroleum-derived fuels), strong corrosiveness (pH = 2-4), high viscosity, immiscibility with conventional fuels and poor chemical stability with polymerisation of components observed on storage. Consequently, biomass pyrolysis into liquid fuels suffers from important

limitations that can be only overcome if the bio-oil is subjected to upgrading treatments8 to improve its properties. The magnitude of this challenge showing that the production of advanced liquid fuels from solid lignocellulose by biomass pyrolysis/bio-oil upgrading requires a decrease in the O/C ratio (by removal of oxygen) and an increase in the H/C ratio (by the addition of hydrogen).


The following scientific and technological challenges have to be faced in the project:

1. Optimization of the lignocellulose catalytic pyrolysis (1

st step in the cascade process proposed for

CASCATBEL). Tailored nano-structured catalysts, with mild acidity or basicity, are being tested at different scales and optimised to obtain partially deoxygenated bio-oil in order to avoid overcracking of the pyrolytic vapours and to reduce the coke deposition for increased catalyst durability. Compared to conventional catalytic pyrolysis, this should result in higher bio-oil yields, lower production of gases and coke and reduced catalyst deactivation.

2. Optimization of the bio-oil upgrading through intermediate deoxygenation (2

nd step in the cascade

process proposed for CASCATBEL). Condensation reactions of the small molecules present in bio-oil may increase their chain length, stabilize the bio-oil, decrease its oxygen content and facilitate the separation of organic and aqueous phases. Three different types of reactions (ketonization, aldol condensation and esterification) are being investigated in order to identify and select which one is the most effective intermediate bio-oil upgrading treatment for application in between catalytic pyrolysis and hydrodeoxygenation. The selection is to be taken based on technical, economical, safety, environmental and toxicological criteria. In the

three cases, different types of nano-structured catalysts, tailored for the targeted chemical reactions, are being explored.

3. Optimization of the ultimate bio-oil hydrodeoxygenation (3

rd step in the cascade process

proposed for CASCATBEL). In this last step, bio-oil deoxygenation will be completed at moderate temperatures (200-350 ºC) and under moderate to high hydrogen pressures (20-150 bars). Since at least 50% of the oxygen should have been removed in the previous treatments, the hydrogen consumption should be substantially lower compared to HDO of the entire pyrolysis bio-oil. The catalysts tested consist of transition metal phases in the form of nanoparticles with HDO activity loaded with very high dispersion onto supports specially designed to stand the aggressive conditions present in the bio-oil, minimizing leaching of the active phase.

4. Enhancing the fundamental understanding of the different catalytic reactions considered in the project, which is of relevance for aiding in the selection of the optimum characteristics of the nano-catalysts to be employed. Quantum mechanical modelling is carried out to establish the interactions between components in the catalysts, as well as between reactant molecules and active sites (in particular DFT, Density Functional Theory13). Similarly, in-situ spectroscopic techniques are applied to characterize the behaviour of the catalysts under real operating conditions and to determine the mechanism of the reactions at a molecular scale, as well as for in-situ monitoring of coke formation and catalyst deactivation.

5. Nano-catalyst performance at different reaction scales, with in-situ catalytic tests, laboratory and bench-scale reactors, as well as pilot plant reaction systems being employed. Pilot plant experiments will be performed using nano-catalysts showing the best performance at smaller scales.

6. Viability of the cascade process according to economic (production and investments costs), social (impact on the employment and the rural development), environmental (life cycle analysis, LCA), safety and toxicological (regarding both nano-catalysts and bio-oil) criteria.

5. Objectives

CASCATBEL aims to design, optimize and scale-up a novel multi-step process for the production of second-generation liquid biofuels from lignocellulosic biomass in a cost-efficient way through the use of next-generation high surface area tailored nano-catalysts. On one hand, the sequential coupling of catalytic steps will be an essential factor for achieving a progressive and controlled biomass deoxygenation


17

and reduce hydrogen consumption, avoiding the previously highlighted problems that hinder one/two-step bio-oil upgrading processes. On the other hand, the use of tailored nano-catalysts will allow optimising reaction yields (increasing liquid yield and preventing bio-oil contamination) and facing limitations of current catalysts in terms of selectivity and deactivation rates. Finally, the scaling-up of the process will be important for fully exploring and understanding the catalytic and reaction dynamics, assessing catalysts life-cycles and demonstrating the viability of the CASCATBEL process in relevant environments, from both technical and economic perspectives.

The strategy proposed in CASCATBEL will lead to the preparation of advanced biofuels having composition and properties very similar to petroleum-derived fuels. This is a very relevant advantage regarding the commercial implementation of this technology, as it would not require any significant changes in the already existing infrastructures and engines.

These four aspects (cascade processing of lignocellulosic biomass, synthesis of competitive tailored nano-catalysts, demonstration at pilot plant scale and synthesis of low-oxygen advanced biofuels) are the main elements of the CASCATBEL project.


The use of commercially viable nano-structured catalysts, mainly based on abundant elements such as Si, Al, Ti or C, is the strategy for obtaining, in each chemical step of the cascade process, the optimum combination of catalytic properties, degree of deoxygenation and bio-oil yield, as well as high efficiency, in terms both of matter and energy, while minimizing possible environmental impacts. Availability of these catalytic materials during the project is guaranteed by the participation into the consortium of 5 academic partners with wide experience in the development of nanocatalysts and 3 catalyst manufacturer companies with complementary profiles. For achieving the project aim and optimizing the different chemical transformations included in the biomass conversion cascade process, catalytic materials with tailored properties at the nano-scale are being designed and synthesized. These materials have been selected because they possess high surface areas, narrow pore size distribution and large pore volumes.

Moreover, a number of effective methods are being applied for the functionalization of solid surfaces with acid/base moieties, as well as for the preparation of metals and metallic compounds with a narrow nanoparticle size distribution.

Another important aspect, is the use of reaction systems with progressively larger size and higher complexity:

i) Laboratory scale catalytic tests. The use of small reactors allow a wide range of nano-catalysts to be screened in the different chemical steps of the cascade process. Thereby, mainly model substrates and reactions, representative of those occurring with real biomass and bio-oil, are employed at this scale. These tests are being performed using both batch and continuous systems, whereas the catalysts are used mainly as powders.

ii) Bench scale catalytic tests. Medium-size reactors are being employed to probe and compare the catalytic properties of a reduced number of nano-catalysts, selected among those exhibiting the best catalytic properties in laboratory experiments. A great difference regarding the previous step is the use of real bio-oils as feedstock in these tests, which is also in contrast with most of the previous literature works. Accordingly, it is being checked whether the selected catalysts exhibit also a good performance with real bio-oils. At this scale, both batch and continuous reactors are employed. Another significant difference regarding to the laboratory experiments is related to the shaping and pelletization of the nano-catalysts into technical shapes and particle sizes, which will make possible to assess the influence of the physical transport phenomena on the overall catalyst performance and to study the reaction kinetics in more realistic conditions. iii) Pilot plant catalytic tests. They will be carried out feeding real biomass and bio-oils and using continuous reactors with a feed capacity of about 1 kg/h. Under these conditions the possible effects of the scale-up will become more evident for the previously selected catalysts (at least 3 samples per chemical transformation). Likewise, continuous operation for periods of several days will provide information about the nano-catalyst stability and resistance to the deactivation. Results at pilot plant scale will allow the optimum catalysts and operation conditions to be finally selected.

Exploitation activities have a high relevance in the CASCATBEL project, as one of the main expected outcomes is to establish the feasibility of a cascade process for the production of advanced biofuels at commercial scale. Consequently, exploitation activities began within WP10 at the onset of the entire project, and elaborated through the Results Exploitation Strategy. Although many of the dissemination activities developed are also expected to have a significant impact on the project exploitation goals, the Exploitation Strategy is reinforced and structured around additional elements, described below:

i) Intellectual property rights (IPR) management. IPR issues may affect both the project progress and exploitation of the project results, hence they are being


18

addressed as early as possible. Accordingly, in the CASCATBEL project, IPR regulations have been detailed within the Consortium Agreement, taking into account the applicable legislation. The principles applied in the CASCATBEL consortium have been delineated with regard to recommendations from the Guide to Intellectual Property Rules for FP7 projects, alongside aid from the IPR-Helpdesk.

ii) Innovation Committee. This body has been implemented to play a major role in promoting IPR protection as a necessary step prior to any results dissemination and/or exploitation. It consists of the Coordinator and representatives of the industrial partners in the CASCATBEL project. The main function of the Innovation Committee is to analyse the project achievements in order to identify those that can be considered as valuable foreground for exploitation and commercial implementation. In such cases, the Innovation Committee advises the partners owning that foreground on the appropriate actions necessary to protect the IPR of their results, and also inform the Governing Board. It must be emphasized that, although the role of the Innovation Committee is mainly advisory and not executive, this body is being an essential element within the Exploitation Strategy, fostering the protection of the IPR of results generated in the project.

Taking into account the activities carried out in the CASCATBEL project, it can be anticipated that the main types of foreground that could be the subject of IPR actions will be as follows:

Novel nano-catalytic systems having singular properties.

Application of nano-catalysts in biomass catalytic pyrolysis showing a remarkable performance.

Application of nano-catalysts in bio-oil upgrading by ketonization, aldol condensation and esterification, showing a remarkable performance.

Application of nano-catalysts in bio-oil HDO, showing a remarkable performance.

Novel methods for biomass and bio-oil treatment to increase the stability of the latter.

Integrated process including several cascade steps.

7. Expected impact

The CASCATBEL project aim is driven by the European critical need of reducing the external European fossil fuel dependency and decreasing the overall CO2 emissions, in line with Europe 2020 Strategy41 and related SET Plan. For this purpose, biofuels are recognized as one of the greatest alternatives. However, first generation biofuels have shown important limitations to achieve targets for

oil-product substitution, climate change mitigation and economic growth, while having in many cases negative impacts in terms of land use change and interaction with the food market. The cumulative impacts of these concerns have increased the interest in developing biofuels produced from non-edible parts of the plants (second-generation biofuels, also known as advanced biofuels). Lignocellulosic biomass, either from forestry or agriculture, offers such potential, and the purpose of CASCATBEL project is to contribute importantly to make it possible to take full advantage of it at industrial level, in a sustainable and profitable way and with minimum toxicological and environmental impact.

Accordingly, achieving the CASCATBELs aim would allow Europe exploiting a wide range of residues of domestic, agricultural and industrial activities, which have the potential to be valorised as raw materials, but which are being currently underutilised.

Valorisation of residues into raw materials is also another of the key objectives within the Europe 2020 Strategy. Fossil fuels represent about 80% of the total primary energy consumed in the EU. Europe currently imports more than half of the energy it uses. If significant changes do not occur in the near future, EU dependency on fossil fuel imports will rise by 2030, with negative consequences in terms of strategic, economic and environmental aspects. In this context, one of the priorities of EU policy is to implement new instruments and technologies that may contribute to delivering competitive, secure, low carbon and sustainable energy for Europe. Accordingly, one of the 5 main targets established by the Europe 2020 Strategy is Climate change and energy sustainability, with the following goals:

Reduce greenhouse gas (GHG) emissions by 20% (or even 30% if conditions are right) with respect to those of 1990.

Increase the share of energy from renewable sources up to 20% (10% share in the case of biofuels).

Reduce energy consumption by 20% relative to the current levels through improved energy efficiencies.

A variety of recent initiatives clearly denote that the CASCATBEL project, aimed at the production of advanced biofuels, is perfectly aligned with the European Union energy and climate strategies. Accordingly, CASCATBEL offers great potential impact in contributing towards the objectives marked by the Energy Strategy 2020 within the bioenergy field.


19



David Serrano IMDEA Energy

Avda Ramón de la Sagra, 3. Parque Tecnológico de Móstoles. 28935 Móstoles, Madrid. Spain.

[email protected]

Jordi Aguiló ENCE Paseo de la Castellana 35. 28046 Madrid. Spain.

[email protected]

Gianfranco Pacchioni UNIMIB Via Cozzi 53. 20126 Milano. Italy.

[email protected]

Petr Nachtigall CUNI Albertov 6. Prague 2. 128 43. Czech Republic.

[email protected]

Jiri Cejka HIPC Dolejskova 2155/3. Prague 8. 182 23. Czech Republic.

[email protected]

Bert M. Weckhuysen UU Universiteitsweg 99. Utrecht. 3584 CG. Netherlands.

[email protected]

Karen Wilson AU European Bioenergy Research Institute (EBRI) Aston University, Aston Triangle Birmingham, B4 7ET, UK.

[email protected]

Maria Pilar Ruiz ABR Campus Palmas Altas. C/ Energía Solar, 1. 41014 Sevilla. Spain.

[email protected]

Javier Pérez-Ramirez ETH Wolfgang-Pauli-Strasse 10 Zurich CH-8093. Switzerland.

[email protected]

Ferdi Schueth MPIK Kaiser Wilhelm Platz 1. Mulheim and der Ruhr. 45470. Germany.

[email protected]

Steve Tennison MASTCARBON

Jays Close Viables. Basingstoke. RG22 4BA. United Kingdom.

[email protected]

Andrej Horvat SILKEM Tovarniška c.10. Ptuj 2325. Slovenia.

[email protected]

Moa Lihammar NANOLOGICA

Drottning Kristinas Väg 61 Stockholm 114 28. Sweden

[email protected]

Angelos Lappas CERTH/CPERI

Charilaou Thermi Road 6th Km. Thermi Thessaloniki. 57001. Greece.

[email protected]

Vincenzo Calemma ENI Via Maritano 26. San Donato Milanese. 20097. Italy..

[email protected]

Martin Kaltschmitt TUHH Eissendorfer Strasse 40. Hamburg. 21073. Germany.

[email protected]

Christian Binder OUTOTEC Ludwig-Erhard-Strasse 21. Oberursel. 61440. Germany.

[email protected]


© 2015, IMDEA Energy, Avda Ramón de la Sagra, 3. Parque Tecnológico de Móstoles, 28935 Móstoles, Madrid, Spain, on behalf of the CASCATBEL consortium. CASCATBEL is a Large Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




CASCATBEL and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;





















20




21

CEOPS CO2 - loop for Energy storage and conversion

to Organic chemistry Processes through advanced catalytic Systems

Proposal full Name: CO2 - Loop for Energy storage and conversion to Organic chemistry

Processes through advanced catalytic Systems Acronym: CEOPS Call Identifier: NMP. 2012.2.1-2 Fine chemicals from CO2 Duration: 01/02/2013 – 31/01/2016 Grant Agreement No: 309984 Total Budget: 3 508 268,6 € Coordinator: Laurent Bedel Website: www.ceops-project.eu

Consortium List


1 Commissariat à l’Energie Atomique et aux Energies Alternatives

CEA France

2 C.T.G. SPA C.T.G. Italy 3 Instituto Superior Tecnico IST Portugal 4 OMNIDEA LDA OMNIDEA Portugal 6 Faculdade de Ciencias e Tecnologiada / Universidade Nova

de Lisboa NOVA Portugal

6 GDF SUEZ Energy Romania SA GDF Romania 7 Fundacio Institut de Recerca de l'Energia de Catalunya IREC Spain 8 European Materials Research Society EMRS France 9 Chemie Cluster Bayern GmbH CCB Germany 10 Université Pierre et Marie Curie UPMC France

Contents

1. Summary .......................................................................................................................................... 21 2. Keywords ......................................................................................................................................... 22 3. Background – Current state of the art ............................................................................................. 22 4. Scientific and technological challenges ........................................................................................... 22 5. Objectives ........................................................................................................................................ 23 7. Expected impact .............................................................................................................................. 24 8. People involved in the project ......................................................................................................... 24 9. Copyright statement ........................................................................................................................ 25

1. Summary

The CEOPS project will focus on a sustainable approach for the production of methanol from CO2, which is a precursor for fine chemicals products. The approach will reinforce the link between large CO2 emitters and fine

chemical industries at the European level. The concept relies on two chemical pathways, CO2 to CH4 and CH4 to CH3OH with the intermediate carbon vector: methane. Methane benefits from the extended and existing natural gas network infrastructure. Its distribution will prevent additional CO2 emissions (rail & road

http://www.ceops-project.eu/


22

transportation). This approach will favor the emergence of small and flexible production units of fine chemicals from methanol. The technological work is based on advanced catalysts and electro-catalytic processes. CEOPS will develop advanced catalysts for application in three promising electro-catalytic processes (Dielectric barrier discharge plasma catalysis, Photo-activated catalysis and Electro-catalytic reduction) to increase their efficiency overtime for both pathways. The performances of the studied catalyst and process schemes will be benchmarked and the most efficient one, for each pathway, will be selected for a prototype. This prototype will be realized at a scale of 3m3.h-1 of methane, it will validate the concept and generate the required data for the techno-economic assessment. The consortium merges the skills of 2 research organizations, 3 universities, 1 SME, 1 non-profit organization, 2 industries and 1 cluster. The project is led by CEA-LITEN. Italcementi, GSER and CCB will bring respectively their expertise in CO2 emissions, CH4 injection and transportation and on methanol use for the fine chemical industry. They also contribute to the techno-economic and environmental assessments. IST, IREC, OMNIDEA will develop advanced catalysts. UPMC, CEA, IREC, NOVA will develop electro-catalytic processes. CEA assisted by the consortium will implement the prototype. EMSR and CCB will ensure the dissemination of the CEOPS concept and results.

2. Keywords

- CO2 utilisation

- Nanostructured zeolite, mesoporous metal oxides, TiO2 nanotubes, mesoporous tungsten oxides, beta zeolites, multifunctional cathode including bimetallic nanoparticles. - Dielectric Barrier Discharge plasma catalysis, photo-activated catalysis, electro-catalytic reduction - Methane, Methanol


For the CO2 conversion into methane the presence of water as reaction product remains the main reason for metal sintering, thus for catalysts deactivation (5000-7500 h). Other major problem of Ni-based catalysts is the deactivation at low temperature (< 300°C) due to the interaction of the metal particles with CO and formation of mobile nickel carbonyls.

For the direct conversion of methane into methanol, this chemical pathway faces low methane conversion (<30%), low selectivity (10-15%) to methanol and relatively high temperatures and pressures.


CEOPS is devoted to a sustainable approach for the production of methanol from CO2, which is a precursor for fine chemicals products.

While large CO2 emitters like cement plants and fine chemicals producers are currently and geographically dispersed throughout Europe, CEOPS concept proposes to use of the existing wide natural gas network via the injection and transportation of an intermediate product: methane. Indeed, whereas CH4 is easily transported, the instability of CH3OH makes its transportation more hazardous by truck. Furthermore, methane already benefits from the extended and existing European natural gas network infrastructure, so its distribution will prevent additional CO2 emissions (rail & road transportation). This sustainable approach will thus enable the decentralisation of methanol production which will favour the emergence of distributed, small and flexible production units of fine chemicals. This vision will pave the way for several novel and sustainable production schemes.

The concept of the project (cf figure below) relies on the development of two chemical pathways based on:

One sub-system A: Upstream, CO2 to methane (pathway A) conversion will be realised with advanced catalysts to promote the efficiency of CO2 CH4 electro-catalytic process at the point of CO2 emission (cement works). Methane will act as an easy storable and transportable carbon vector (from intermittent sources).

A second sub-system B: Downstream, the direct conversion of methane to methanol (pathway B) will be done at the point of fine chemicals production with advanced catalysts to promote the efficiency of the direct pathway instead of using the current pathway consisting of a steam reforming of CH4 which represents 60-70% of cost production of current methanol, followed by the CO hydrogenation reaction.


23

5. Objectives

CEOPS focuses on the following objectives:

The first objective of the CEOPS project is the development of advanced catalysts:

Catalysts are developed in order to increase the conversion rate and selectivity of both chemical pathways:

- Synthesis of zeolite based catalysts and mesoporous ceria zirconia based catalysts for the DBD plasma catalysis process;

- Nanostructured TiO2 (nanotubes) and mesoporous tungsten oxides and beta zeolites for photo-activated catalysis;

- Develop copper and carbon based cathode for the direct electro-reduction process of CO2 into methane in ionic liquid.

The second concerns the development of electro-catalytic processes:

Electro-catalytic processes are developed to promote the sustainable production of fine chemicals from emitted CO2 via pathway A and pathway B:

- DBD plasma reactor in fixed bed and in fluidized bed conditions for both pathways

- Two compartments photo-reactor for CO2 conversion into methane (pathway A)

- Photocatalytic reactor for partial oxidation of methane into methanol (pathway B)

- Electrocatalytic reactor with the use of ionic liquid in which CO2 is dissolved. (Pathway A)

The third objective targets an upscaling of most performing process for each chemical pathway:

The most efficient process for each pathway will be selected for an upscaling and integrated in a prototype bench test for an evaluation of performance. The size of each sub-reactor will allow the evaluation of thermal balance, electricity consumption, and catalytic efficiency.

The last objective focuses on the techno-economic and environmental assessments of the CEOPS concept:

The economic and environmental competitiveness of the CEOPS process routes from industrial CO2 emitters to fine chemical customers will eventually be determined in terms of:

- Industrials flow sheet based on CEOPS concept; - Techno-economic performances assessment; - Environmental impact assessment for industrial CO2

valorisation and low carbon footprint methanol market;

- Comparison of the competitiveness and the overall efficiency of the low carbon footprint methanol with the one produced today from fossil source by current technology (thermal catalysis).


Catalyst developments:

IST developed Ni-zeolite catalysts, promoted with rare earth oxides and alkaline metals (Pathway A) and iron-based zeolites for pathway B, for plasma DBD catalysis. They have also modified zeolite catalysts for photocatalysis (pathway B);

1- Ni supported FAU structure-zeolite catalysts were prepared for methanation (pathway A) plasma processes.

Different promoters were added to increase Ni-based catalysts activity and selectivity to methane. Best performance catalysts were achieved after the introduction of rare-earth and alkaline promoters.

2 - Iron-zeolites (FAU and MFI) were prepared for methanol synthesis (pathway B) from methane selective oxidation. Different methods for iron introduction on zeolite were used.

IREC developed and characterized (i) modified mesoporous ceria and zirconium based catalysts (Pathways A and B) for DBD plasma catalysis, (ii) three-dimensional titanium oxide-based photocatalysts (pathway A) and (iii) mesoporous tungsten–based catalysts (pathway B) for photo-activated catalysis. Using DBD reactor, the former catalyst shows high performances. Likewise, high surface tungsten-based and bismuth-based catalysts have been proved as candidate to obtain methanol at competitive efficiencies.

OMNIDEA developed a methodology for cathode preparation, incorporating micro/nanoparticles obtained by electro-deposition method (pathway A) for electro-catalytic reduction. The electrode materials prepared by this methodology were effective in promoting the reduction of water, with increased production of hydrogen. Their effect on the production of methane was, however, not clear, as it turned out that the extent of reduction of CO2 to methane depended more critically on electrolyte composition.

Electrocatalytic processes:

During this first period of the project, lab scale reactors were designed, and built up. Advanced catalysts were tested in each electro-catalytic process.

DBD plasma catalysis process:


24

According to the DoW, UPMC has implemented a lab scale DBD plasma reactor in fixed bed and CEA in fluidized bed conditions for both pathways.

In fixed bed configuration, experiments performed in a wide range of temperatures with plasma and catalyst and without plasma (catalyst alone). In the isothermal regime, the action of the plasma is highlighted, because total conversion of CO2 without plasma is between 5% and 30%, while under plasma action total conversion of CO2 (Xtp) lies between 70 and 90%, increasing with temperature. The key step of the reaction, at this range of temperatures should be the water desorption from the catalytic sites enhanced by the plasma.

In fluidized bed configuration, a reference working point was determined in order to meet the project’s objectives as regards methanation (CO2 conversion higher than 65% and CH4 selectivity higher than 90%) to analyse the DBD plasma effect. A CO2 conversion of 68% was performed at 2bar during a 2 hour-experiment and both a stable conversion and temperature inside the bed (320-325°C at the centre and 305°C near the wall) were observed. The selectivity in CH4 was very close to 1, without CO detection.

IREC has implemented two reactors: first, a two compartment reactor for CO2 conversion into methane (pathway A) and secondly, a photocatalytic reactor for partial oxidation of methane into methanol (pathway B). The former reactor allows fulfilling the project requirement having an energy consumption of less than 1.2 kJ/mol of CH4 whereas the photocatalytic reactor, using tailored bismuth based catalyst, has selectivity higher than the required 50%.

NOVA and OMNIDEA have implemented an electrocatalytic reactor with the use of ionic liquid in which CO2 is dissolved for pathway A. First results for the evaluation of the catalysts in terms of conversion rate, selectivity and electricity consumption were obtained. Conditions of applied voltage, electrode

composition and quantity of water added to the ionic liquid electrolyte required for the full reduction of carbon dioxide to methane were studied. Faradaic efficiencies in the range 60 to 66 % were attained in experiments where methane was the only species obtained.

7. Expected impact

The CEOPS consortium orientates its effort toward creating new scientific knowledge in catalysts preparation and structural properties that will impact the fields of electro-catalytic processes.

A bottom-up approach is proposed whereby the rational design of various relevant advanced catalysts (chemical contents, morphology, size, density, structure, conductivity) will result in CO2 conversion and CH4 conversion processes with low energy consumption at the system scale.

The investigations of physico-chemical properties between catalysts and (CO2, H2, CH4, O2) under plasma activated species, under radiation and/or under electric field conditions, is expected to generate new significant scientific knowledge. Indeed, this approach has not been largely reported so far on chemical synthesis despite its expected potential. Furthermore, such benchmark of these emerging processes has not been performed before as proposed by CEOPS. It will allow a comparison of catalytic efficiency (conversion rate and selectivity) and identify the advantages and disadvantages of each process.

More specifically, CEOPS expected results on the tuning and optimisation of catalysts and catalytic processes will be exploitable for a wider range of chemical processes. The potential applications of the CEOPS studied processes, regardless of the project main application dealing with CO2 conversion. Results of catalytic researches will be transferable to industrial processes targeting syngas and hydrocarbons production.



Laurent Bedel CEA CEA-Grenoble - LITEN-DTBH 38054 Grenoble Cedex 9 France

[email protected]

Piero Negro CTG Via Camozzi 124 24121 Bergamo Italy

[email protected]

Carlos Henriques IST Avenida Rovisco Pais 1 1049-001 Lisboa Portugal

[email protected]

Ana Machado OMNIDEA Trav. António Gedeão 9 3510-017 Viseu

[email protected]






25

Portugal

Manuel

Nunes Da Ponte

NOVA Campus da FCT/UNL Monte de Caparica 2829-516 Caparica Portugal

[email protected]

Razvan Grecu GSER Bd Marasesti nr 4-6, Sector 4. 040254 Bucharest Romania

[email protected]

Juan Ramon

Morante IREC Jardins de les Dones de Negre, 1, 2ª pl. 08930 - Sant Adrià de Besòs Barcelona Espagne

[email protected]

Jacques Amouroux EMRS 23 Rue du Loess BP 20 67037 Strasbourg Cedex 02 France

[email protected]

Melanie Poehlmann CCB Chemie-Cluster Bayern GmbH Hansastr. 26 80868 Munich Germany

[email protected]

Siméon Cavadias UPMC 4 Place Jussieu 75005 Paris France

[email protected]


© 2015, CEA, Grenoble - LITEN-DTBH 38054 Grenoble Cedex 9, France, on behalf of the CEOPS consortium. CEOPS is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




CEOPS and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;












26

CyclicCO2R Fine chemicals from CO2

Proposal full Name: Production of Cyclic carbonates from CO2 using Renewable feedstocks Acronym: CyclicCO2R Call Identifier: NMP.2012.2.1-2: Fine chemicals from CO2 Duration: 01/01/2013 – 31/12/2016 Grant Agreement No: 309497 Total Budget: 5,180,818 € Coordinator: Dr. Erin Schols Website: www.cyclicco2r.eu

Consortium List


1 Netherlands Organization for Applied Scientific Research TNO Netherlands 2 STIFTELSEN SINTEF SINTEF Norway 3 Carbon Recycling International CRI Iceland 4 FeyeCon Carbon Dioxide Technologies FEY Netherlands 5 University of York UNEW Great-Britain 6 Technical University Aachen, Institute for Technical and

Macromolecular Chemistry ACH Germany

7 University of Twente UT Netherlands 8 Evonik Industries AG EVO Germany

Contents 1. Summary .......................................................................................................................................... 26 2. Keywords ......................................................................................................................................... 27 3. Background – Current state of the art ............................................................................................. 27 4. Scientific and technological challenges ........................................................................................... 28 5. Objectives ........................................................................................................................................ 29 6. Significant results / exploitable results ........................................................................................... 29 7. Expected impact .............................................................................................................................. 29 8. People involved in the project ......................................................................................................... 30 9. References ....................................................................................................................................... 31 10. Copyright statement ...................................................................................................................... 31

1. Summary

The overall objective of CyclicCO2R is the development of a continuous process that converts CO2 and bio-based renewables into high value-added products in a sustainable manner which is competitive with conventional fossil-based processes. The highly efficient integrated process will remove the dependency on fossil fuels and increase the energy efficiency such that it creates a reduction in CO2 emissions. These aims will be achieved by focusing on the use of bio-based materials and waste CO2 from several sources (power plants,

cement factories, chemical plants, etc.). As an inexpensive waste product from bio-diesel production, glycerol will be the main raw material, along with CO2, ensuring cost effectiveness and, thereby, a maximum commercial potential. With the potential to use CO2 directly from flue gas streams, the cost and energy requirements of carbon capture can be reduced such that, through realization of the process by industrial end-users, CyclicCO2R will decrease industrial CO2 emissions

http://www.nextgencat.eu/


27

while driving the implementation of the entire carbon capture and utilisation chain.

The basis of CyclicCO2R is the creation of a new continuous and highly efficient process which produces industrially relevant cyclic carbonates, especially glycerol carbonate. The overall concept, based on bio-based renewables, is depicted in Figure 1 the schematic of below.

Figure 1. CyclicCO2R process schematic

The project is divided into three parts: catalyst development combining high throughput screening with optimisation of state-of-the-art catalysts utilising advanced molecular modelling; integrated process development to ensure high efficiency with in-situ product separation and catalyst recovery in order to achieve the maximum product yield; and demonstration of the technology to be a showcase in proving the potential of CO2 as a chemical feedstock and accelerating the implementation of CO2 chemistry within the European chemicals industry.

2. Keywords

Cyclic carbonates, glycerol, epoxides, heterogeneous catalysis, homogeneous catalysis, water removal, catalyst immobilization, process design, modelling, scale up, electrochemistry, photochemistry.


The rationale behind CyclicCO2R is the recognition that the current state-of-the-art in the chemicals industry is such that 90% of all commercially available organic chemicals are sourced from crude oil. This is unsustainable since world–wide production of crude oil is predicted to peak within the next twenty years. Cyclic carbonates have been identified as a class of chemicals which are currently derived from crude oil, but which have the potential to be prepared from renewable resources and waste CO2. Achieving this goal will require the development of novel robust catalysts to allow the desired transformations to be achieved under optimal reaction conditions in a continuous process. Cyclic carbonates have numerous commercial applications, including electrolytes for lithium–ion batteries, solvents (sustainable replacements for polluting solvents widely used in the fine chemicals/pharmaceuticals industries,

such as DMF, DMSO, NMP), degreasing agents, and chemical intermediates (e.g. for ethylene glycol and dimethyl carbonate production).

1 The replacement of

conventional solvents is especially interesting as solvents constitute a major source of waste, especially in the pharmaceuticals industry where solvent recycling is often not feasible for legislative reasons. By progressing beyond the current state-of-the-art, glycerol carbonate and other cyclic carbonates will become sustainable organic materials with several important applications in the chemicals industry.

State-of-the-art processes that are used for the synthesis of glycerol carbonate (GC) focus on the use of either urea , or on the transesterification of reactive organic carbonates, such as ethylene carbonate (EC) (Compound A, Figure 2) or dimethylcarbonate. The use of urea has as a drawback the formation of ammonia, which has to be recovered and must be transformed back into urea. This requires substantial energy input and in some cases involves the formation of salts for neutralisation. The drawback of transesterification is the use of a fossil-originated raw material.

Figure 2. Schematic representation for the trans-esterification of organic carbonates, such as ethylene carbonate (Compound A), with glycerol to form glycerol carbonate

While these reactions are able to give good yields and selectivities for GC, production of GC via trans-esterification does not address the root of the problem, as the issue of direct CO2 incorporation still remains. The transesterification reaction is only a viable sustainable technology if the alcohol or diol by-product (represented by ethylene glycol (B) in Figure 2) formed at the end of the transesterification reaction, together with GC, can be reacted with CO2 to give the starting carbonate (represented by EC, compound A in Figure 2). The transesterification does not address the efficient incorporation of CO2 into glycerol to create glycerol carbonate. The challenge resides in the creation of the cyclic carbonate backbone using CO2 and renewables. Transesterification could be used to transform the glycerol carbonate to other cyclic carbonates of interest.

A third method for the production of glycerol carbonate is the direct carboxylation of glycerol to GC. The first example was reported in 2006, using n-Bu2SnO or n-Bu2Sn(OMe)2 as catalysts. A promising result from this


28

work is that the transesterification of glycerol with dimethylcarbonate is slower than the direct carboxylation of glycerol, indicating that the direct carboxylation might be more suited for an industrial continuous process. The equilibrium conversion of GC is reported to be 0.42 % at 5 MPa CO2 and 453 K, although a conversion as high as 6.9 % was reported when using higher catalyst loadings and molecular sieves to remove water from the gas phase.

2 This work was extended by

Munshi, et. al., who showed that MeOH was a very effective solvent for this transformation, increasing the GC yield to 30% under supercritical conditions (13.8 MPa, T = 393 K) when the MeOH/GC molar ratio was 11.4.

3 In a biphasic system consisting of glycerol and

tetra(ethyleneglycol)dimethylether, CeO2 supported on Al2O3 or Nb2O5 catalytically produced 2.5% GC.

4

However, in this work, the above effect of the addition of MeOH could not be repeated.

The synthesis of cyclic carbonates from epoxides and CO2 (Figure 3) has been a commercial process for over 50 years and is currently an area of substantial research activity due to the usually required high temperatures and pressures. The leader of WP1 has thoroughly analysed all of the literature in this area and has authored two detailed surveys of the area. The first of these

5 focuses on the academic literature, while the

second6 focuses on commercially applicable catalysts

and covers both relevant academic work and extensive commercial work reported in the patent literature. Both of these reviews contain over 200 relevant citations to work in the area.

Figure 3. Schematic representation of the synthesis of cyclic carbonates from CO2 and epoxides.

The reaction between epoxides and CO2 does not occur spontaneously and requires a catalyst to lower the activation barrier. Quaternary ammonium halides (R4NX) were amongst the first catalysts developed, though elevated temperatures and pressures are usually required (typically 100-200 °C and 20-100 bar). The literature indicates that Huntsman uses tetra-ethylammonium bromide (Et4NBr) as a catalyst in their commercial process

7 and that Ashai Kasei uses an

immobilized tetramethylammonium chloride catalyst.8

Mitsubishi and Shell have developed an integrated process for the synthesis of ethylene glycol from ethene with ethylene oxide and ethylene carbonate as intermediates. The patent literature suggests that tetraalkylphosphonium halides (R4PX) are also used as catalysts

9, again at elevated temperatures and pressures.

The harsh reaction conditions associated with these commercial processes negate any environmental benefit achieved from the use of CO2 in cyclic carbonate synthesis, since more CO2 is released generating the required energy than is consumed by the reaction.


The biggest challenge in incorporating CO2 into (fine) chemicals is its high thermodynamic stability. Energy, in some form, has to be added to CO2 in order to activate it to a level at which it can take part in a reaction. With the production of this energy, CO2 is usually generated. This makes the net use of CO2 as a raw material inherently coupled with the efficiency of the process, the increase of which will be a main focus of CyclicCO2R. A key advantage of bio-based sources over fossil-based sources is the degree of oxygenation of the starting materials. A bio-based material starts out more activated than a fossil-based material. Fossil-based materials will always require some selective oxidation—a difficult and energy-intensive process—prior to their use as chemicals. The result is less energy input required for the reaction with CO2. Furthermore, in recent years new catalytic systems and reactor concepts have been developed that have the potential to continue to reduce the energy that goes into the process.

10-11

One path to a sustainable process is to produce the epoxide in a renewable manner, for example directly from bio-ethanol.

12-13 However, more advantageous is

the use of glycerol, as it is a readily available renewable raw material that is cheap and usually regarded as a waste product. This is directly related to the goal of CyclicCO2R to develop a sustainable, continuous process for the production of cyclic carbonates from CO2 and renewables as raw materials. The CO2 resulting from the production of the energy used in the process should be less than the CO2 utilised as a raw material in the process.

Progress beyond the state-of-the-art for the catalytic system is achieved through the following activities:

Repeating, understanding, and thereafter exploiting the effect of methanol, a potentially renewable solvent, on the equilibrium yield of glycerol carbonate.

Development of catalysts which can utilise impure, waste CO2 (e.g. from flue–gas) as a raw material.

Understanding and thereafter improving the new catalyst systems through fundamental catalyst characterization and molecular modelling.

Development of commercially viable homogeneous catalysts for cyclic carbonate synthesis at optimal operating conditions.


29

Increased molecular understanding of the formation of cyclic carbonates from CO2 and glycerol or epoxides.

Development of suitable ways of immobilizing the catalysts onto appropriate supports for use in continuous flow reactors.

5. Objectives

The consortium behind CyclicCO2R wants to kick-start the implementation of CO2 utilisation. This ambition is captured in the high-level aim of CyclicCO2R: Develop-ment of a showcase continuous process combining CO2 and renewables in a manner competitive with fossil fuel-based processes while reducing the stress on the environment. The CyclicCO2R consortium will reach this high level objective by:

Positioning the project on producing valuable chemicals of industrial interest, thereby valorising CO2 and renewable raw materials;

Developing active and robust catalytic systems that are cost-effective and environmentally acceptable with the potential to be used directly with industrial flue gas streams, eliminating the need for expensive capture plants;

Demonstrating a continuous process which efficiently converts CO2 into a value-added chemicals and can be extended to other industrially important products, thus increasing the overall impact;

Investigating the feasibility of alternative technologies that can produce intermediates of the reaction directly from CO2 and water, giving the project access to state-of-the-art results in photo- and electrocatalytic technologies and working to secure the supply of raw materials;

Analysing the entire chain from sustainably produced feedstocks and CO2 to end-products in order to ensure CO2 emissions reduction, product market potential, and the development of an implementation plan.


One-component homogeneous catalysts have been developed, based on the aluminium(salen) and aluminium(acen) complexes, that can perform cyclic carboxylations at mild conditions with glycidol (the epoxide of glycerol), but also with other commercially important epoxides. These complexes have high activity in epoxide activation and result in efficient epoxide ring opening. To counter the loss of activity during continuous reaction, different substitutions on the salen and acen groups have been explored (for example pyridinium) which do not have these alkyl groups. The catalyst is being optimized, using the knowledge in the

consortium and computational studies, by changing the position of substituents and the interaction between salen ring and onium salt. This has resulted result in a greater understanding of how this class of catalyst works in ring-opening reactions for epoxides, while giving insights applicable to other reactions involving metal(salen) complexes.

To further understand the catalytic mechanism, a model and method have been established to come to trustworthy calculations using state of the art as a basis. Benchmark calculations on published data, such as geometries, thermodynamic and kinetic data, have been used to form first test cases, allowing for the missing gaps to be filled in in order to come to an extended and consistent physical description of the studied systems. Work is continuing with proposing and modelling different reaction mechanisms for the catalytic systems developed in the project for glycerol carbonate production. Thermodynamic data has been generated on proposed and detected intermediates that are otherwise difficult to assess experimentally. The issues around kinetic resolution and substituent influences are addressed with the proposed reaction mechanisms and determined rate determining steps (states) with the catalytic models. Once new lead catalyst structures have been identified, the modelling will be refocused and the methodology repeated for possible new models and mechanisms, allowing for optimization of these types of catalysts for the reaction systems of interest.

7. Expected impact

The re-use of CO2 is connected to the greenhouse gas challenge. The World Economic Forum has estimated that, in the coming 10 years, 500 billion US$ are required to put the world on the trajectory that will stabilize greenhouse gas emissions.

One of the key tools used in Europe to create an incentive to reduce greenhouse gas emissions is the Emissions Trading System. Its goal is to lower the 2020 emissions by 21% in comparison to 2005, while maintaining growth (in line with the Kyoto Protocol which wants a “stabilization of greenhouse gases in the atmosphere”). This system has resulted in considerable reductions of emissions, for example, in the paper industry and by road transport. It was also an incentive for the creation of carbon capture and storage technologies to prevent CO2 emissions to the atmosphere. However, this can be taken even further with carbon capture and utilisation. With the potential to make use of CO2 directly from industrial waste streams; from power plants, cement factories, and chemicals plants, for example; the costs of CO2 capture can be eliminated, saving 30 – 60 €/tonne CO2, no longer requiring substantial energy inputs for capture solvent


30

regeneration, and removing the threat of toxic emissions from the capture solvents into the environment.

The strategy paper “EUROPE 2020 – Smart, Sustainable and Inclusive Growth” shows the commitment of the European Union to enhance a more resource efficient, greener and more competitive economy. The utilisation of CO2 should be an integral part of this strategy. One of the targets of 2020 is the reduction of greenhouse gases by 20% (even 30%) in comparison to 1990. This ambitious goal will require investing in short-term practical applications and long-term breakthrough solutions. Effective utilisation connects the use of CO2 through energy efficient processes with the renewable fuel and chemicals markets. The potential is huge. Markets and Markets (M&M) estimates that the renewable chemicals market is expected to grow from €30 billion in 2010 to €52 billion in 2015, which would mean a growth of 11% each year. Sustainability in EUROPE 2020 means, amongst other things, a more competitive, low-carbon economy and new green technologies capitalizing on the leadership of the EU in this field. While the chemicals market will not have a large enough impact on overall CO2 emissions, the high value products will be used to develop technologies that will eventually lead to the production of bulk chemicals and fuels from CO2, which will have the dramatic impact necessary to achieve the Europe 2020 goals.

CyclicCO2R supports this strategy as it will use state-of-the-art knowledge to create a showcase sustainable process to incorporate CO2 in high-value added materials. The target compound, cyclic glycerol carbonate, is a fine chemical with a promising outlook. It is currently marketed at 2.5 €/kg and concurrently has a limited market size (10

3 tons/yr). The potential of this bi-

functional molecule is much larger, as market studies have indicated that when the price drops below 2 €/kg, the market will increase tenfold and its use as a replacement for ethylacetate and isopropyl alcohol, two

bulk chemicals used in large quantities, would become realistic. The potential for production cost reduction is illustrated by the estimate of 1.7 €/kg in the future for glycerol carbonate.

14

EUROPE 2020 specifically addresses sustainability. By connecting the project with the use of glycerol, CyclicCO2R ensures a viable sustainable industrial route for the utilisation of CO2 while giving the alternative routes towards utilisation of CO2 (photocatalytic and electrocatalytic reduction) the time to mature. Implementation of these future breakthrough technologies will be given due attention through the alternative technologies work package, WP5, assessing the feasibility of the application of state-of-the-art developments to the production of glycerol carbonate and other cyclic carbonates. As the intermediate of cyclic carbonate production, ethene, is a widely used chemical, the impact of successful results will extend far beyond CyclicCO2R.

A key element is the development of added value materials. The catalysts that will be developed are added value materials themselves, especially with the integration into the flow reactor. That, combined with the catalyst modelling knowledge that will be developed, will increase the industrial competitiveness of European industry. To be able to develop these catalysts, a combined approach of catalyst designers, reactor designers, organic chemists, material specialists, and chemical engineers is required. The potential of producing, on a considerable scale, chiral cyclic carbonates (more specifically chiral glycerol carbonate) will open new potential markets and can be used in new products in the pharmaceutical and polymer industry. The production of materials from CO2 and glycerol directly connects with environmentally friendly and sustainable production processes, ensuring long-term impact.


First Name Last Name Affiliation

Address email

Erin Schols TNO Leeghwaterstraat 46 2628 CA Delft, Netherlands

[email protected]

Katina Kiep Evonik Paul-Baumann-Straße 1 45772 Marl, Germany

[email protected]

Ómar Sigurbjörnsson CRI Borgartúni 27 105 Reykjavík, Iceland

omar.sigurbjornsson@ carbonrecycling.is

Daniela Trambitas FeyeCon Rijnkade 17A, 1382 GS Weesp, Netherlands

Daniela.Trambitas@ feyecon.com

Richard Heyn SINTEF Rickhard Birkelands vei 7465 Trondheim, Norway

[email protected]

Michael North York Green Chemistry Centre of Excellence Department of Chemistry University of York

[email protected]


31

York, United Kingdom, YO10 5DD Willy Offermans RWTH CAT Catalytic Center

Institut fur Technische und Makromolekulare Chemie RWTH Aachen Worringerweg 2, Raum 38C-150 D-52074 Aachen, Germany

[email protected]

Gido Mul UTwente Faculty of Science & Technology University of Twente, PO Box 217 Meander 225 7500 AE, Enschede, Netherlands

[email protected]

9. References

1. A. Börner et al, Chem. Rev. 2010, 110, 4554–4581. 2. A. Dibenedetto et al. J. Mol. Catal A: Chem. 2006, 257, 149–153 3. P. Munshi et al. J. Mol. Catal A: Chem. 2009, 304, 1–7 4. A. Dibenedetto et al. Tetrahedron 2011, 67, 1308–1313 5. M. North et al Green Chem. 2010, 12, 1514–1539. 6. M. North ‘Synthesis of cyclic carbonates from CO2 and epoxides’ to be published in ‘Activation of CO2’; S. Suib (Ed.) Elsevier, 2012 7. W. J. Peppel Ind. Eng. Chem. 1958, 50, 767–770; US2873282 1959 Jefferson Chemical Company; M. Yoshida et al. Chem. Eur. J. 2004, 10, 2886–2893. 8. S. Fukuoka et al. Green Chem. 2003, 5, 497–507. 9. Patent no. WO2004089866(A1); WO2009140318(A1); WO2005051939(A1); WO2008128956(A1); US20070197802(A1). 10. J. Melendez et al., Eur. J. Inorg. Chem.; 2007; 21; 3322 – 3326 11. A. Berkessel et al., Organic Letters ; 2006 ; 20 ; 4401-4404 12. M.J. Lippits et al.; Catalysis Today; 2010; 154; 127-132 13. US2011137096 14. Personal communication with Huntsman Chemical, 13 March 2012.


© 2015, TNO, Leeghwaterstraat 46, 2628 CA Delft, Netherlands on behalf of the CyclicCO2R consortium. CyclicCO2R is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




CyclicCO2R and the European Commission's 7th Framework Programme must be given credit, but not in any way that

suggests that they endorse you or your use of the work;




32

DECORE Direct ElectroChemical Oxidation

Reaction of Ethanol: optimization of the catalyst/support assembly for

high temperature operation

Proposal full Name: Direct ElectroChemical Oxidation Reaction of Ethanol: optimization of the

catalyst/support assembly for high temperature operation Acronym: DECORE Call Identifier: NMP4-SL-2012-309741- Rational design of nano-catalysts for sustainable

energy production based on fundamental understanding Duration: 01/01/2013 – 31/12/2016 Grant Agreement No: 309741 Total Budget: 3,070,020.54 € Coordinator: Prof. Gaetano Granozzi Website: https://decore.eucoord.com/

Consortium List


1 Università degli Studi di Padova UNIPD Italy 2 Technische Universitaet Muenchen (terminated) TUM Germany 3 Università degli Studi Milano Bicocca UNIMIB Italy 4 Københavns Universitet UCPH Denmark 5 Universidad de La Laguna ULL Spain 6 Consiglio Nazionale delle Ricerche ICCOM Italy 7 Elcomax Gmbh (terminated) ELCO Germany 8 Elcore Gmbh ELCOR Germany 9 Universitaet Innsbruck UIBK Austria

Contents 1. Summary .......................................................................................................................................... 33 2. Keywords ......................................................................................................................................... 33 3. Background – Current state of the art ............................................................................................. 33 4. Scientific and technological challenges ........................................................................................... 34 5. Objectives ........................................................................................................................................ 35 6. Significant results ............................................................................................................................. 35 7. Expected impact .............................................................................................................................. 35 8. People involved in the project ......................................................................................................... 36 9. List of Publications of DECORE ........................................................................................................ 37 10. Copyright statement ...................................................................................................................... 37

https://decore.eucoord.com/


33

1. Summary

The main general goal of DECORE is to achieve the fundamental knowledge needed for the development of a fuel cell (FC) electrode, which can operate efficiently (both in terms of activity and selectivity) as the anode of a direct ethanol (EOH) FC (DEFC, see Figure 1) in the temperature range between 150-200 °C (intermediate-T). Such a technology is still lacking in the market. The choice for EOH as an alternative energy source is well founded on the abundance of bioethanol, and on the relatively simpler storage and use with respect to other energy carriers. The intermediate-T is required for an efficient and selective total conversion of EOH to CO2, so exploiting the maximum number of electrons in the DEFC. DECORE will explore the use of fully innovative supports (based on titanium oxycarbide, TiOxCy) and nano-catalysts (based on group 6 metal carbides, MCx, M=Mo,W), which have never been tested in literature as anodes for DEFCs. The new support is expected to be more durable than standard carbon supports at the targeted temperature. The innovative nano-catalysts would be noble-metal free, so reducing Europe’s reliance on imported precious metals. To tailor the needed materials, the active role of the support and nano-catalyst is studied at atomic level. Demonstrating an activity of such nano-catalyst/support assembly at intermediate-T would open a novel route where DEFCs with strongly reduced production costs would have an impact on a fast industrialisation. The power range for the envisioned application is of the order of hundreds of Watts, i.e. the so called distributed generation, having an impact for devices such as weather stations, medical devices, signal units, auxiliary power units, gas sensors and security cameras. By the end of the project, a bench-top single DEFC operating at intermediate-T will be built and tested.

Figure 1: Schematics of a DEFC

2. Keywords

DEFC, intermediate-T, innovative supports, noble metal-free catalysts


Alternative supports at intermediate-T. High temperature PEM-FCs (HT-PEM FC, T > 90°C) are considered to be the next generation of PEM-FC

technology because they have several advantages over cells operated at low T:

(1) improved reaction kinetics;

(2) increased catalyst tolerance toward contamination;

(3) improved heat rejection capability;

(4) improved water management.

Unfortunately, when PEM-FCs are operated at high temperatures (90-200 °C), catalyst support corrosion is severe, leading to a rapid degradation of the performance. Typically, during long-term HT-PEM FC operation (> 500 h), the oxidation of the carbon support has clearly been observed, resulting in the separation of Pt NPs from the carbon support and loss of performance. Other failure modes also contribute to catalyst degradation such as particle growth due to Pt dissolution and precipitation (Figure 2), sintering and agglomeration, all causing a decrease of the catalyst electro-active surface area.

Figure 2: Coarsening of catalyst particles

Therefore, it is necessary to explore alternatives to replace carbon materials as catalyst supports to improve the durability of PEM-FCs.

This point becomes strategic when DEFCs are considered, because of the higher operation temperature needed to obtain complete EOH oxidation to CO2 at the anode. Conductive oxides have been already considered in literature as emerging candidates for catalyst support in FC applications, having reasonable surface area, mechanical strength, thermal, and hydrothermal stabilities. In order to increase the intrinsic electron conductivity of the oxide, TiOxCy have been chosen as an alternative support.

Specific catalysts for EOR. In recent years, an increasing interest in the development of catalyst for DEFC has risen. EOH, with its high energy density (8 kW kg-1), production from renewable sources and easy storage and transportation, is almost the ideal combustible for FCs where its chemical energy can be directly converted into electrical energy. However, there is still a lack of catalysts that can perform complete oxidation of EOH at


34

a high rate, which limits its potential application in DEFCs.

While Pt tends to be one of the best suited catalysts for EOR because it can activate the C-C bond, it requires a significant overpotential and its rate is rather slow. The current density produced via the total conversion to CO2 as the result of C-C bond activation, only amounts to a few % even for the most active alloys (i.e. binary PtSn and PtRu based materials). Most of the current is produced from the partial EOR to acetaldehyde or acetic acid. All these considerations are valid at room temperature. In addition, there is a cost and abundance issue with noble metals. So, alternative noble metal-free catalysts are needed for reducing the DEFC and, in general, the PEM-FC costs.

A review of transition metal carbides and nitrides used as electrode materials for low temperature FCs has been recently published. It is known that group 6 metal carbides (MCx, M=Mo and W), can mimic the catalytic behaviour of certain noble metals, and studies on the electrocatalytic behaviour of WCx towards hydrogen and methanol electro-oxidation have been performed in recent years. Even more interesting is the increase in activity towards the EOR obtained with Pt/WCx bimodal electrocatalysts, also for the oxygen reduction reaction. On the other hand, research on MoCx for application in FCs is at its first stages. In DECORE metal carbides have been chosen as candidates to be tested for EOR at intermediate-T.


Implementation of suitable model system to increase the understanding of the innovative materials.

An important task of DECORE is to “expand” the knowledge on the targeted innovative materials. To accomplish such a task, two WPs have been devoted to i) preparation and characterization of flat model systems to be studied on the premises of a rigorous surface science approach (WP2) and to ii) their theoretical modelling by Density Functional Theory (DFT) calculations (WP3), respectively. Tracking the steps of the carburization process of TiO2 to prepare TiOxCy is a major challenge of DECORE. Within this approach, also high surface area supports formed by titania nanotubes (TiNTs) are considered (see Figure 2). Also drawing the complex interfacial chemistry of the model MCx/TiOxCy

systems is a scientific challenge of DECORE.

Figure 2: SEM micrographs of the TiNTs:

a) after anodization and b) after a thermal acetylene treatment at 850°C for 10 min. The lower insets are the corresponding cross-sectional views.

Implementation of scalable methods for the preparation of nanopowders of TiOxCy and of group 6 metal carbides (MCx, M=Mo and W).

The challenge is obtaining, by sustainable and scalable methods, nanopowders of the support and of the catalysts suitable to be used for the preparation of the final electrode to be implemented in the Membrane Electrode Assembly (MEA) (WP4 and WP5). The powders currently present in the market are not suitable for the targeted application and many efforts are devoted in DECORE to obtain high surface area system.

Implementation of suitable techniques to validate the electrochemical activity and stability of the catalyst/substrate assembly at intermediate-T.

Developing EC as well as mass spectrometric methods for the study of EOR at intermediate-T is a major challenge of DECORE (WP6). A standardization of the methods is crucial for allowing tests of the individual systems by the different groups under comparable conditions. This certainly represents a step beyond the-state-of-the-art and enables objective criteria for choosing the most promising materials for further exploitation in a MEA.

As an example of a state-of-the-art characterization tool we adopt the Identical-Location Transmission Electron Microscopy (IL-TEM) and Scanning Electron Microscopy (IL-SEM) for the investigation of the degradation mechanisms. A big challenge is to gradually extend this methodology to the application on innovative supports at intermediate-T.

Specific catalysts for EOR. Application of MCx for EOR has not been explored in literature and presents an interesting alternative to Pt-based materials based on the results obtained for CO and methanol. This certainly represents a challenge well beyond the state-of-the-art. Moreover, the use of temperatures in the 150-200 ºC range, as one of the goals of DECORE, increases the


35

possibilities to apply these nano-catalysts. Finally, the incorporation of small amounts of Pt or other metals to the carbide will be the alternative if only insufficient activities are achieved.

Assembling a MEA with the new catalysts and a PBI membrane for HT-PEM-FC. In DECORE, we adopt membranes based on phosphoric acid doped poly[2,2’-(m-phenylene)-5,5’-bibenzimidazole] (usually refereed as PBI), which can be operated at temperatures between 120 °C and 180 °C. These are state-of-the-art membranes developed by the Elcore Gmbh partner. Testing them for DEFCs (WP7) goes beyond the state-of-the-art.

5. Objectives

The general goal of DECORE is to build up the basic knowledge needed for the development and industrialization of an innovative nano-catalyst/support assembly to be integrated as the anode of a DEFC operating at intermediate-T.

The main objectives are: 1. complete electro-oxidation of ethanol (EOR) to CO2 at intermediate-T (150-200 °C); 2. development of innovative TiOxCy and MCx (M= Mo, W) supports specifically tailored to avoid degradation of the active catalyst and corrosion of the support at intermediate-T, and having sufficient electrical conductivity and porosity; 3. development of noble metal-free or -poor catalysts based on group 6 metal carbides (MCx, M=Mo,W); 4. characterization of response of the MCx/TiOxCy assembly to the temperature and electrochemical environment; 5. development of tools for determining the electrochemical activity at intermediate-T in half-cells; 6. laboratory-scale validation of the nano-catalyst/support assembly compared to state-of-the-art benchmarks; 7. mechanistic studies of the electro-oxidation of EOH to CO2; 8. testing the nano-catalyst/support assembly using industrial standards in a existing test rigs of high-T FCs using hydrogen or synthethic reformate as energy carrier at the anode and air at the cathode; 9. development and test of a bench-top single DEFC operating at intermediate-T.

6. Significant results

At the end of the first Reporting Period (M18) the following main achievements were obtained:

Thanks to the advancement of the work on model systems (WP2 and WP3), the intrinsic stability of TiOxCy and of MCx particles

(M=Mo,W) toward oxidation has been derived

in (a) UHV, (b) ambient conditions (i.e. in presence of oxygen) and (c) electrochemical conditions (i.e. in water solution).

TiOxCy nanopowders were synthesized with a new procedure developed within the project (WP4). They are characterized by a nano crystalline morphology, have grain sizes of less than ~30 nm and surface areas of the order of hundreds of m

2/g, and their electrochemical

characterization at 25°C and 150°C in conc. H3PO4 has been carried out.

Preparation of MCx (M=Mo,W) particles with sizes below 20 nm has been achieved following two different procedures (WP5).

Electrochemical half-cells for intermediate-T characterization were designed, built and distributed among the Consortium partners (WP6).

A suitable atomic-scale methodology (IL-SEM) for mechanistic degradation studies at intermediate-T was developed (WP6).

It has been demonstrated that the ethanol oxidation activity at 0.5 V vs. RHE with a standard Pt electrode is enhanced by a factor 100 increasing the temperature from 55 °C to 158 °C. These figures can have a relevant impact on the DEFC at intermediate-T.

A standardized protocol for EC half-cell tests at intermediate-T was developed (WP6).

Several papers with the DECORE acknowledgments have been published in relevant Journals of the field (see list at the end).

Expected final results and their potential impact and use

The results so far accumulated are strengthening the original ideas behind DECORE. After the experiments in the first Reporting Period, it seems that it is now demonstrated that switching from ambient to intermediate-T gives a very large boost to ethanol oxidation. Developing supports alternative to standard carbon-based ones, which can withstand the required temperature of exercise, and nano-catalyst/support assemblies (noble metal-free) properly active at intermediate-T would open a novel route where DEFCs with strongly reduced production costs would have an impact on a fast industrialisation. In case of achievement of the targeted performances for the catalyst/support assemblies, by the end of the project a bench-top single DEFC operating at intermediate-T will be built and tested.

7. Expected impact

1 Exploitation of renewable, efficient, and inexpensive sources for alternative energy production. EOH is an


36

inexpensive source: it can be produced as bioethanol by fermentation of lignocellulose, which uses crop or wood as precursors (resulting in a neutral carbon footprint). It is an abundant resource, easily prepared and storable, with a high volumetric energy density. Reaching the goal of a FC capable of efficiently transforming the chemical energy of EOH into electricity (DEFC) would have a real economic and social impact on the current scenery of alternative energy production.

2. Improving the performance of existing industrial processes for energy production. Low-temperature DEFCs have been already developed as prototypes. As an example, various prototypes of DEFC based mobile phone chargers were built featuring voltages from 2V to 7V and powers from 800mW to 2W. However intermediate-T is required for an economic and efficient conversion of EOH into CO2. A rational search for the appropriate materials required to accomplish such a task has not yet been explored.

3. Rational catalyst design. The programmed activities of DECORE will imply studies both on model systems and on real high-surface area catalysts (MCx/TiOxCy assemblies between TiOxCy porous powders and MCx nano-powders), exploring also scaling up economical procedures, which would take the proposal up to the final application of the designed anodes for intermediate-T DEFCs.

4. Reduce Europe's reliance on imported rare earths/precious metals. Among the components in a PEM-FC, Pt-based electrodes contribute over 55% of the total costs. DECORE will explore the use of innovative nano-catalysts (based on group 6 metal carbides, MCx, M=Mo,W), which have the capability to mimic the electronic properties of Pt.

Demonstrating an activity of such catalysts towards EOR at intermediate-T would open a novel route where the DEFC production cost reduction would have an enormous impact on DEFC industrialisation. If the activity of the carbide catalysts would be inadequate, a

contingency plan will be developed where small amounts of Pt would be introduced to enhance the final performances.

The potential economic impact of DECORE is threefold:

•on the cost and management of the energy carrier (EOH), due to its low price, abundance and ease of storage;

•on the production costs of the FCs, due to the elimination (or reduction) of a very expensive component (Pt or other noble metals);

•on the durability (expected higher catalyst/support interactions) and efficiency (due to the intermediate-T) of the resulting FCs.

The expected gain in the production costs is essentially bound to the reduction (or even elimination) of noble metals as active catalysts: all the raw materials needed to produce the innovative MCx nano-catalysts are cheap (roughly an average factor 10

-3 with respect to Pt). The

cost of rough starting materials (titania precursors and the carbon sources) for the production of the TiOxCy support is rather low, while the energy costs for their production strongly depends on the actual method implemented in DECORE. In any case we expect that an eventual higher cost for the production of supports alternative to standard carbon ones will be overcompensated by the expected higher efficiency and durability of the innovative anode based on the MCx/TiOxCy assembly.

As an important part of the goals of DECORE, we have planned the development of a bench-top single DEFC, where to implement efficiency calculations, especially in comparison with similar standard HT-PEM-FCs. The obtained numbers will be the basis for the development of a concept of an intermediate-T DEFC stack for delivering power up to 1kW range.



Gaetano Granozzi UNIPD Department of Chemical Sciences University of Padova Via Marzolo 1 35131 Padova, Italy

[email protected]

Julia Kunze TUM/UIBK Institut für Physikalische Chemie, Leopold-Franzens-Universität Innsbruck Innrain 52c (Josef-Möller-Haus) A-6020 Innsbruck, Austria

[email protected]

Cristiana Di Valentin UNIMIB Materials Science Department, University of Milano Bicocca, Via Roberto Cozzi, 55

[email protected]





37

20125 Milano, Italy

Matthias Arenz UCPH Department of Chemistry, Københavns Universitet, Universitetsparken 5 2100 København, Denmark

[email protected]

Elena Pastor Tejera ULL Departemento de Química-Física, Universidad de La laguna, Av Astrofísico Francisco Sánchez Avenida Astrofsico Francisco Sanchez, 38206, La Laguna, Tenerife, Spain

[email protected]

Alessandro Lavacchi ICCOM ICCOM CNR Via Madonna del Piano, 10 50019 - Sesto Fiorentino (FI), Italy

[email protected]

Martin Batzer elcomax/ elcore

elcomax GmbH Bayerwaldstr. 3 81737 München, Germany

[email protected]

9. List of Publications of DECORE

C. Rüdiger, J. Brumbarov, F. Wiesinger, S. Leonardi, O. Paschos, C. Valero Vidal, and J. Kunze-Liebhäuser, Ethanol Oxidation on TiOxCy Supported Pt Nanoparticles, ChemCatChem, 2013, 5 , 3219-3223, (http://dx.doi.org/10.1002/cctc.201300217).

Y. X. Chen, A. Lavacchi, H. A. Miller, M. Bevilacqua, J. Filippi, M. Innocenti, A. Marchionni, W. Oberhauser, L. Wang and F. Vizza, Nanotechnology makes biomass electrolysis more energy efficient than water electrolysis, Nat Commun, 2014, 5, 4036, (http://dx.doi.org/10.1038/ncomms5036).

G. K. H. Wiberg, M. J. Fleige , M. Arenz, Design and test of a flexible electrochemical setup for measurements in aqueous electrolyte solutions at elevated temperature and pressure, Review of Scientific Instruments, 2014, 85, 085105 (http://dx.doi.org/10.1063/1.4890826).

Zana, C. Rüdiger , J. Kunze-Liebhäuser , G. Granozzi , N. E. A. Reeler , T. Vosch , J. J. K. Kirkensgaard , M. Arenz, Core-shell TiO2@C: towards alternative supports as replacement for high surface area carbon for PEMFC catalysts, Electrochimica Acta, 2014, 139, 21-28 (http://dx.doi.org/10.1016/j.electacta.2014.07.002).

L. Calvillo, D. Fittipaldi, C. Rüdiger, S. Agnoli, M. Favaro, C. Valero-Vidal, C. Di Valentin, A. Vittadini, N. Bozzolo, S. Jacomet, L. Gregoratti, J. Kunze-Liebhäuser, G. Pacchioni, G. Granozzi, Carbothermal Transformation of TiO2 into TiOxCy in UHV: Tracking Intrinsic Chemical Stabilities, J. Phys. Chem. C, 2014, 118 (39), 22601–22610 (http://pubs.acs.org/doi/abs/10.1021/jp506728w).

G. K. H. Wiberg , M. J. Fleige , M. Arenz, Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures, Review of Scientific Instruments, 2015, 86 , 024102 (http://dx.doi.org/10.1063/1.4908169).

M. Favaro, S. Leonardi, C. Valero-Vidal, S. Nappini, M. Hanzlik, S. Agnoli, J. Kunze-Liebhäuser, Gaetano Granozzi, In-situ Carbon Doping of TiO2 Nanotubes via Anodization in Graphene Oxide Quantum Dot Containing Electrolyte and Carburization to TiOxCy Nanotubes, Advanced Material Interfaces, 2015, 2, 1400462 (http://onlinelibrary.wiley.com/doi/10.1002/admi.201400462)


© 2015, UNIPD, Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy on behalf of the DECORE consortium. DECORE is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:









38

DECORE and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




39

DEMCAMER Design and Manufacturing of Catalytic

Membrane Reactors by Developing New Nano-architectured Catalytic and

Selective Membrane Materials

Proposal full Name: Design and Manufacturing of Catalytic Membrane Reactors by Developing New Nano-architectured Catalytic and Selective Membrane Materials

Acronym: DEMCAMER Call Identifier: NMP.2010.2.4-1 New materials and/or membranes for catalytic reactors Duration: 01/06/2011 – 30/06/2015 Grant Agreement No: 262840 Total Budget: 10,834,742.24 € Coordinator: Dr. José Luis Viviente Website: www.demcamer.org

Consortium List

No Beneficiary Name Short name Country 1 Fundación Tecnalia Research and Innovation TECNALIA Spain

2 Flemish Institute for Technological Research VITO Belgium

3 University of Calabria UNICAL Italy

4 Eindhoven University of Technology TUE The Netherlands

5 Agencia Estatal Consejo Superior de Investigaciones Científicas AEl CSIC Spain

6 Fraunhofer-Gesellschaft zur Foerderung der Angewandten Forschung E.V.

FhG-IKTS Germany

7 Boreskov Institute of Catalysis BIC Russian Federation

8 Institut National de l’Environnement Industriel et des Risques INERIS France

9 Rauschert Klosterveilsdorf GmbH RKV Germany

10 Ceramic Powder Technology AS CERPOTECH Norway

11 Hybrid Catalysis BV HYBRID The Netherlands

12 HyGear BV HYGEAR The Netherlands

13 Abengoa Bioenergia Nuevas Tecnologias S.A ABENGOA Spain

14 Guascor Ingeniería S.A. (Terminated) GUASCOR Spain

15 Quantis Sàrl QUANTIS Switzerland

16 Höganäs AB HOGANAS Sweden

17 TOTAL Petrochemicals Research Feluy TOTAL PB Belgium

18 TOTAL Petrochemicals France SA TOTAL PF France


http://www.demcamer.org/


40

1. Summary

The DEMCAMER project proposes an answer to the paradigm met by the European Chemical Industry: increase the production rate while keeping the same products quality and reducing both production costs and environmental impacts. Through the implementation of a novel process intensification approach consisting on the combination of reaction and separation in a “Catalytic Membrane Reactor” single unit. The aim of DEMCAMER project is to develop innovative multifunctional Catalytic Membrane Reactors (CMR) based on new nano-architectured catalysts and selective membranes materials to improve their performance, cost effectiveness (i.e.; reducing the number of steps) and sustainability (lower environmental impact and use of new raw materials) over four selected chemical processes (Autothermal Reforming of methane (ATR), Water Gas Shift (WGS), Fischer-Tropsch (FTS), and Oxidative Coupling of Methane (OCM)) for pure hydrogen, liquid hydrocarbons and ethylene production. The DEMCAMER project comprises activities related to the whole product chain: development of materials / components (membranes, supports, seals, catalysts) through integration/validation at lab-scale, until development/validation of four pilot scale CMRs prototypes. Additionally, three research lines dealing with: 1) collection of specifications and requirements, 2) modelling and simulation of the developed materials and processes, and 3) assessment of environmental, health & safety issues in relation to the new intensified chemical processes- will be carried out.

2. Keywords

Catalysts, membranes, Catalytic Membrane Reactors, Autothermal reforming, Fischer Tropsch, Water Gas Shift, Oxidative Coupling of Methane.


Process Intensification (PI), which is defined as “any chemical engineering development that leads to a substantially smaller, cleaner, safer and more energy efficient technology”, is the actual revolution of the chemical industry. The need for more efficient processes, including further flexible engineering designs and, at the same time, increasing the safety and environmental impact of these processes, is pushing the industry to novel research in this field. The chemistry and related sectors have already recognised the benefits of PI and estimate a potential for energy saving of about 1000 ktoe / year using these processes. The technology of membrane reactor plays an important role in PI and is based on a device combining a membrane based separation and a catalytic chemical

reaction in one unit. Every catalytic industrial process can potentially benefit from the introduction of catalytic membranes and membrane reactors instead of the conventional reactors. According to SusChem

1 more

than 80% of the processes in the chemical industry worth approximately 1,500 billion€, depend on catalytic technologies, and one the shorter-term (5-10 years) objectives of this Platform is to “integrate reactor-catalyst-separation design: integration and intensification of processes requires the development of new catalytic concepts which break down the current barriers (for example, low flux in catalytic membranes)”. However, in spite of these expectations, the industrial application of membrane reactors in the chemical industry is currently very limited and only at a small scale operation (e.g. MRT from Canada and Tokyo Gas from Japan are using membrane reactors for producing 99.99% purity H2 from reformed natural gas

2). This fact

is related to the current state of the technology, suffering from limited performance, durability and robustness of membrane reactors, but also to the conservative nature of this industrial sector.


The objective of industrialisation of catalytic membrane reactors can only be achieved with interdisciplinary research between R&D institutions and industry, covering all the aspect of the chain, from materials development (catalysts and membranes) to design, engineering and test of integrated reactors and evaluation of related safety and environmental issues. A sharing of the technological risk is also a strong incentive to face the conservative nature of such industrial sector. The key research fields to solve these technological drawbacks are: new materials with improved performance and durability (membranes and catalysts), advanced design (including modelling) for membrane reactor module integration, and exhaustive testing and validation of new modules on selected chemical processes using representative industrial prototypes. This research must take always into account the environmental impact, health & safety and cost issues, in order to allow the large-scale industrialization of the technology. All these fields are covered by the DEMCAMER project that proposes developments to implement this technology in representative chemical processes. Figure 1 shows this new concept with steps reduction for ATR process). Main challenges in DEMCAMER are summarized hereafter: Development of novel catalyst materials with

enhanced properties for improved catalytic conversion of the considered processes:


41

A novel class of ATR catalysts based on perovskites generically represented by the formula La1-xSrxCryB’B’’yO3 (where B’ and B’’ are selected from Ru, Fe, Mn, Co, Ni) and Ni based catalysts with low amounts of promoters over supports with optimized oxygen mobility.

WGS catalysts based on Pt alloys supported on modified ceria and titania with improved catalytic activity.

Development of OCM catalysts based on on La-Sr-Ca oxides and Na2WO4/SiO2. type catalysts..

FTS: core-shell type bimetallic nanocatalysts based on Ru@Co, Co@Ru and Co@Fe.

Catalyst materials for each type of process obtained by POSS® nanotechnology.

Development of innovative membranes for catalytic reactors designed for gas and water separation (ATR, WGS, OCM and FTS).

Mixed ion electron conductive (MIEC) membranes (dense nanostructured coatings and hollow fibres) for O2 and H2 separation.

Metal based membranes for H2 production based on Pd-multi alloys and non-Pd alloys fulfilling the DOE 2015 target.

Zeolite membranes based on defect free NaA stabilised sodalite (SOD) and FAU membranes with entrapped catalytic nano-sized particles.

Novel catalytic membrane reactors will be designed on the basis of catalysts and membranes previously developed and using new reactor configurations supported by simulation.

Previous development will be supported by modelling and/or simulation at different levels: materials (membranes and catalysts), transport in membranes, CMRs and reactor prototypes.

Further to lab scale reactor validation, prototype reactors will be constructed, tested and validated under industrial requirements for each process: ATR, WGS, OCM and FTS.

Life Cycle Analysis to assess the environmental impact of the novel CMRs as well as industrial risk assessment study of the considered processes and technologies.

5. Objectives

The aim of DEMCAMER is to develop innovative multifunctional Catalytic Membrane Reactors (CMR) based on new nano-architectured catalysts and selective membranes materials to improve their performance, durability, cost effectiveness and sustainability (lower environmental impact and use of new raw materials) over four selected chemical processes (ATR, WGS, FTS, and OCM) for pure hydrogen, liquid hydrocarbons and ethylene production. The scientific and technical objectives to achieve this general objective are the following: To develop new membrane materials with improved

separation properties, long durability, and with reduced cost.

To develop new nano-architectured catalysts with better performance and at reduced cost.

To understand the fundamental physicochemical mechanisms and the relationship between structure / property / performance and manufacturing process in membranes and catalysts, in order to achieve radical improvements in membrane reactors.

To design, model and build up novel more efficient (e.g. reducing the number of steps) membrane reactor configurations based on the new membranes and catalysts.

To validate the new membrane reactor configurations, at semi-industrial prototype level, in the four selected processes for pure hydrogen, liquid hydrocarbons and ethylene production.

To improve the cost efficiency of membrane reactors by increasing their performance, decreasing the raw materials consumption and associated energy losses.

Figure 1. DEMCAMER concept (ATR process).

To enable the use of new raw materials (i.e.; convert non-reactive raw materials).

To assess the health, safety and environmental impact of the four CRM developed processes, a


42

complete LCA of the developed technologies will be performed.


Many progresses have been achieved especially in the development of the catalysts, membranes and lab-scale validation of the reactors as well as on the modelling and simulation (i.e. ab-initio calculation for membranes and catalysts, transport in membranes, catalytic membrane reactors simulation, process design and simulation). Besides, designs and construction of the pilot prototypes and the initial assessment of the health, safety and environmental impact of the four CRM have been also finalised. Main work performed since the beginning of the project is described hereafter. Definition and identification of the specific industrial

requirements for the intensification of the four processes being in the focus of development within the project DEMCAMER (ATR, WGS, OCM, FTS).

Final catalyst generation developed for each processes (ATR: Ni promoted catalysts supported on modified alumina oxides

3; WGS: Pt promoted

catalysts supported on cerium based oxides; OCM: tungsta promoted catalysts supported on silica

4; FTS:

Ru promoted catalysts supported on titanium oxides) showed improved activity, selectivity and stability over catalytic formulations described in the state-of-the-art achieving for the DEMCAMER objectives.

Development and supply of membranes for the ATR, WGS, OCM and FTS lab scale catalytic membrane reactors and selection of membranes for the ATR, WGS and OCM pilot prototypes. Main achievements in the frame of the membranes development have been the following:

The development of materials for Mixed Ion-Electron Conducting membranes, zeolite membranes, ceramic supports, metallic supports and interdiffusion layers and selection of improved materials for the target application.

The development of the ceramic membrane supports, metallic membrane supports and interdiffusion layers and selection of the improved membrane supports.

The development of MIEC based membranes and selection of improved membranes and sealing techniques (using gold layers or RAB techniques) for lab-scale reactors and pilot prototype reactors.

The development of metal based membranes (Pd-based) for hydrogen separation with fluxes and perm-selectivities above the targets of the project. Perm-selectivities over 10000 and high fluxes were achieved as reported

5 in Selection

of the membrane for the lab-scale reactors and pilot prototype reactors.

The development of the optimized zeolite membranes for the FTS lab-scale reactor.

Different lab-scale membrane reactors have been designed and constructed. In addition, different integration strategies for the CMR components: catalysts, membranes and supports, sealing based have been identified. For the WGS reaction, the fluidized bed reactor has been successfully demonstrated. For the ATR reaction, the target has been partially achieved. While the catalyst has been fully characterized and the membranes where tested with single tubes with fluxes as high as 5 ml/(cm

2

min), the latest batches of membranes were of different qualities and did not allow testing the full reactor. For OCM the reactor has been constructed and preliminary tests carried out, however the same problem with the oxygen membranes as for ATR did not allow complete demonstration of the concept. For FTS, the hydrogen concept with palladium membranes has been demonstrated, although better tests need to be carried out.

Design and construction of the pilot prototypes reactors for the ATR, WGS, FTS and OCM processes.

Modelling and simulation activities were focused on the design of specific catalysts and membranes as well as the lab-scale reactors simulation starting from the ab-initio calculation for membranes and catalysts up to the analysis of the membrane reactor performance. i) Ab- initio calculations for membranes and catalysts:

Using the Density functional theory (DFT) method for the ATR, FTS and OCM catalysts, information has been obtained on the potential energy-optimized atomic structures of active components, modes of their interaction with support materials, and behavior upon interaction with reagent molecules.

ii) Transport in membranes

Mathematical models describing the permeation in metal, MIEC and zeolite membranes have been developed.

Elementary steps affecting the permeation through the membrane and their influence on mass transport properties have been identified.

Iii) Membrane reactors

Reliable models and simulation codes have been developed to analyse the performance of the membrane reactors on a wide spectrum of operating conditions for ATR, FTS, OCM and WGS. Three different reactor configurations have been considered for WGS: fluidized bed membrane micro-reactors, micro-reactors and fixed bed membrane reactors. In some cases, the results achieved with the simulations


43

carried out in the “transport in membranes”, on the analysis of the gas permeation through the membranes, have been integrated in these models, so that the simulations are as much as possible correspondent to the experimental system studied.

Preliminary Life Cycle and Environmental Analysis (LCA) has been performed on the CMR technologies, comparison of CMR technologies with conventional ones has been performed. Database on explosivity has been constructed, modelling approach has been formalized to assess safety of CMR process, risk assessment performed and safety recommendations proposed (methodology proposed according to ISD (inherently safe design) principles, technical and organizational recommendations); Framework of Socio-Economic analysis (SEA) has been defined, preliminary data from safety and LCA collected, review for production cost data has been performed.

7. Expected impact

The project will directly impact the reduction of production steps, the alternative use of (new) raw materials and will lead to a major reduction of environmental footprint. In comparison to a conventional configuration in which a reactor is combined with a downstream separation unit, the use of membrane reactors can bring various potential advantages such as reduced capital costs (due to the reduction in size of the process unit), improved yields and selectivities (due to the equilibrium shift effect) and reduced downstream separation costs (separation is integrated). In the case of Hydrogen production, process steps can be reduced from 4 (Steam reforming, High Temp WGS, Low Temp WGS and H2 separation through PSA) to one single unit (see Figure 1) or when using a WGS CMR the last three steps can be reduced to 1 single unit. On the other side FTS and OCM process can be reduced from two to one process steps. Additionally, for OCM the air separation unit can be avoided with big advantages in terms of capital and operating costs. The new catalytic membrane reactors could open the new possibilities for the use of raw materials such as:

Processing of gasified liquid hydrocarbon streams (previously gasified): alcohols produced from biomass and residual streams of liquid and gaseous hydrocarbons produced from oil refining.

Processing of syngas produced from several sources (coal, oil and biomass).

Processing of C1-C4: natural gas, liquid petroleum gases, to obtain ethylene and H2.

Figure 2. Water Gas Shift Membrane Reactor pilot prototype and test setup. On the other side, the new process will lead to a major reduction of environmental impact by decreasing the Equivalent CO2 emissions

as well as the CO2 emissions to

50% by intrinsic CO2 capture (i.e. ~48% for OCM/CMR). In addition, all CMR configurations will allow the CO2 to be captured and liquefied “on site”. In addition, DEMCAMER will foster green transportation and energy supply technologies due to lower H2 prices. Energy consumption will be also decreased having process in which high conversion at low temperature (i.e. ~500 ºC instead of 850 ºC for Steam Methane Reforming (SMR)), reduced steps and reaction volume by ≥1 order of magnitude with respect to a traditional reactor, increased C2, C5+, and H2 yield (improved reforming efficiency). The reduction of raw materials consumption is another expected impact:

Minimization of by-products formation, high recovery (i.e. H2 recovery > 90% for ATR and WGS), high conversion and selectivity.

Reduction of raw materials (i.e. 10% for WGS-CMR) and reusing of purge/retentate streams.

Under the risk that the EU chemical industry could become soon a net importer of chemicals, SusChem outlined strategic R&D strategies aimed to help this sector in maintaining a large global share. DEMCAMER will contribute herewith by providing decisive step-changes in the bulk chemical industry that will not only safeguard its global market position and employment but also enable it to enter new markets and create new workplaces.


44



José Luis Viviente TECNALIA Mikeletegi Pasealekua, 2 E-20009, San Sebastián, Spain

[email protected]

Frans Snijkers VITO Boeretang 200, 2400 Mol, Belgium

[email protected]

Enrico Drioli UNICAL Via Pietro Bucci, Cubo 44ª 87036 Rende, Italy

[email protected]

Fausto Gallucci TUE Den Dolech 2, 5612 AZ Eindhoven, The Netherlands

[email protected]

José Luis García Fierro AE-CSIC Inst. de Catalisis y Petroleoquimica, Marie Curie 2; 28049 Madrid, Spain

[email protected]

Hannes Richter FhG-IKTS Michael-Faraday-Strasse, 1 07629 Hermsdorf, Germany

[email protected]

Ylias Ismagilov BIC Laborat. of Environmental Catalysis, Prospekt Ak. Lavrentieva, 5 630090 Novosibirsk, Russian Federat.

[email protected]

Alexis Vignes INERIS Accidental Risk Division Parc Technologique Alata - BP 2 60550 Verneuil-en-Halatte

[email protected]

Volker Prehn RKV Industriestrasse 1, 98669 Veilsdorf, Germany

[email protected]

Sophie Labonnote-Weber

CERPOTECH Kvenildmyra 6 N-7072 Heimdal, Norway

[email protected]

Erik Abbenhuis HYBRID Den Dolech 2, 5612 AZ Eindhoven, The Netherlands

[email protected]

Leonardo Roses HYGEAR Westervoortsedijk 73, 6802 AV Arnhem, The Netherlands

[email protected]

Juan Luis Sanz ABENGOA Campus Palmas Altas C/ Energia Solar, 1; 41014 Sevilla, Spain

[email protected]

- - GUASCOR TERMINATED

Arnaud Dauriat QUANTIS Parc Scientifique EPFL, Batiment D 1015 Lausanne, Switzerland

[email protected]

Per-Olof Larsson HOGANAS Bruksgatan, 35 SE 26383Höganäs, Sweden

[email protected]

Kai Hortmann TOTAL PB Zone Industrielle C 7181 Feluy, Belgium

[email protected]

Xavier Marcarian TOTAL PF PERL - Pôle d'Etudes et de Recherche de Lacq BP 47 - Pôle économique 2 64170 Lacq, France

[email protected]

9. References

1. European Technology Platform for Sustainable Chemistry (SusChem), Strategic Research Agenda 2005 2. Y. Shirasaki et al. International Journal of Hydrogen Energy, 34 (10) (2009) 4482-4487. 3. I.Z. Ismagilov et al., Int. J. Hydrogen En. 39 (2014) 20969-20983. 4. I.Z. Ismagilov et al., Kinet. Catal. 56 (4) (2015) in press. 5. E. Fernandez et al., Int. J. Hydrogen En., 40 (2015) 3506 – 3519.


© 2015, TECNALIA, Mikeletegi Pasealekua, 2E-20009, San Sebastián, Spain on behalf of the DEMCAMER consortium. DEMCAMER is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:























45



DEMCAMER and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




46

European Structured Research Area on Catalysis and Magnetic Nanomaterials

Proposal full Name: European Structured Research Area on Catalysis and Magnetic Nanomaterials

Acronym: eCAMM Call identifier: FP7-NMP-2011-CSA-5 Duration: (48 months)

Start date: 1/03/2012 End date: 29/02/2016 Grant Agreement n°: 290455 Total budget: € 445.000 Coordinator: Prof.Gabriele Centi

Website: www.ecamm.eu

Consortium List

Contents

1. Summary .................................................................................................................................................. 47 2. Keywords ................................................................................................................................................. 47 3. Objectives ................................................................................................................................................ 47 4. Benefits and perspectives of CSA ............................................................................................................ 47 5. Spreading excellence, Exploiting results and Disseminating Knowledge ................................................ 47 6. Contact information ................................................................................................................................ 48 7. Copyright statement ................................................................................................................................ 48

Partip. No

Participant organisation name /Acronym

Country Organization type

1 European research Institute of Catalysis aisbl / ERIC

Belgium DIS of NoE IDECAT

2 European Institute of Molecular Magnetism S.c.a.r.l. / EIMM

Italy DIS of NoE MAGMANet

http://www.instm.it/


47

1. Summary

The objective of the proposal is to support the creation of a European structured research area for catalytic and magnetic nanomaterials by integrating two DISs (ERIC and EIMM) operating in the fields of catalysts and nanomagnetism, and their plan to expand current activities in order to (1) obtain a larger coverage of industrial technologies/sectors and (2) extend the involvement to the activities of the relevant industrial partners. The aim is to create a realistic basis to achieve financial sustainability of the two DISs which will keep their own individual personality, but share knowledge and expertise, structure, equipment and other resources, to offer a broader and cost-effective range of services to companies, and in the long-term the vision is to provide new competences (deriving from the integrated collaboration) to new industrial sectors such as materials for nanomedicine, health care and diagnostics, to ICT, environment protection, and nanomaterials’ risk. Functional to this objective are also the possibilities a) to realize efficient synergies to reduce the management costs of the DISs, and to be more cost-effective for a structuring effect inside ERA, b) create a larger critical mass, and a broader spectrum of expertise and equipment, c) improve the attractiveness towards young researchers through a combination of high-profile science and educational activities in their favor, and d) enhance the visibility and develop more efficient politics for incorporating new partners in order to progressively expand the actual core partners. Reaching the objectives, implementing these activities will thus result in 1) an improved coordination in both research and innovation, through the management and cultural synergies between the two DISs (ERIC and EIMM); 2) a more robust critical mass of the durable integrated structure; 3) a boosted dynamism of research, technological development and innovation in the field(s); and 4) an improved structuring of the European Research Area.

2. Keywords

Catalysis magnetic materials industrial chemistry chemical processes molecular magnetism

3. Objectives

The objective of the CSA is to prepare an increased the FV of ERIC and EIMM by supporting their strategy of extending industrial participation in their activities, also by expanding application sectors through their

integration of competences, and by strengthening their impact and visibility. The two DISs will keep their own individual personality, but share knowledge and expertise, struc-ture, equipment and other resources to improve their capacity of collaboration with companies. In a long-term vision the integration of competences will allow to open to new industrial sectors such as materials for nanomedicine, health care and diagnostics, to ICT, environment protection, etc.

4. Benefits and perspectives of CSA

The objectives of this CSA will be underpinned by the integration of the two DISs’ activities toward industry. The organisational work involved of the NoE type will be conducted outside the CSA. To un-derpin the CSA objectives a new research roadmap (RRM) and joint databases will be established. A highly specialized but all-round expertise and know-how at the excellence level provided by DISs partners cannot be easily reached by industries in Europe. Especially for SMEs, whose limited turn-over does not allow heavy investments in R&D, the chance of having all the best Institutions and core competencies, usually spread around Europe, within reach is invaluable. It is quite common for industries and private companies to ask for services from the laboratories of the local University but it is very rare that a complete range of techniques, from project to prototype for example, can be per-formed by a single University or Institution. With eCAMM, the quality and breadth of the expertise available amongst its Members make this task within the grasp of most Small Medium Enterprises just contacting only one organization. A powerful Network like the one deriving from the two DISs can provide a wide choice of business services, both for Members and external customers.

5. Spreading excellence, Exploiting results and Disseminating Knowledge

Spreading of excellence, dissemination and education are part of the mission of the two DISs (ERIC and EIMM) and as a consequence these aspects are fully retained as eCAMM objectives. eCAMM plans to continue the training and spreading activity already well developed by the two former DISs, and in particular further implement the European Doctorates and to give continuity to educational activities, and high-profile thematic workshops or conferences.


48

6. Contact information

ERIC & EIMM legal office Rond Point Robert Schuman,14 8° floor B-1040 Brussels - Belgium Phone: +32 474654412 E-mail: [email protected] ERIC & EIMM operative office c/o Consorzio INSTM Via Giusti,9 Firenze 50121 Italy Phone + 39 055 2338713 Scientific contacts: Prof. Gabriele Centi President of ERIC University of Messina Salita Sperone, 31 Messina 98122, Italy Phone: +39-090-6765609 Skype: merlinowiz E-mail: [email protected] Prof. Andrea Caneschi Managing Director of EIMM

University of Florence Via della Lastruccia 3 50019 Sesto Fiorentino (FI), Italy Phone: +39-055-4573327

E-mail: andrea.caneschi unifi.it Skype: kai_lamm Management contacts: Dr. Stefano Vannuzzi INSTM (www.instm.it) Via G. Giusti, 9 50121 Firenze, Italy Phone: +39-055-233-8713 (direct line) E-mail: [email protected] Skype: svannuzzi Dr. Serena Orsi ICCOM-CNR (www.iccom.cnr.it) Via Madonna del Piano,10 50019 Sesto F.no (FI) Italy Phone: +39-055-5225279 E-mail: [email protected] Skype: serewinnie


© 2015, ERIC & EIMM legal office, Belgium, on behalf of the eCAMM consortium. eCAMM is a CSA project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




eCAMM and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;






49

FREECATS Doped carbon

nanostructures as metal-free catalysts

Proposal full Name: Doped carbon nanostructures as metal-free catalysts Acronym: FREECATS Call Identifier: NMP.2011.2.2-4 - Novel materials for replacement of critical materials Duration: 01/04/2012 – 31/03/2015 Grant Agreement No: 280658 Total Budget: 5,070,665.40 € Coordinator: Professor Magnus Rønning Website: www.freecats.eu

Consortium List

No Beneficiary Name Short name Country 1 NORGES TEKNISK-NATURVITENSKAPELIGE UNIVERSITET NTNU NTNU Norway 2 AGENCIA ESTATAL CONSEJO SUPERIOR DE INVESTIGACIONES

CIENTIFICAS CSIC Spain

3 UNIVERSIDADE DO PORTO UPORTO Portugal 4 CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE CNRS France 6 CONSIGLIO NAZIONALE DELLE RICERCHE CNR Italy 6 THE UNIVERSITY OF WARWICK Warwick UK 7 SICAT SARL SICAT France 8 PROTOTECH AS Proto Norway 9 ADVENTECH - ADVANCED ENVIRONMENTAL TECHNOLOGIES LDA Adven Portugal

10 OF THE UNIVERSITY OF CAMBRIDGE UCAM UK

Contents

1. Summary .................................................................................................................................................. 49 2. Keywords ................................................................................................................................................. 50 3. Background – Current state of the art ..................................................................................................... 50 4. Scientific and technological challenges ................................................................................................... 50 5. Objectives ................................................................................................................................................ 51 6. Significant results / exploitable results ................................................................................................... 51 7. Expected impact ...................................................................................................................................... 53 8. Principal investigators involved in the project ........................................................................................ 54 9. References ............................................................................................................................................... 55 10. Copyright statement .............................................................................................................................. 55

1. Summary

FREECATS is primarily aimed at generating new fundamental knowledge and fostering new prospects and frontiers in the field of catalysis for the sustainable production of chemicals and commodities. New tailored metal-free catalytic architectures are designed and fabricated starting from nanoscale building blocks.

During the project a complete investigation on the influence of the synthesis parameters on the physical properties of N-CNTs has been accomplished. Development of organic functionalization as an alternative ex-situ approach to the hetero-decoration of carbon nanomaterials that allows an easy and precise control of the doping groups using mild reaction conditions has allowed, for the first time, to establish an

http://www.freecats.eu/


50

unambiguous relationship between structure and catalytic activity for ORR paving the way to the design of more active catalysts. The development of a radically new scalable synthesis method starting from food residue for the production of N-doped carbon metal-free catalyst with controlled shape and size is demonstrated.

Direct CFD simulation of mixing in complex SiC foam structure using real structure models and comprehensive mechanistic models of oxidative dehydrogenation and catalytic ozonation on non-metallic catalysts have been obtained. Stability tests of ORR catalysts have been performed in a FC stack for 400 hours, and for CWAO in continuous flow for 100 hours.

Regarding AOPs, the screening tests with N-doped carbon materials using different target compounds revealed the positive effects of N-surface groups directly linked to the carbon nanotubes surface; SiC foams as structured catalysts presented a better catalytic performance than monoliths. The synthesis methods used for preparing the N-CNTs/SiC composite require the use of relatively low cost and non-toxic raw materials along with lower energy consumption for use in AOP processes. The life cycle study performed in the project also shows significant reduction in environmental impact due to replacement of noble metals.

Sustainability metrics were evaluated for the developed new catalytic processes and benchmarked against conventional (PGM) catalysts. The new ball-milled CNT catalyst outperforms PGM catalysts and clearly has a potential to replace the noble metal catalysts in both studied AOPs. An industrial CWAO plant was designed and on the basis of catalytic performances obtained during the project. The business plan for the AOP shows that the new metal-free catalyst developed in the FREECATS project may be applied in both Catalytic Ozonation (COZ) and Catalytic Wet Air Oxidation (CWAO) with positive cash-flow after two years of activity.

A 10-cell fuel cell stack was produced for demonstrating feasibility for ORR scale-up. The initial performance of the fuel cell MEAs featuring the new catalyst has been significantly improved by changing the technology of layer formation (spraying instead of roll-printing) and introducing pore-forming agents. Both measures improved the mass-transport by increasing the layer porosity. Based on the results, an economic and market application assessment of the new metal-free N-doped nanostructured carbon catalyst for ORR reaction in a PEM fuel cell has been performed. Fuel cell catalyst regarded as PGM replacement has to yield a similar fuel cell performance to PGM to be competitive in the market. The N-CNF catalytic material is still a promising ORR FC catalyst, and its development should be continued. It is likely that combining N-CNF and PGM in the catalysts should lead to significant reduction of PGM content in fuel cell catalysts.

The 6th International Symposium on Carbon for Catalysis, CARBOCAT-VI was hosted in 2014. A large number of publications in prestigious journals have been produced in the project, several with contributions from more than one FREECATS partner, demonstrating excellent collaboration. 6 PhD candidates and 21 post-doctoral fellows have been working in the project, with a good gender balance.

2. Keywords

Metal-free catalysts, replacement of PGMs, oxygen reduction reaction, advanced oxidation processes, dehydrogenation of light alkanes.


FREECATS is primarily aimed at generating new fundamental knowledge and fostering new prospects and frontiers in the field of catalysis for the sustainable production of chemicals and commodities. New tailored metal-free catalytic architectures are designed and fabricated starting from nanoscale building blocks.

The expanding global production and consumption of goods has created serious concern about problems related to the overall demand for critical materials. Heterogeneous catalytic processes are currently essentially based on the use of noble metals. Heterogeneous catalysis is considered as the backbone of the industrial chemistry with an approximate total turnover of about 14 billion US $ in 2007 (environment (44 %), chemistry industry (29 %) and refinery (27 %)) with a continuous growth of the solid catalysts market in the 5-8 %/year range. In 2009, global platinum sales totalled 193 tons with a following repartition: 48 % for jewellery industry, 23 % for the auto-catalyst industry, 18 % for other industries including catalysis, and about 11 % was used as investment.

Carbon nanomaterials have received increasing scientific and industrial interest due to their unique properties, and are becoming increasingly important as catalyst supports in heterogeneous catalysis.

Recent reports have shown the possibility of using this material as metal-free catalyst in several demanding catalytic reactions. It has been demonstrated that N-doped CNT exhibit enhanced catalytic activity compared to traditional platinum catalyst. Recent reports suggest that N-CNTs show comparable electrochemical activity and high stability compared to commercial Pt/C catalysts.


The autocatalyst industry currently represents about one third of the total platinum demand. The transport sector is thus highly dependent on the supply of platinum and


51

other platinum group metals (PGM) (e.g. Rh, Ru). The European Commission has targeted to replace all internal combustion engines (ICE) in the transport sector by 2050. The ICE will most likely be replaced by a portofolio of power-trains where fuel cells are believed to be one of the main contributors.

1 Replacing ICE with

current FC technology will not change the PGM dependency, since the most promising FC technologies for automotive applications (PEM and DM FC) also contain a large amount of noble metals. Thus only replacing the noble metals in the emerging technology can ease the European transport sector PGM dependency. See section 3.1 for details.

The increasing demand for polyolefin products (plastics) causes an annual 4%-4.5% growth rate in ethylene and propene demand in Europe. Increasing demand calls for dedicated plants for olefin production. Acceptable energy efficiency and 50% waste reduction can only be achieved through oxidative routes.

2 The current state of

the art Pt-based catalysts are proven to suffer from competitive disadvantages such as high cost, low selectivity, poor durability and detrimental environmental effects.

Doped carbon nanomaterials have been demonstrated as adequate and even superior alternatives for noble-metal based catalysts both for the ORR reaction and for ODH of light alkanes. The carbon nanomaterials are widely available, corrosion resistant, environmentally acceptable and posess tuneable surface properties.

The third emerging technology where the metal-free carbon nanomaterials have shown to outperform noble metal and rare-earth-based alternatives are in the advanced oxidation processes (AOP). There is an urgent need to exploit novel metal-free catalysts (such as doped CNTs) for AOP applications in order to avoid increasing European noble metal dependency and to secure clean water supply.

5. Objectives

The approach used in FREECATS is outlined in the objectives for each WP:

WP 1: New materials and novel reactor concepts

The objective is to prepare nitrogen and boron-doped nanocarbons using an optimized and scalable procedure giving controllable nitrogen content presenting the following physical properties:

High surface reactivity with an homogeneous dispersion of the

Strong and stable interface with the macrostructured host matrix (SiC and C foam and cordierite monolith)

Efficient heat and electron transfer for the subsequence catalytic applications

WP 2: Hydrodynamics modelling

The main objectives are to

Develop a detailed process model describing reactions, heat and mass transfer, and hydrodynamics with the foam structure as a parameter.

Generate experimental data for model validation, specifically relating to heat transfer, mass transfer and foam structure.

WP 3: Catalytic testing - Optimization

The focus of this WP is to test the performance of the materials prepared in WP1 in the following targeted catalytic reactions:

Oxygen reduction reaction (ORR) for use in proton exchange membrane fuel cells (PEMFC), using N-CNT.

Oxidative dehydrogenation of short chain alkanes (ODH) using P and B doped CNF.

Advanced oxidation processes (AOP) for water and wastewater treatment: catalytic ozonation of organic micropollutants (COZ) and catalytic wet air oxidation (CWAO) using N-CNT.

WP 4: Validation of materials and process in integrated micropilot plant

The objectives of this WP were mainly to

Scale-up the catalyst preparation

Validate performances expected from previous WPs, namely lab scale testing (WP3) coupled with hydrodynamic modelling (WP2).

Generate technical data requested for the benchmarking vs Pt based catalyst in WP5.

WP 5: Technical, Economic and Ecologic assessment for scale-up

The objective was to evaluate sustainability metrics for the developed new catalytic processes and benchmark against conventional catalytic technologies.

WP 6: Dissemination, training and exploitation

The objectives for the dissemination WP were to

Promote the project and disseminate the results to a wider community.

Provide protection for the intellectual property developed within the project.

Provide a communication plan to assist exploitation of the results.


The results from FREECATS will allow more insights about the influence of the dopant loading on the physical and chemical properties of the composite materials, which could be exploited for other applications far beyond the scope of the present project.


52

Efficient catalytic processes require the development of a catalyst with high stability; this is one of the most important parameters in order to reduce the need for the cost-intensive catalyst replacement. The combination of the knowledge generated from the nitrogen loading and the stability of the catalyst under reaction conditions will allow us to perform optimization studies to find the most appropriate catalytic system for the targeted reactions. This fundamental knowledge will be further developed for building metal-free catalysts with applications far beyond the present project.

The understanding of the relationship between the nature of the doped nitrogen species and their catalytic performance, i.e. activity, selectivity and stability, is a key issue in the development of new metal-free catalytic systems and also for their optimization

The data collected from the project will allow us to develop novel structured reactor concepts with well controllable heat and mass transfer and chemical potential gradients with improved selectivity and also to allow a final economic, environmental and energy-efficiency assessment of the system with respect to further industrial development. The combined results obtained from the theoretical simulations and catalytic reactivity will enable one to understand and to control the characteristic of the heat and mass transfer within this structured reactor which can be further transferred to other catalytic processes, i.e. multi-phase reactors for one of the most demanding reactions like the Fischer-Tropsch synthesis reaction.

The project seeks to replace traditional noble metal-based catalysts processes of strategic importance. 3 different cases have been selected:

The Oxygen Reduction Reaction (ORR) mechanism still remains poorly understood. It is expected that the identification of the real mechanism will be helpful for developing a higher-performance catalytic system. Carrying out this reaction with carbon nanostructures, could replace the noble metals used in certain applications like PEMFC (polymer electrolyte membrane fuel cells), which could replace the combustion engines as the EC targets after 2050.

An economic and market application assessment of the new metal-free N-doped nanostructured carbon catalyst for ORR reaction in a PEM fuel cell has been performed using a case of 1 kW backup power unit. Capital and operating expenses combined for the projected lifetime of the system were compared and the assessment clearly shows that the performance and durability of the new catalyst must be improved to become competitive on the market. The key focus of FREECATS is on reduction in the use of resources and replacement of noble metals. The results of our life cycle study indicate

a significant reduction in environmental impacts due to removal of noble metals.

The conversion of alkanes into valuable olefins is of continuing interest with regard to the current technological restructuring of the petrochemical industry. Ethylene and propylene are economically very important commodities in polymer production and the demand of olefins is expected to grow further. FREECATS aims to replace the vanadium and platinum based catalysts with environmentally friendly ODH processes based on carbon nano-structured catalysts. Several consortium members have close collaboration with potential industrial end-users of this technology.

In advanced oxidation processes (AOPs), most of the original ozonation (OZ) and wet oxidation (WO) technologies are based on non-catalytic processes or homogeneous catalysts. The homogeneous catalysts represent a secondary source of pollution and a separation step of the catalyst is required. Pt-based materials and cerium oxide base materials are very active catalysts for these processes. However, besides the associated cost of the metals, deactivation is a major concern. Therefore, the use of carbon materials as catalysts should be considered as a cost/environmental effective option. Based on the strong indications that modified carbon-based catalysts have even larger potential for these reactions and can efficiently replace the metal-based catalysts, the FREECATS consortium has selected AOP as one of the tree cases since this is an emerging technology which may create increasing demand for PGM and rare-earth materials.

The introduction of noble metals on the surface of both CNTs (CNT-O and CNT-BM-M) led to a decrease of their performance as catalysts in ozonation of oxalic acid. In the case of CWAO the CNTs impregnated with platinum exhibit similar phenol removals as correspondent supports, but produce higher amounts of toxic intermediates. The rare earth metal based catalysts are shown to be clearly inferior in both studied AOP processes.

From an industrial point of view, the most viable and challenging industrial process is the CWAO. Regarding the support, the use of foams would represent certain advantages vs monolith supports. As a consequence, reactor design has been described for a CWAO industrial process using beta SiC foams as a support. All the equipment needed to set up this plant and the P&ID have been described. Based on the data obtained a full industrial process of the CWAO technology was done. The project was performed in a 3D CAD software including piping, electrical and pneumatic components. Improvements to optimize the entire process have also been proposed.


53

Sustainability metrics data related to nitrogen-doped carbon nanofibres was performed by University of Cambridge using the data on the synthesis of carbon nanofibres provided by NTNU. In the FREECATS project the main objective was to eliminate noble metals from catalysts and develop new materials containing non-metal dopants, while retaining catalytic activity and selectivity. For environmental assessment of the impact of transition from noble metal to non-noble metal-based catalyst the most important consideration is the removal of all the impacts associated with mining and refining of noble metals and manufacture of noble metal-based catalysts. For this reason within FREECATS a new life cycle assessment case study was developed and compared directly with the previous case study. Here we compare manufacture of Pd-CNF/SMF (Pd deposited on carbon nanofibres, deposited onto sintered metal fibres) with the manufacture of N-CNF (nitrogen-doped carbon nanofibre) catalysts, produced by similar CVD methods. Evaluations were performed using UMBERTO life cycle assessment platform, using EcoInvent database and in-house developed inventories for the species not available in the database. The laboratory-scale composition of CO/NH3/H2 gas feed stream was scaled to the pilot set-up available at NTNU. The same pilot-scale set-up was used for the growth of the CNF/SMF support for the Pd-based catalyst and thus offers a good basis for comparison.

The comparative life cycle assessment performed here is a cradle-to-gate evaluation that was designed to reveal the contribution of raw materials on the environmental impacts from the process. In this case the new LCA case study for the nitrogen doped carbon nanofibres shows the significant reduction in the impacts compared to the metal-based catalyst. This illustrates the significance of eliminating noble metals in catalysts not only from the point of view of cost and availability, but also from the point of view of environmental impact of technology. The up-scaling of catalyst manufacture and first commercial implementation that are likely to follow from the FREECATS project will provide the necessary data for evaluation of in-use and end-of-life environmental performance of the new catalysts.

The key focus of the project is on reduction in resource use and elimination of the use of scarce materials, such as noble metals. This is completely supported by the results of the life cycle study, which shows the significant reduction in environmental impacts due to removal of noble metals.

FREECATS results are disseminated through publications, conference contributions, and our website (www.freecats.eu). In turn these activities will facilitate exchange of information between the FREECATS consortium and potential end-users of the materials and processes – other than those already involved in the

project and with the wider community. A large dissemination event was organised in Trondheim in June 2014: The 6th International Symposium on Carbon for Catalysis, CARBOCAT-VI. An impressive number of publications and presentations have emerged from the project work. Plans have been drawn up to commercially exploit the catalyst technology developed within the project and possible markets, prices and distributors.

Adventech have defined two models for the studied CWAO unit with different capacities. The two chosen capacities take into account the usual industry needs where this technology could be applied. These two models were used in developing a business plan. The business plan includes the assessment of costs of goods sold and materials consumed, the prevision of sales and services provision. Sales and costs of goods were estimated and projected in a timeline of 6 years after the FREECATS project. From the business and financial plan it was possible to conclude that the project is profitable, with positive cash-flow after two years of activity.

The new metal-free catalyst developed under the FREECATS project may be used in both Catalytic Ozonation (COZ) and Catalytic Wet Air Oxidation (CWAO). The main advantages of the use of the FREECATS catalyst are the absence of expensive metals, lower cost and equivalent efficiency. The metal-free structure of the new catalysts avoid the fluctuation on price caused by the frequent variation in price of rare earth metals and PGM commonly used in these kind of conventional catalysts. The treatment of wastewater an end-of-line technology in an industry layout, which means that the wastewater treatment unit is of the last equipment installed in new industrial plants. This leads to long delays between the commercial contract and the effective installation of the treatment unit. The variation in price of conventional metal based catalyst cause cash flow problems and even some significant losses in large installations. The lower cost of the new catalyst associated to equivalent efficiency improves the competitive edge of both AOP’s technologies. The business plan presented in FREECATS is based on two different models of the CWAO technology with different capacities of treatment. The capacities of each model were selected according the previous experience of Adventech in the treatment of industrial wastewater.

In addition, the requirements needed for the new N-CNT catalyst to be competitively commercialised for the FC stack is highlighted.

7. Expected impact

The results will allow more insights about the influence of the dopant loading on the physical and chemical properties of the composite materials, which could be exploited for other applications far beyond the scope of the present project.

http://www.freecats.eu/


54

Efficient catalytic processes require the development of a catalyst with high stability; this is one of the most important parameters in order to reduce the need for the cost-intensive catalyst replacement. The combination of the knowledge generated from the nitrogen loading and the stability of the catalyst under reaction conditions will allow us to perform optimization studies to find the most appropriate catalytic system for the targeted reactions. This fundamental knowledge will be further developed for building metal-free catalysts with applications far beyond the present project.

The understanding of the relationship between the nature of the doped nitrogen species and their catalytic performance, i.e. activity, selectivity and stability, is a key issue in the development of new metal-free catalytic systems and also for their optimization

The data collected from the project will allow us to develop novel structured reactor concepts with well controllable heat and mass transfer and chemical potential gradients with improved selectivity and also to allow a final economic, environmental and energy-efficiency assessment of the system with respect to further industrial development. The combined results obtained from the theoretical simulations and catalytic reactivity will enable one to understand and to control the characteristic of the heat and mass transfer within this structured reactor which can be further transferred to other catalytic processes, i.e. multi-phase reactors for one of the most demanding reactions like the Fischer-Tropsch synthesis reaction.

The Oxygen Reduction Reaction (ORR) mechanism still remains poorly understood. It is expected that the identification of the real mechanism will be helpful for developing a higher-performance catalytic system.

Carrying out this reaction with carbon nanostructures, could replace the noble metals used in certain applications like PEMFC (polymer electrolyte membrane fuel cells), which could replace the combustion engines as the EC targets after 2050.

The conversion of alkanes into valuable olefins is of continuing interest with regard to the current technological restructuring of the petrochemical industry. Ethylene and propylene are economically very important commodities in polymer production and the demand of olefins is expected to grow further. FREECATS aims to replace the vanadium and platinum based catalysts with environmentally friendly ODH processes based on carbon nano-structured catalysts. Several consortium members have close collaboration with potential industrial end-users of this technology.

In advanced oxidation processes (AOPs), most of the original ozonation (OZ) and wet oxidation (WO) technologies are based on non-catalytic processes or homogeneous catalysts. The homogeneous catalysts represent a secondary source of pollution and a separation step of the catalyst is required. Pt-based materials and cerium oxide base materials are very active catalysts for these processes. However, besides the associated cost of the metals, deactivation is a major concern. Therefore, the use of carbon materials as catalysts should be considered as a cost/environmental effective option. Based on the strong indications that modified carbon-based catalysts have even larger potential for these reactions and can efficiently replace the metal-based catalysts, the FREECATS consortium has selected AOP as one of the tree cases since this is an emerging technology which may create increasing demand for PGM and rare-earth materials.

8. Principal investigators involved in the project


Magnus Rønning NTNU Department of Chemical Engineering, N-7491 Trondheim, Norway

[email protected]

Enrique García-Bordejé

CSIC Miguel Luesma Castán 4, 50018 Zaragoza, Spain

[email protected]

Manuel Fernando Ribeiro

Pereira UPORTO Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto, Portugal

[email protected]

Cuong Pham-Huu CNRS LMSPC, UMR 7515 CNRS, Université de Strasbourg, 25, rue Becquerel, 67087 Strasbourg, France

[email protected]

Giuliano Giambastiani CNR Via Madonna del Piano 10 50019, Florence, Italy

[email protected]

Petr Denissenko Warwick University of Warwick Coventry CV4 7AL, UK

[email protected]

Nelly Batail SICAT 20 Place des Halles [email protected]










55

67000 Strasbourg, France

Dmitry Bokach PROTO Prototech AS P.O. Box 6034 Postterminalen NO-5892 Bergen, Norway

[email protected]

Sergio Silva ADVEN Adventech Rua de Fundoes 151 3700-121 Sao Joao da Madeira, Portugal

[email protected]

Alexey Lapkin UCAM Chemical Engineering and Biotechnology Pembroke Street, Cambridge CB2 3RA, UK

[email protected]

9. References

1. http://www.zeroemissionvehicles.eu/ 2. Technology Roadmap Catalysis, The Nedherlands: http://www.viran.nl/Technology%20Roadmap%20Catalysis%20Report.pdf


© 2015, NTNU, Department of Chemical Engineering, N-7491 Trondheim, Norway on behalf of the FREECATS consortium. FREECATS is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




FREECATS and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;






http://www.viran.nl/Technology%20Roadmap%20Catalysis%20Report.pdf


56

Integration of Nanoreactor and multisite CAtalysis for a Sustainable chemical production

Proposal full Name: Integration of Nanoreactor and multisite CAtalysis for a Sustainable chemical production

Acronym: INCAS Call identifier: FP7-NMP-2009-LARGE-3- NMP-2009-3.2-1 - Innovative pathways for

sustainable chemical production Duration: 48 months Start date: 01/10/2010 End date: 30/09/2014 Grant Agreement n°: 245988 Total budget: 8.314.737 € Coordinator: Prof.Gabriele Centi, then prof. Siglinda Perathoner Website: http://www.incasproject.eu/

Consortium List

Benef. no. Beneficiary name and short name (acronym) Country

1 (coord.) INSTM - Consorzio InterUniv. per la Scienza e Tecnologia dei Materiali , Firenze Italy 2 ERIC (European Research Institute for Catalysis), Bruxelles Belgium 3 SHELL (Shell Global Solutions International BV), Amsterdam Netherlands 4 INNOVAL (Innoval Technology Limited), Banbury - Oxfordshire UK 5 SASOL (Sasol Technology UK Ltd), St Andrews UK 6 REPSOL (Technology Centre), Móstoles (Madrid) Spain 7 HYBRID CAT (Hybrid Catalysis BV), Eindhoven Netherlands 8 BAYERTECH (Bayer Techn. Services GmbH, React. Eng. & Catal.), Leverkusen Germany

9 TUM (TU München, Department Chemie), München Germany

10 TUe (Eindhoven Univ. of Techn.), Eindhoven Netherlands

11 CSIC-ITQ (Inst. de Tecnología Química), Valencia Spain

Contents 1. Summary .................................................................................................................................................. 57 2. Keywords ................................................................................................................................................. 57 3. Objectives ................................................................................................................................................ 57 4. Ambition .................................................................................................................................................. 57 5. Expected impact ...................................................................................................................................... 57 6. Contact informations ............................................................................................................................... 58 7. Copyright statement ................................................................................................................................ 59


57

1. Summary

The project concept is to combine nanoreactor technology with multisite solid catalyst design to achieve a safer, cleaner and intensified chemical production. The project ideas are the following: - From micro- to nano-reactors. Actual micro-reactors

have channels of micrometric size. We will develop a new concept based on the use of nanometric size channels.

- Vectorial pathway for multisite catalytic reactions. A limit in cascade (or domino) reactions is that there is no possibility to control the sequence of reactions of transformation of a reactant in a multisite catalyst. The concept of vectorial pathway for multisite catalytic reactions is based on the idea of an ordered sequence of catalytic sites along the axial direction of the channels of a membrane, in order to control the sequence of transformation.

- Dynamic nanoreactor. The concept of dynamic nanoreactor is based on the transient generation of toxic reactants inside the nanoreactor and the immediate conversion, in order to eliminate the storage of these reactants (which is minimized, but not eliminated in on-site or on-demand approaches).

The project concept is that the implementation of innovative and safer pathways for sustainable chemical production requires making a step forward in the development of catalyst-reactor design along the lines indicated above. The project applies above ideas to three reactions of synthesis of large-volume chemicals which are relevant example of innovative pathways for sustainable chemical production: 1. direct synthesis of H2O2, 2. PO synthesis with in-situ generated H2O2 and 3. solvent-free synthesis of DPC with in-situ transient

generation of phosgene. The consortium has a clear industrial leadership, with sixth major companies and two SMEs, and four academic partners, plus the participation of the durable institution of the NoE IDECAT.

2. Keywords

Nanoreactor H2O2, synthesis and use Safer chemical processes Catalyst design for process intensification

3. Objectives

INCAS general objective is to provide new tools for process intensification and enhanced selectivity by catalysis. In addition, the methodologies facilitate safer and more energy-efficient production routes.

Higher-yield, cleaner and more resource-efficient synthesis of large volumes of chemicals will be a benefit not only to the process routes highlighted but also to applications including fine chemical production and environmental clean-up or remediation.

Finally, the project will provide a much-needed framework to analyse the sustainability of various manufacturing processes.

INCAS project concept to promote a sustainable chemistry and more eco-efficient chemical syntheses is to integrate nanoreactor, membrane and advanced catalytic concepts. These concepts are applied to two reactions:

- line 1: the direct synthesis of H2O2 and its in-situ use in propene oxide synthesis;

- line 2: the safer synthesis of diphenylcarbonate (DPC).

4. Ambition

INCAS aim is to increase efficiency with a reduced number of unit operations via process integration.

The concept goes beyond state-of-the-art microreactors that employ microchannels to confine chemical reactions and enhance speed, yield and safety. It exploits nano-size channels and an ordered sequence of catalytic sites along the axial direction of those channels in a membrane providing a vectorial pathway for multi-site catalytic reactions.

The concept applies to reactions (as those indicated above), where cascade processes are not possible. The use of nano-designed catalytic membrane for transient generation of risky intermediates will go beyond the on-site/on-demand production concept for safer operations. Toxic reactants produced as a result of transformations are immediately converted into harmless entities to completely eliminate storage, which is minimised but not eliminated in on-site/on-demand microreactor production concepts.

5. Expected impact

The project final expected impacts are to develop:

i. new approaches in process intensification through a novel concept of multiphase nanoreactor design,

ii. new approaches in multifunctional catalyst design by integrating catalyst and membrane functionalities in an approach aimed at process intensification,

iii. new approaches for intrinsically safer design for reactions involving risky reagents.

The expected final result of the project is to verify the applicability and scalability of new concepts in catalysis


58

related to the development of novel nanoreactors and related catalysts for the two listed target reactions and how they can improve (in these industrially-relevant multistage reactions) process intensification, sustainability (in terms of resource and energy efficiency) and safety of operations.

Functional to this general objective are the development of catalytic nanomembranes, and of the associated novel reactor concepts. Due to challenging objective of developing novel nanoreactor concepts, the demonstration activities in the project are limited to the proof-of-the-concepts.

In line 2 the expected impacts are achieved, with a new type for scaled reactor for intrinsically safer design, new more active and stable catalysts developed, relevant knowledge/catalysts for alternative processes. Further research, however, is needed to exploit these results.

In line 1 the integration between the two stages, even if many different configurations have been explored, has been not proven successfully. However, project results in this line showed new concept of ceramic hollow fiber

reactor which are relevant and innovative for a new process of direct H2O2 synthesis, solving potentially issues of current approaches – autoclave, fixed bed, microreactors – that have inhibited commercial direct H2O2 synthesis. In the integrated process approach, progresses and new advances have been made in membrane reactor modelling, in preparing multicomponent membranes and in understanding role of gradients on performances. These results indicate the need to extend current extimations and consider further alternatives in process design, in particular regarding alternative heat removal solutions, membrane optimization from modeling, alternative reactors as hollow fiber, etc. Some of the results development within the project may also be exploited outside the project specific field. In addition, the research was proven quite successful in having a decisive impact to SMEs involved in the project to overcome general crisis and open new markets. Therefore, research in this line has generated new knowledge and concepts which

translate (later) to innovation.

6. Contact informations

Scientific coordination (INSTM – UdR Messina) Prof. Gabriele Centi initial, from 01/01/2012 prof. Siglinda Perathoner (project coordinator) University of Messina (http://ww2.unime.it/catalysis/) V.le F. Stagno D’Alcontres , 31 Messina 98166, Italy Tel: +39-090-6765609 Fax: +39-090-391518 E-mail: [email protected] Management coordination - ERIC aisbl (operative office in Florence & legal office in Brussels): Dr. Stefano Vannuzzi INSTM (www.instm.it) ERIC (www.eric-aisbl.eu) Via G. Giusti, 9 50121 Firenze, Italy Tel: +39-055-233-8713 (direct line) Fax: +39-055-2480111 E-mail: [email protected] Skype: [email protected] Dr. Serena Orsi ICCOM-CNR (www.iccom.cnr.it) ERIC (www.eric-aisbl.eu) Via Madonna del Piano,10 50019 Sesto Fiorentino (Firenze), Italy Tel: +39-055-5225279 Fax: +39-055-5225203



http://www.iccom.cnr.it/


59

E-mail: [email protected] Skype: serewinnie


© 2015, INSTM – UdR Messina, Italy, on behalf of the INCAS consortium. INCAS is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




INCAS and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




60

LIMPID Nanocomposite Materials for

Photocatalytic Degradation of Pollutants

Proposal full Name: Nanocomposite Materials for Photocatalytic Degradation of Pollutants Acronym: LIMPID Call Identifier: NMP.2012.2.2-6 Photocatalytic materials for depollution Duration: 01/12/2012 – 30/11/2015 Grant Agreement No: 310177 Total Budget: 3,934,377.61 € Coordinator: Dr. Maria Lucia Curri Website: www.limpid.eu

Consortium List


1 Consiglio Nazionale delle Ricerche a) Istituto per i Processi Chimico Fisici CNR IPCF b) Istituto per la Ricerca Sulle Acque CNR IRSA

CNR Italy

2 Universidad del Pais Vasco UPV Spain 3 Fraunhofer Institute FRAUNHOFER Germany 4 Ecole Polytechnique Federale De Lausanne EPFL Switzerland 6 Universiti Teknologi Malaysia UTM Malaysia 6 Chulalongkorn University CU Thailand 7 Mc Gill university MCGILL Canada 8 Johnson Matthey PLC. JM United Kingdom Solvay Specialty Polymers Italy SsPI Italy 10 XYLEM Services GMBH XYLEM SERV Germany 11 ACCIONA Infraestructuras S.A. ACCIONA Spain 12 AQUAKIMIA AQUAKIMIA Malaysia


1. Summary

LIMPID aims at achieving new photocatalytic materials and processes in order to develop novel depollution treatments with enhanced efficiency and applicability.

The main goal of LIMPID is to develop materials and technologies based on the synergic combination of different types of nanoparticles (NPs) into a polymer host to generate innovative nanocomposites, which can be actively applied to the catalytic degradation of

http://www.limpid.eu/


61

pollutants and bacteria, both in air or in aqueous environment. While single component nanocomposites, based, for instance, on TiO2 NPs are already known for their photocatalytic activities, LIMPID aims at going a big step forward and include, into one nanocomposite material, different oxide NPs and metal NPs in order to increase the photocatalytic efficiency and allow the use of solar energy to activate the process. The incorporation of NPs in polymers allows to make available the peculiar nano-object properties and to merge the distinct components into a new original class of catalysts. At the same, time nanocomposite formulation also prevent NP leakage, thus strongly limiting the potential threat associated to dispersion of NPs into the environment.

One of the main challenge of LIMPID is the selection of a suitable host matrix. Therefore, since photocatalysts can destroy the organic materials, proper organic-inorganic hybrids and fluorinated polymers have been selected.

Nanocomposites developed in LIMPID are going to be used as coating materials and products for the catalytic degradation of pollutants and bacteria in water and air, i.e. deposited onto re-usable micro-particles, or in pollutant degradation reactors, and even onto large surfaces, as a coating or paint. Moreover, such new class of nanocomposites will be also exploited for the fabrication of porous membranes for water treatment. In order to fulfil its objectives, the LIMPID consortium has been designed to combine leading industrial partners with research groups coming from Europe, ASEAN Countries and Canada.

2. Keywords

Nanocomposites, oxide nanoparticles, metal, semiconductors, magnetic nanoparticles, photodegradation, organic-inorganic hybrids, fluorinated plymers, visible light photodegradation, emergent pollutants, NOx, membranes, bactericidal action.


Photoactive nanomaterials have got paramount relevance during the last 20 years due to their ability to generate electron-hole pairs, under appropriate irradiation. Such a property can be exploited for potential application in photocatalysis, environmental remediation.

1 Two crucial processes are known to define

the overall catalytic efficiency, namely the competition between the recombination and the trapping of the charge carriers, followed by the competition between the recombination of the trapped carriers and the interfacial charge transfer. Accordingly, improved charge separation and inhibition of charge carrier recombination are essential in enhancing the overall quantum efficiency for interfacial charge transfer.

2

In this scenario semiconducting NPs represent highly innovative materials thank to their extremely high surface active area, the dependence on size of their physical and chemical properties and their possibility to tune their specific characteristics towards catalytic degradation tasks in the depollution process. Finally, the reduced dimensions of nanocatalysts are expected to allow the photogenerated charges to readily migrate at catalyst surface thus reducing the probability of undesired bulk recombination. In particular TiO2 NPs are among the most used photocatalysts due to their chemical stability, commercial availability and excellent catalytic properties. In order to further increase their photocatalytic efficiency, suitable modification of the NP properties can be achieved by means of selective surface treatments and coupling of the semiconductor particles with redox couples or noble metals.

3 In addition, such

systems tend to aggregate, when not suitably functionalized, and they are anyway extremely difficult to recover from the reaction media, thus envisaging a crucial technological problem. The other critical issue is given by drop in performance due to the reduction of the overall active surface area upon immobilization onto substrates. Use of nanosized catalysts is reasonably expected to reduce such losses of performances due to the extremely high surface-to-volume ratio which can greatly increase the density of active sites available for adsorption and catalysis. The fundamental idea in LIMPID is to design, fabricate and exploit nanocomposite materials obtained by synergically combining different types of catalytically active NPs within a polymer for (photo)catalytic degradation of pollutants and bacteria, both in air or aqueous environment.


Inorganic-organic hybrid materials are considered to play a major role in the development of future oriented advanced functional materials. LIMPID supports the research in functional materials by the opportunity to create new smart materials from the combination of inorganic and organic components, and the possibility of their assembly using nanostructured phases. In a time of increasing concern on pollution of the environment, strong focus is placed upon saving resources and on reduction of material usage which automatically also affects the development and usage of multifunctional catalytic coatings, especially in technological applications. LIMPID is going to open new ways for applications of innovative materials by using unique combinations of matrix compositions and NPs as catalytic fillers. Such combinations of functional oxides and metallic NPs and CNT provide original properties and new opportunities for their applications. The incorporation of multiple functions deriving from distinct nanocomponents in a polymer matrix would cope with


62

these inconveniences, at the same time enabling the combination in one functional material of properties deriving from coupling of semiconductor NPs, i.e. TiO2, with metals, i.e. Ag, magnetic oxides, or CNTs. Such peculiarity allows to suitably tune the photocatalytic properties of the final nanocomposite, to extend the range of wavelength useful for photocatalysis to the visible region, to make them re-coverable by using magnetic field or to increase their efficiency by using CNTs. The use of a chemically and mechanically stable host, making promptly accessible the multiple functions deriving from distinct nanocomponents in a polymer matrix, provides a readily applicable material for coatings, reactors, membranes.

Therefore LIMPID proposes a clear progress beyond the state of the art by achieving defined nanocomponents to combine with suitable host polymers, such as hybrid materials

4 and PVDF, in order to define an essential

toolbox for the fabrication of a versatile and technologically viable class of nanocomposites. Modern material science allows to flexibly design and prepare such class of materials for catalytic applications. In particular, one of the major challenge is the carefully design of suitable host matrix, since nanocatalyst can degrade organic matter and thus also any organic host matrix in which the nanoparticles may be embedded.

5. Objectives

LIMPID focuses on the following objectives:

• Synthesis, characterization and functionalization of UV-Vis active TiO2-based photocatalysts, metallic NPs (Ag and Cu) and other functional nano-objects such as CNTs and magnetic NPs (Fe2O3) with tailored size, shape and photocatalytic properties

• Photocatalytic investigation of synergic combinations of TiO2 NPs and metal NPs, CNTs or dopant agents (Ag, Cu, V,N)

• Synthesis and functionalization of polymer hosts (perfluorinated polymer microparticles-latexes, sol-gel siloxane polymers

and polymeric beads)

• Preparation of nanocomposites composed of a polymer/organic-inorganic hybrid matrix and a combination of two or more types of NPs by wet methods (solvent casting, spraying, dip coating)

• Preparation of complex polymer nanocomposites by sputtering of TiO2 NPs and metal NPs (Ag, Cu and Ag/Cu)

• Complete structural and physical-chemical characterization of the novel nanocomposites

• Processing of nanocomposites in the form of membranes, filters, coatings/paints and recoverable catalytically active magnetic beads.

• Use of polymer nanocomposites for photocatalytic degradation under UV and visible/solar light (400-700 nm) of a selected range of organic emergent pollutants in water and in air, including PPCPs, EDCs, VOCs, NOx

• Design and development of water treatment processes based on LIMPID nanocomposites involving (photo)catalytic degradation of emerging pollutants exploiting solar light

• Integration of LIMPID nanocomposites into building façade units, characterization and test of the catalytic and bactericide performance

• Scale up of the materials and processes and investigation the industrial viability of the LIMPID materials and technologies.

Thus, research within LIMPID will provide an enormous amount of information to both enhanced fundamental understanding of structure-property relationships between hybrid film matrices and incorporated functional nanocomponents, ultimately leading to highly innovative products and technologies.


Within LIMPID project a range of UV-Vis active photocatalysts, with tailored size, shape, chemical composition and crystallinity have been designed and prepared. A specific focus has been devoted to the synergistic combination of TiO2 and metallic NPs, low band gap, semi-conductor oxides, carbon nanotubes (CNTs), magnetic NPs and doped NPs, in order to increase the photocatalytic activity and extend the applicability to visible light spectrum.

Figure 1: TiO2 nanorods onto CNT

Distinct routes have been explored for the preparation of the different nanomaterials, namely TiO2, nanorods and nanodots, along with multifunctional heterostructures: TiO2/Ag,TiO2/Fe2O3, TiO2/Fe2O3/Ag, TiO2/CNT, have been achieved by means of colloidal routes. The flame spray pyrolysis process has been used to prepare different doped TiO2 with Fe, Si, Zr and has revealed flexible enough to have access to segregated


63

systems and ZrO2/TiO2, CeO2/TiO2 mixed oxides. Finally, the solvothermal and sol-gel methods have been also studied to prepare Si doped TiO2 and SiO2/TiO2 core/shell NP. These materials have been fully characterized and preliminary tests have assessed their photocatalytic activity by monitoring model dye degradation and/or E. Coli inactivation. As a result a library of well characterized TiO2 based nanostructured materials with enhanced photocatalytic activity has been made available for further incorporation into polymeric matrices, membranes and beads to allow further safe technological applications. Polymer materials, synthesized in the form of processable polymer latexes or dispersible pre-polymers, provide suitable host for embedding the different NPs, and at the same time for sustaining the photocatalytic activity of the NPs therein. Hybrid coatings and waterborne PVDF/acrylic nanocomposites, to be applied on selected substrates, such as stainless steel sheets, on PVDF based membranes, on concrete substrates or as binders in paint formulations have been successfully synthesized by the different beneficiaries by means of sol-gel and emulsion polymerization techniques and proved to be suitable hosts for TiO2 NPs. In addition, pickering latexes synthesized by miniemulsion polymerization stabilized solely by surface modified TiO2 NPs have been successfully produced and showed a uniform distribution of the NP across the film. In general, the hybrid materials synthesized and tested are very promising as polymer matrices for TiO2 NPs for photocatalytic coatings. Starting from the prepared photocatalytic NPs and the suitable polymer host matrix, the preparation of photocatalytically active nanocomposites has been performed. The following different technologies are used to produce these materials:

- wet chemical methods using either organic polymer based or sol-gel derived inorganic-organic hybrid lacquers containing TiO2 NPs to coat surfaces like concrete, stainless steel and fluoro polymer based membranes

- deposition of TiO2 by sputtering techniques onto textiles from polymers like polyethylene and polyesters

- chemical grafting of PMMA films with nano-TiO2

- Fabrication of special structured porous membranes of PVDF with incorporated nano-TiO2.

Both rod-like and spherical TiO2 NPs have been surface modified to facilitate the incorporation into the various liquid matrices for coating applications. Significant photocatalytic activity has been demonstrated in all cases. As an alternative approach, TiO2 has been sputtered, either pure or in combination with other metals and metal oxides, on textiles, in order to obtain photocatalytic surfaces.

Figure 2: E. Coli survival on TiO2/Cu sputtered samples under simulated solar light for multiple cycles

Bactericide effects of the catalytic surfaces have been observed. Direct manufacture of polymer films with inherent photocatalytic properties has been also performed and surface modified PMMA has been made reacting with chemically modified TiO2 to obtain photocatalytically active PMMA. For the applications in filtration technology nano-TiO2 has been incorporated in PVDF based membranes. Membranes have been manufactured from special TiO2 containing hollow fibers. The effective photodegradation of toluene in air, as a model VOC, has been demonstrated for several TiO2 catalysts nanoparticulate hybrid cross-linked sol-gel finally supported on glass under UVA irradiation. TiO2 NPs based catalytic films have demonstrated able to degrade NOx up to 17% within 6h under UVA irradiation. Also self-cleaning of cement-like materials has been assessed by using as a probe system discoloration of methyl-red under sunlight. TiO2, Cu and Cu/TiO2 sputtered on polyester have been tested under actinic/sunlight to inactivate bacteria (E. coli) at the solid-air interface. Remarkably, the total bacterial inactivation was observed for TiO2-polyester after 40 min, for Cu-polyester within 60 min and Cu/TiO2 polyester within 10min. Disinfection has been also observed in the dark for Cu-polyester due to the high oxidation potential of the Cu-NPs. Design of lab-scale photocatalytic reactors has been performed in order to suite various nanocomposite types realized within the project. A 15-L submerged membrane photocatalytic reactor has been specifically customized to study the performance of the prepared PVDF/TiO2 nanocomposite hollow fibre membrane as both photocatalyst and water.

A standard procedure has been established in order to safely compare photo degradation performance of the different types of nanostructured materials developed in the project. Degradation experiments were performed on a carefully designed mixture of 22 pharmaceuticals and personal care products (PPCPs) and endocrine disrupting compounds (EDCs) at low concentration (μg L-1 range) by means of a photocatalysis process based on the developed nanocomposite catalysts.

0 5 10 15 20 25 30 35 40 4510

0

101

102

103

104

105

106

(4)(3)(2)

E.

coli

(CF

U/m

l)

time (min)

(1) 1st cycle

(2) 2nd

cycle

(3) 4th cycle

(4) 8th cycle

(1)


64

Figure 3: Hollow fibre membrane module and TiO2 NPs

containing PVDF membrane

Results demonstrated that nano-sized TiO2 supported on CNTs is much more effective than conventional Degussa P25 in distilled water for degradation of a range of products in the mixtures. Such a material present a quite high specific efficiency when compared to the available standards, being at the same time easy to remove from degradation batch and reusable for a further photocatalytic treatments. Photocatalytic treatments performed on the same set of organic pollutants employed also TiO2 supported on PET and the results demonstrated that nano-sized TiO2 supported on PET is more effective than suspended standard reference catalysts in distilled water for degradation of iopamidol, iopromide, diatrizoic acid, diclofenac and sulfamethoxazole in UV photocatalytic treatments.The technological viability of the investigated multifunctional materials has been investigated highlighting the peculiar processability deriving from the characteristics of the polymeric matrix. The design and fabrication of pilot scale photocatalytic membrane reactor (PMR) has been successfully delivered, and their investigation of the reactor in pollutant degradation is going to be performed.

The use of LED lamps in lab-scale reactors has been evaluated and a prototype based on suitable UV-LED lamp is planned to be developed. Also flow reactors of appropriate size with supported composite nano-sized catalysts are planned to be implemented.

Different possibilities for the application of the LIMPID materials in real work sites within the construction sector, are considered, taking into account both outdoor and indoor applications. The knowledge and results obtained in the project have been disseminated by means a significant number of publications on scientific journals highly relevant in the field, several conference contributions and workshops (http://www.limpid.eu). A project website has been launched and maintained. Among the different dissemination activities it is worth to notice the organization of the "Workshop on

Nanomaterials for Photocatalytic Depollution" that has been held in the frame of the ASEAN-EU STI Days in Bangkok (Thailand) on 22-23 January 2014.

7. Expected impact

In the last decade advances in nanoscale science and engineering suggest that several problems involving water and air quality could greatly benefit by using nanocatalysts, bioactive NPs, nanostructured catalytic membranes and NP enhanced filtration, among other products and processes resulting from the development of nanotechnology. Nanoscience developments facilitate a number of emerging technologies that could work to threat contaminants. In particular nanotechnology derived products that reduce concentration of toxic compounds can assist the attainment of water quality standards and health advisories. Improvement in performance have been strongly correlated to advances in nanotechnology. It is expected that both the technological and economic importance of photocatalytic materials will increase considerably in the future. minimizing the environmental and health impact of the traditional catalysts.

In this respect significant is the impact of LIMPID project towards:

- inexpensive but highly efficient multicomponent photocatalysts, capable of utilizing high portion of solar light

- multifunctional photocatalytic nanocomposites suitable for coating macro and micro surfaces, like concrete walls of open water and facades of buildings, as well as parts and active components of photocatalytic devices and photoreactors

- simple and cost competitive devices that can be promptly recovered from water matrices and at the same time can effectively perform solar light activated photocatalytic treatment of air and water.

The outcome of LIMPID project will not be only able to provide original solution to environmental issues, but also to improve the nvironmental situation in South East Asia, and ensure a transfer of results to geographic regions with similar environmental problems.

On the other hand, for European enterprises in the environmental sector, access to new market could be facilitated. Finally LIMPID will promote the multilateral cooperation in the environmental sector and foster cooperation between environmental industry and science.

http://www.limpid.eu/


65



Maria Lucia

Curri CNR-IPCF c/o Dipartimento di Chimica, via Orabona 4, Bari, 70126, Italy

[email protected]

Giuseppe Mascolo CNR-IRSA Via F. De Blasio, 5 70132 Bari, Italy

[email protected]

Jose Ramon David

Leiza Mecerreyes

UPV

Jose Mari Korta Building, Avenida de Tolosa, 72, 20018 Donostia-San Sebastián, Spain

[email protected] [email protected]

Klaus Rose FRAUNHOFER Friedrichstr. 10a 97082 Würzburg, Germany

[email protected]

Cesar John

Pulgarin Kiwi

EPFL

Route Cantonale

1015 Lausanne vaud Switzerland


Ahmad Fauzi

Ismail UTM 81310 UTM Jonor Bahru, Johor, Malaysia

[email protected]

Piyasan Praserthdam CU 154 Chareonnakorn Road. Klosan, Bankok 10600

[email protected]

Viviane Yargeau MC GILL 845 Rue Sherbrooke O, Montreal, QC H3A 0G4, Canada

[email protected]

Virginie Buche JM Technology Centre , Blounts Court, Sonning Common Reading RG4 9NH, United Kingdom

[email protected]

Alessandro Veneroni SpPI Viale Milano, 78/80 Ospiate, Bollate MI, Italy

[email protected]

Achim Joerg

Ried Mielcke

Xilem Serv. Biebigheimer Straße 12Großostheim, 63762 Germany


Maria Casado ACCIONA Avda. de Europa, 18. Parque Empresarial La Moraleja 28108 Alcobendas, Spain.

[email protected]

Boon Ping Chow AQUAKIMIA Lot 803, Jalan Subang 5, 47610 Subang Java, Selangor Darul Ehsan, Malaysia

[email protected]

9. References

1. T M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev. 95 (1995) 69-96 2. W. Bahnemann, M. Muneer, M.M. Haque, Catal. Today 124 (2007) 133-148 3. P.D. Cozzoli, R. Comparelli, E. Fanizza, M.L. Curri, A. Agostiano, D. Laub, J. Am. Chem. Soc. 126 (2004) 3868-3879

4. K. Rose, S. Dzyadevych, R. Fernández-Lafuente, N. Jaffrezic, G. Kuncová, V. Matejec, P. Scully, Journal of Coatings

Technology and Research 5 (2008) 491-496


© 2015, CNR-IPCF, Dipartimento di Chimica, via Orabona 4, Bari, 70126, Italy ,on behalf of the LIMPID consortium. LIMPID is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:









66


LIMPID and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




67

MEMERE MEthane activation via integrated

MEmbrane Reactors

Proposal full Name: MEthane activation via integrated MEmbrane Reactors Acronym: MEMERE Call Identifier: SPIRE-05-2015:New adaptable catalytic reactor methodologies for

Process Intensification Duration: 01/10/2015 – 30/09/2019 Grant Agreement No: 679933 Total Budget: 5,745,108.75 € Coordinator: Dr. Fausto Gallucci Website: www.Memere-O2.eu ww.spire.com

Consortium List

No Beneficiary Name Short name Country 1 Eindhoven University of Technology TUE The Netherlands

2 Fundación Tecnalia Research and Innovation TECNALIA Spain

3 Flemish Institute for Technological Research VITO Belgium

4 Technical University of Berlin TUB Germany

5 Marion Technologies MARION France

6 HyGear BV HYGEAR The Netherlands

7 Quantis Sàrl QUANTIS Switzerland

8 Finden FINDEN UK

9 Johnson Matthey JM UK

10 Rauschert Heinersdorf-Pressig GmbH RHP Germany

11 Ciaotech s.r.l. (100% PNO Group B.V.) PNO Italy

Contents

1. Summary ...................................................................................................................................................... 68 2. Keywords ..................................................................................................................................................... 68 3. Background – Current state of the art ......................................................................................................... 68 4. Scientific and technological challenges ....................................................................................................... 68 5. Objectives .................................................................................................................................................... 70 6. Expected impact .......................................................................................................................................... 71 7. People involved in the project ..................................................................................................................... 72 8. Copyright statement .................................................................................................................................... 72

http://www.memere-o2.eu/


68

1. Summary

The key objective of the MEMERE project is the design, scale-up and validation of a novel membrane reactor for the direct conversion of methane into ethylene with integrated air separation. The focus of the project will be on the air separation through novel MIEC membranes integrated within a reactor operated at high temperature for OCM allowing integration of different process steps in a single multifunctional unit and achieving significantly higher yields in comparison with the conventional reactor technologies, combined with improved energy efficiency. The results of MEMERE will contribute to the competitiveness of the European process industry in a field (ethylene production) that is an important part of the chemical sector. To achieve this MEMERE aims at developing novel, cheap yet more resistant oxygen selective membranes for efficient air separation and distributive oxygen feeding to the reactor(target module costs < 5000 €/m2). The objective is to give a robust proof of concept and validation of the technology (TRL 5) of the new technology by designing, building, operating and validating a prototype module based on the OCM technology that will be integrated in a mini-plant built in containers. MEMERE technology will deliver direct conversion of methane to C2+ with a reduced energy penalty in a much more effective way (target C2 yields >30%) as compared to currently available techniques contributing to the implementation of the Roadmap and Implementation Plan for process intensification of the SET-Plan. Additionally, as air separation is integrated in an efficient way in the reactor, the MEMERE technology can also be used at small-to-medium scales to convert methane produced in remote areas where conventional technologies cannot be exploited today.

2. Keywords

Catalysts, membranes, Catalytic Membrane Reactors, Oxygen membranes, Oxidative Coupling of Methane.


The combination of the continuous depletion of oil reserves and exploitation of technologies for more difficult extraction reservoirs from one side, and the discovery of non-conventional natural gas resources, the gap between the cost of natural gas and oil has increased dramatically in the last years and is believed to be stable for the coming future, as described by the Annual energy outlook 2014 of EIA

1. With an oil-to-gas

price ratio over 3 (even in this local period of low oil price), it becomes more and more attractive to convert methane to higher hydrocarbons that are conventionally produced by cracking of oil (fractions).

Additionally, a large amount of natural gas is annually wasted as it is produced in remote areas where its conversion with conventional systems or its transportation is uneconomical. One of the most interesting building blocks that can be produced from methane is ethylene, a very important base component for the chemical industry with a production of up to 200 million tons/year (forecast 2020). Current industrial production of ethylene, usually by steam cracking of expensive naphtha, is very energy intensive. It is the most energy consuming process of the chemical industry corresponding with 30% of the total energy consumption of the chemical industry.

A possibility to convert methane to ethylene is the very well-known indirect route, which consists of converting methane to syngas, further conversion of the syngas to higher hydrocarbons (via Fischer Tropsch) and final cracking of the high hydrocarbons to ethylene. The main problems of the indirect route are the large number of process steps and the enormous amount of methane formed as by-product when C2 is the target product, resulting in low C2 yields and a poor energy efficiency of the system.


To obtain its overall goal, MEMERE is divided in different scientific, technical, environmental, economic and exploitation objectives. To achieve these objectives also a number of challenges have to be solved, as elaborated below:

Scientific objectives and work program proposed

S1. The development of novel membrane reactors requires the development of stable and high flux membranes with life-time of at least 5 years. In DEMCAMER

2 we have developed dense tubular oxygen

transport membranes with high flux (see Figure 1) and

perm-selectivity that have been tested up to 2000 hr.

Figure 1. Permeation fluxes for a BSCF hollow fiber membrane with 0.5 mm thickness as a function of helium flow rates and temperature [results from DEMCAMER project].

0 100 200 300 400 500 600 700 800 900

0

1

2

3

4

5

6

J O

2 [S

ml/cm

2/m

in]

He flow [Sml/min]

850 °C

875 °C

900 °C

950 °C

975 °C

1000 °C

A


69

However, before scale-up of these membranes to TRL5 is possible, a few challenges have to be overcome: in particular, how to increase the mechanical stability of these membranes and how to avoid temperature runaway in case of hot spot formation. In MEMERE we will develop capillary membranes with larger thickness/diameter ratio and in parallel further develop the supported membranes by using pore-filled perovskite membranes that will be easier to handle and seal inside the reactor and that will also solve the challenge of a temperature runaway. In fact, as soon as the membrane flux increases due to a temperature hotspot formation, the porous support of the membrane will start to impose a mass transfer limitation to the flux, which cannot increase further thereby circumventing temperature runaways. Thus, the new membranes will also increase the safety of the membrane reactor.

S2. While catalysts for direct conversion of methane to ethylene have been developed over the last 20 years, still many scientific challenges need to be faced before these catalysts can be applied in membrane reactors. From one perspective, OCM catalysts have not, in general been fully characterized in conditions of high methane conversion and C2 yields. In particular, the possible reforming of C2 has been largely ignored in the available reaction kinetic models. MEMERE will solve this problem with a dedicated and detailed kinetic study of the catalysts over a larger range of operating conditions, so that the model will be applicable to membrane reactor operation as well. Furthermore, the membrane reactor will allow much higher yields of ethylene because it allows supplying a large amount of oxygen but in a distributive manner resulting in low oxygen partial pressures. This implies that also the catalyst will see very low partial pressures of oxygen and thus many catalysts for OCM cannot be directly applied in membrane reactors as these would be deactivated by the low oxygen content (reduction of active sites) or by formation of carbonaceous species blocking the active sites. This will be addressed in MEMERE by producing a stable catalyst for low oxygen content and also by designing reactors that allow the low oxygen content to be distributed along the catalyst bed (via structured catalyst or structured reactors).

S3. Detailed reactor models for the membrane reactors are not available. For instance, packed bed membrane reactors for partial oxidation reactions have often been modelled with simplified 1D models. However, the low partial pressure of oxygen at the membrane surface will also imply a large pressure gradient in the radial direction. As far as the fluidized bed membrane reactor is concerned, the available models are based on closure equations originally derived for reactors without inserts. It has been recently demonstrated that permeation through membranes dramatically changes the

hydrodynamics of fluidized beds. Thus the models should be further improved before a final design and scale-up of the reactors is possible. MEMERE will improve the models by adding radial dispersion in packed bed models and correct hydrodynamics closures for fluidized beds and by validating the new models with experimental results under reactive conditions. Additionally we will integrate the newly developed models with Aspen for the correct mass/energy balance of the full plant.

S4. The performance and longevity of the component materials (catalysts, membranes and supports) of the membrane reactors is an important requirement towards their commercial realisation. Especially for high temperature applications, the detailed understanding of the phenomena prevailing in and the interactions between the main reactor components is essential to assess the longevity of these components. In MEMERE we will apply state-of-the-art experimental techniques such as dynamic (synchrotron) X-ray diffraction computed tomography (XRD-CT), and potentially Pair distribution function computed tomography (PDF-CT) under real working conditions. These chemical imaging technique methods are sensitive to both the chemical state and physical form and allow materials/objects to be studied intact.

S5. Design, building and testing of the prototype system to be tested for methane activation in membrane reactors (WP5 and WP6). The design of the reactor requires a careful tuning of the membrane flux and catalytic activity with proper heat management. The membrane reactor module will be able to withstand 1000 °C at a pressure of up to 5 bar to be able to test various OCM scenarios. The aim is to test the concept at the minimum scale required to ensure that the process works for industrially relevant conditions. The flanged design will allow changing the type of oxygen selective membranes designed and produced in the project.

Technical challenges T1. The definition of a specific procedure for the scaling up of the production of the new catalysts for OCM (from TRL3 to TRL5). This will be carried out in WP2. One of the partners, Johnson Matthey (JM) is a leader in catalysts production at low and high volumes ranging from tailored custom made catalysts up to producing conventional catalysts in multi-kg scale. T2. Improve the procedure for the preparation of the new membranes for high temperature oxygen separation at larger scale. In particular, different supports will be tested in WP3 to select the best one in terms of stability, permeance performance of the supported membranes and costs. Additional, thicker self-supported membranes will be also tested.


70

T3. Adequate sealing of the new membranes within a membrane module is a basic requirement for operation and commercial use of the technology. The membranes produced in WP3 will be integrated in the lab scale prototype in WP4 and tested and validated in WP5 and 6. An adequate sealing is required and will be studied in WP4, WP5 and WP6. T4. The optimal integration strategies of the new membrane reactors for methane conversion to C2 through OCM will be assessed in WP7. This taks of the System design and modelling work package, is essential to identify the best configuration to minimize the energy penalty and the cost of the new system and to identify the desirable membrane properties and catalyst activities for each scale of application. The results obtained will be also used in defining guidelines for application of the new technology to different industrial plants.

T5. Environmental LCA of the complete system. This will be carried out in WP8 to identify the environmental performance of the new membrane reactor technology compared with the other technologies available.

5. Objectives

MEMERE will develop new O2 selective (supported) membranes for high temperature air separation and integrate these membranes in a novel membrane reactor for direct conversion of methane to C2. This high temperature membrane reactor module will have an immediate result on the significantly increased C2 yields because of the distributive oxygen feeding and improved temperature control of the reactor, combined with improved overall plant efficiency and costs, because a costly cryogenic air separation unit required in competing technologies is avoided, while downstream separation units will be simplified/reduced in volume or operating costs. This new concept will thus combine the advantages of both high temperature membranes and membrane reactors resulting in a breakthrough technology in the field of methane activation to ethylene. The great advantages of the novel membrane reactor are also accompanied by challenges that the MEMERE consortium will tackle via a combination of detailed experimentation and testing to generate feedback to the materials producers. In particular, the development and testing of novel oxygen transport membranes for application under reactive (reducing) OCM conditions. We will also study how to improve the sealing of the membranes for operation at high temperatures and reducing environments. Additionally, the low oxygen partial pressure that will be very beneficial for OCM, could influence the catalyst stability and thus the operational window of existing catalysts will be mapped

and if needed novel catalysts will be developed in the project. The MEMERE process can also be extended to other partial oxidation processes such as methane autothermal reforming as the challenges of the process and advantages of the novel approach are similar. As such, MEMERE will also investigate (via modelling) the applicability of the new reactor concept to other process technologies thus increasing the impact of the results. The following figure shows the approach of the MEMERE project:

Figure 2. MEMERE approach: from process requirements to actual proof of concept. Summarizing, MEMERE will address the following issues:

Development of novel stable membranes for high temperature applications under reductive atmospheres.

Development of novel catalysts active and stable at the low oxygen partial pressure typical of membrane reactors.

Development of new and more stable sealing methods for the membranes at high temperatures and reductive atmospheres.

The study of interactions of catalysts, membranes and supports under reactive conditions at high temperature.

The study of the effect of impurities in the methane (such as H2S) on stability of catalysts and membranes.

The integration of the new membranes in novel membrane reactors to achieve the integration of separation and reaction in a single unit.

Technical validation of the novel membrane reactor modules at lab scale.

The complete energy analysis of the new MEMERE technology applied to different scenarios.

The validation of the novel membrane at prototype scale (TLR 5)


71

The environmental LCA of the complete chain. The dissemination to stakeholders: the scientific

community to share knowledge. Industrial community to support the exploitation of the project results towards market use.

The exploitation of the results including the definition of a targeted and quantified development roadmap to bring the technology to the market.

6. Expected impact

The MEMERE project promises to solve for the first time the technical and process limits which makes the production of ethylene from methane currently not economical, thus opening new horizons for the production of C2 at high yields (expected from current limit of 25% to potential 35-40%) and much lower costs (expected reduction of 20-30% CAPEX and 20% OPEX, see below), at the same time reducing energy intensity (-50%), emissions (- 60% compared to the current state of the art) and increased flexibility. The MEMERE approach is to address, through process intensification and technologic innovation, two of the highest priorities in the petro-chemical industry, namely energy savings and cost competitiveness40. This will allow for a radical step change towards an increase in competitiveness of the EU process industry at global level, with particular focus on the strategic petrochemical sector, rejuvenating its role and re-establishing its leadership at global level, in line with the SPIRE objectives.

The proposed MEMERE solution will bring relevant impacts at different levels, the main ones being:

- Innovation and Advance of Knowledge: the MEMERE integrated MR system is the result of the combination of breakthrough innovations encompassing new membranes and catalysts, as well as new membrane reactor concepts (OCM-based), overall process intensification and optimization (reduction of steps, optimization of flows and improving of efficiencies and yields), through the concerted collaboration among

major players of the EU scientific community and industry. In doing this, important advancements will be achieved in extremely important knowledge areas related to: material science (e.g. catalysts, materials for membranes, etc.), reactor components and optimization; techno-economic analysis of the industrial-scale process with particular focus on combined effects at different levels (process intensification and optimization); market-monitoring and integrated-process analysis. The innovations and advance of knowledge brought by the project can be also used for future applications in the steam reforming sector and beyond.

- EU Market & Competitiveness: MEMERE aims at bringing to high level jobs, green growth and social progress. The novel system will contribute to the strengthening of the competitiveness and growth of EU companies by developing innovations meeting the needs of EU and global markets, and paving the way for delivering the MEMERE innovation to the markets with a coherent strategy led by prime industrial actors in the sector (part of the MEMERE Team). The project will be able to substantially advance the level of competitiveness of the partners and the EU process industry at large in all the value chain (component manufacturers, materials developers, technology providers, plant owners, downstream product transformers, up to final consumers, etc.). In terms of future market scenarios this means that the EU industry will be able to re-establish high-level content production in EU and eventually reclaim part of industrial production from other competing Regions (especially Asia). This specifically fits and completes the capability of the EU companies who are already the main technology providers for Ethylene production, as well as the syngas-chemical conversion processes.


72



Fausto Gallucci TUE Den Dolech 2, 5612 AZ Eindhoven, The Netherlands

[email protected]

José Luis Viviente TECNALIA Mikeletegi Pasealekua, 2 E-20009, San Sebastián, Spain

[email protected]

Vesna Middelkoop VITO Boeretang 200, 2400 Mol, Belgium

[email protected]

Hamid Reza

Godini TUB Straße des 17. Juni 135, 10623 Berlin, Germany

[email protected]

Delphine MAURY MARION Parc Technologique Delta Sud 09340 VERNIOLLE, France

[email protected]

Leonardo Roses HYGEAR Westervoortsedijk 73, 6802 AV Arnhem, The Netherlands

[email protected]

Arnaud Dauriat QUANTIS Parc Scientifique EPFL, Batiment D 1015 Lausanne, Switzerland

[email protected]

Simon Jacques FINDEN 5 East St Helen Street Abingdon, Oxon, UK

[email protected]

Stephen Poulston JM Blounts Court Road, Sonning Common, Reading, UK

[email protected]

Ulrich Werr RHP Bahnhofstraße 1 96332 Pressig, Germany

[email protected]

Marco Molica Colella PNO Via G. Pacini, 11 20131 – Milano, Italy

[email protected]

8. Refernces

1. Annual Energy Outlook 2014 With Projections to 2040, April 2014, U.S. Energy Information Administration, Office of Integrated and International Energy Analysis, U.S. Department of Energy, Washington, DC 20585. 2. www.demcamer.org


© 2015, TUE, The Netherlands, on behalf of the MEMERE consortium. MEMERE is Spire project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




MEMERE and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;


Statutory fair use and other rights are in no way affected by the above













http://www.demcamer.org/


73


74

NEXT-GEN-CAT Development of NEXT GENeration cost

efficient automotive CATalysts

Proposal full Name: Development of NEXT GENeration cost efficient automotive CATalysts Acronym: NEXT-GEN-CAT Call Identifier: NMP.2011.2.2-4 - Novel materials for replacement of critical materials Duration: 01/02/2012 – 31/01/2016 Grant Agreement No: 280890 Total Budget: 5,615,292 € Coordinator: Dr. Fotios Katsaros Website: www.nextgencat.eu

Consortium List


1 National Center for Scientific Research Demokritos NCSRD Greece 2 Centre National de la Recherché Scientifique CNRS France 3 Monolithos Ltd. MONO Greece 4 Lurederra Technological Centre LURE Spain 6 TP Engineering Ltd. TP UK 6 National Technical University of Athens NTUA Greece 7 JMJ Sp.J. JMJ Poland 8 Tecnología Navarra de Nanoproductos S. L. TECNAN Spain 9 University of Padova UNIPD Italy 10 University of Antwerp UA Belgium 11 Johnson Matthey Plc. JM UK

Contents

1. Summary .......................................................................................................................................... 74 2. Keywords ......................................................................................................................................... 75 3. Background – Current state of the art ............................................................................................. 75 4. Scientific and technological challenges ........................................................................................... 76 5. Objectives ........................................................................................................................................ 76 6. Significant results / exploitable results ........................................................................................... 77 7. Expected impact .............................................................................................................................. 78 9. References ....................................................................................................................................... 79

1. Summary

The main objective of NEXTGENCAT proposal is the development of novel eco-friendly nano-structured automotive catalysts utilizing transition metal nanoparticles (Cu, Ni, Co Zn, Fe etc.) that can partially or completely replace the PGMs. Based on nanotechnology, low cost nanoparticles will be incorporated into different substrates, including advanced ceramics (SiO2,

perovskite etc.) and silicon carbides, for the development of efficient and inexpensive catalysts. The main idea of the proposal is the effective dispersion and the controllable size of the metal nanoparticles into the substrate that will lead to improved performance. To this end a modified polyol process as well as chemical and physical treatment of selected substances will enable the introduction of transition metal nanoparticles on the catalyst substrate precursors via adsorption and ion-

http://www.nextgencat.eu/


75

exchange. The presence of metal ions sorbed on fixed precursor sites will inhibit the agglomeration during heating and final products with very fine particle dispersion and tunable metal content will be obtained. It is expected that the developed catalysts will exhibit increased catalytic performance, even at low temperatures (200-250

oC).

Other key properties of the proposed nanostructured catalysts include: increased thermal stability (avoiding aggregation), improved durability, capability of reuse and recovery of transition metals as well as low health and environmental impact. The properties of the developed nano-structured catalysts will be fine-tuned to fulfill the industry’s needs in terms of processing ability (precursor rheological properties) as well as performance (mechanical and thermal properties, catalytic conversion etc.) in both lab scale and existing prototypes. NEXT-GEN-CAT also targets on the development of a novel method for commercial (large-scale) preparation of nanostructured materials in the monolithic form, providing not only the research platform for their development but also the necessary engineering tools for their effective adaptation in the automotive fields. Besides the performance, special attention will also be given to cost reduction, longevity and low consumption of resources. In addition, recyclability studies will be performed, in order to provide economic routes to obtain and reuse the transition metal nanoparticles. Furthermore, despite the technical and economic factors, health and environmental parameters will also determine the final justification of the optimum replacement material. Finally safety, environmental compatibility and health risk assessment will be conducted for both the nanoparticles and the final products will be conducted.

2. Keywords

Three-Way Catalysts, autocatalysts, transition metal nanoparticles, partial replacement of PGMs, porous substrates, perovskites, Nitrogen oxides, oxidation of CO and Hydrocarbons.


Automotive catalysts designed to detoxify the exhaust gases were implemented in production in the US on vehicles of the model year 1975 and, as we are reaching a full quarter century of their use, there is ample information available to allow us to declare that these devices, which are the principal automotive emission control tools, have proved to be an undoubtable success. Following the positive experience in the US, in short order Japan and thereafter Europe, in 1986, adopted the use of automotive catalysts. The field is driven by environmental issues whose aim is to mitigate the undesirable side effects of modern

lifestyle. Personal mobility is considered an essential part of this lifestyle and has come to be viewed as almost an inalienable right. The national and international regulatory bodies enforce ever more stringent emission rules so that the field of automotive catalysis is perpetually at the very edge of technology. The most common type of catalyst found on gasoline engines is the so called Three-way catalyst (TWC). The term ‘three-way’ underscores the catalysing of three different reactions (oxidation of CO into CO2, oxidation of HC into CO2 and H2O, reduction of NOx into N2, CO2 and H2O). TWCs operate in a closed-loop system including a lambda sensor (also called oxygen sensor) to regulate the air-fuel ratio. On the other hand, vehicles equipped with lean engines, either diesel or gasoline direct injection engines, produce oxygen-rich exhaust, which prevents the reduction of NOx via the “three-way” catalyst commonly used for stoichiometric engines. This means that, providing the temperature is high enough, the oxidation of CO and HC are both strongly favoured, but the reduction of NOx is not. The new combustion and catalyst technologies (Selective Catalytic Reduction –SCR, NOx adsorbers etc.) for lean engines must meet NOx emission standards as well as those for carbon monoxide, hydrocarbons, and particulate matter (soot). For diesel engines, special exhaust filters have eliminated the unsightly plumes of soot emissions from diesel exhaust.

Figure 1. Traditional TWC

The traditional TWC (Figure 1) is composed of an active phase supported on a honeycomb monolith made of cordierite (2MgO0.2Al203.5SiO2) or of PGMs covered by an alumina wash-coat doped with several elements (Ce, La, Ba) to ensure high specific surface area at high temperature and a good dispersion of the active phase

1.

The active phase usually embeds of two metals: platinum and rhodium. A small quantity of rhodium ensures NOx reduction and platinum is responsible for the total oxidation of CO and residual hydrocarbons. The wash-coat is often doped with ceria in different concentrations, which plays an important role in oxygen storage and in improving the dispersion of the noble metals

2. The role of ceria as an oxygen storage

component is manifested in the ability of ceria-


76

containing catalysts to store oxygen under lean operating conditions and to release it under rich conditions by reaction with CO, hydrogen, or hydrocarbons. The working conditions of the exhaust catalysts are very severe due to thermal shocks, humidity in the gas stream (ca. 10% water), and trace impurities poisons such as sulfur, phosphorus, and/or zinc in the exhaust gas. These problems decrease the lifetime of the catalyst through direct poisoning, sintering of the wash-coat, and loss of dispersion of the active phase by sintering of the noble metals. The lifetime of the catalyst is also decreased by loss of the active phase, especially rhodium, because of solid-solid reactions with the wash-coat

3 that result in the

formation of surface or sub-surface spinel4.

The choice of precious metals or platinum group metals (PGMs) as the active catalytic materials in TWC was the result of three factors: (a) only the precious metals had the required activity needed for the removal of the pollutants in the very short residence times dictated by the large volumetric flows of the exhaust in relation to the catalyst size which could be accommodated in the available space; (b) the precious metals were the only catalytic materials with the requisite resistance to poisoning by residual amounts of sulfur oxides in the exhaust; (c) the precious metals were less prone (but not entirely immune) to deactivation by high-temperature interaction with the insulator oxides of Al, Ce, Zr, etc., which constitute the so-called high surface area “washcoat” on which the active catalytic components are dispersed. While initially Pt and Pd in various proportions were used as oxidation catalysts, Rh was introduced with the advent of the three-way catalysts, having considerably better activity than Pt or Pd for the catalytic reduction of the oxides of nitrogen

5-6.


In a short time span, the automotive use of Rh accounted for the bulk of its production in the world and, since it is produced along with Pt at a more or less constant ratio, market demand created sharp price spikes. Pd has historically traded at much lower prices than Pt and Rh. Efforts to substitute Pt and/or Rh by Pd on a large scale were thwarted, however, by technical limitations, namely the increased sensitivity of Pd relative to Pt and Rh to poisoning by lead and sulfur. By the late 1980s, residual lead levels in US unleaded gasoline had dropped to levels at which Pd could be implemented as a substitute for Pt. Ford introduced Pd/Rh catalysts in some of its models in California in 1989, replacing the long-standing use of Pt/Rh in TWC formulations. The use of Pd/Rh catalyst technology quickly spread within the US, spurred on by improvements in techniques for segregating Pd and Rh into separate washcoat layers, this being to prevent the deleterious formation of bimetallic Pd–Rh particles.

Introduction of Pd/Rh catalysts in Europe and other markets has been much slower due to a much more gradual process of eliminating the sale of leaded fuels. Little scope remains to remove platinum from gasoline catalysts, where a switch to palladium has been underway for some time, so development has focused on introducing palladium into diesel catalysts. This substitution of metals in new catalyst technology is expected to continue for the next few years. Since palladium is mined by the same companies as platinum, this shift will not have much influence on the trade relations. Similar efforts have been focused to the possible application of gold in exhaust gas catalyst. The price of gold is currently nearly over the 80% of the price of platinum (2010) and it has increased dramatically due to the economic crisis. Thus, the research efforts have been focused on the replacement of platinum group metals (PGMs) with eco-friendly transition metals. For example, in a study of the influence of transition metal oxides (Zr, Mn, Co, Cu, Mo) on the performance of Pt Rh, Pd/γ-Al2O3 three way catalysts it was shown that the addition of Zr, Mn, Co, and Cu promoters improved the activity of Pt, Rh, Pd/γ-Al2O3 catalyst remarkably for CO, CH and NOx conversion, respectively. In a more recent study from first principles calculation it has been reported that transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-δ (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru)

7. Moreover Li et al., reported

the strong interaction between transition metals and Pd noble metal and concluded that the presence of Fe and Co in the Ce0.67Zr0.33O2 mixed oxide (CZ) obviously decreases the light-off temperature and significantly enhances the catalytic activity of the catalysts. Simultaneously, the windows of activity over Pd/CZFe and Pd/CZCo catalysts become wider compared to that of Pd/CZ

8.

5. Objectives

NEXT-GEN-CAT focuses on the following objectives:

Partial or complete substitution of noble metals used in catalytic converters (40%-60%) without loss of their catalytic efficiency. Several approaches (grafting, assisted impregnation, co-condensation, modified polyol, wet chemistry and flame spray pyrolysis) were applied for the preparation of efficient catalysts based on transition metal nanoparticles

Development of highly efficient supports and monoliths. Various methodologies were used for the effective wash-coating of the developed nanomaterials onto commercially available porous substrates.

Theoretical Nanoscale modeling. The project addressed also the physicochemical phenomena involved in nanostructured catalysts. The aim of the


77

modelling activities within the NEXT-GEN-CAT was to check initially the validity of the current available models and /or to adjust their parameters in order to comply with the experimental data obtained either by the literature or by experiments performed by the consortium. The validated models were also used to predict the behaviour of a catalytic system without the need to perform the experiments. The results of the nanoscale modeling were also combined with process engineering and the optimization studies of the catalytic performance.

Performance evaluation and process engineering. The developed simulated the performance of the catalytic converters and predicted the concentration distribution of the chemical species in the gas and the temperature profile inside the converter as well as the velocity profile.

Large scale production of nanoparticles – Preparation of prototypes. NEXTGENCAT aims at providing novel tools that will facilitate the large-scale production of the most promising materials. Furthermore, real scale prototypes will be developed and validated.

Development of advanced characterization techniques. Conventional as well as “in situ” or operando characterisation techniques (real time X-Ray diffraction) were applied for the physicochemical and structural characterisation of the developed nano-structured catalysts.

Final real-life testing/ evaluation and Life Cycle Assessment. Apart from performance properties, special attention will also be given to cost reduction, longevity and low consumption of resources. In addition, recyclability studies will be performed, in order to provide economic routes to obtain and reuse the transition metal nanoparticles. Finally safety, environmental compatibility and health risk assessment will be conducted for both the nanoparticles and the final products will be conducted.


The consortium determined the requirements for the optimum replacement of noble metals (partial or complete) from materials automotive catalysts. Additionally, a roadmap for the preparation, characterisation of the materials was delivered. Furthermore, rational benchmarking scenarios for the evaluation of the developed catalysts and guidelines for development of prototypes were also developed. Regarding the synthesis of the materials, the participants focused on the preparation transition metal nanoparticles (TMN) based catalysts using various supports and different transition metals. By applying different methodologies (grafting, impregnation, co-

condensation, wet chemistry and flame spray pyrolysis) the consortium enabled the preparation of the materials that can be used towards the replacement (partial or complete) of PGMs from automotive catalysts. More than 300 samples were prepared and thoroughly characterized by a variety of conventional and operando techniques. The developed catalysts ranked according to their catalytic efficiency and preparation procedures and the most promising samples were selected for upscaling. Additionally, selected materials were wash-coated to form small monoliths. Optimisation studies on the preparation routes were also performed. On the topic of modeling activities, the efforts were focused on the preparation of thin perovskite films that can be used as model active surfaces. The developed LFO-based perovskite films characterized by advanced spectroscopic techniques including Raman spectroscopy, LEIS and ToF-SIMS. The obtained results will provide useful data for the later steps of nanoscale modelling. The characterisation results provided useful knowledge about the mechanisms involved and the optimum conditions for the preparations of the materials. Additionally, the excellent dispersion of the metal nanoparticles mainly inside the porous system of the substrates was identified. Furthermore, stability studies on wash coated monoliths revealed that the nanoparticle dispersions were stable up to 10% in weight. Finally, the applied techniques allowed the investigation of the effect of the catalytic reactions (both CO oxidation and NO reduction) on the materials and the overall mechanism involved during catalysis. Regarding the performance evaluation tests, the consortium agreed to a specific protocol that should be applied for all measurements. Additionally the participants “calibrated” their experimental systems by testing the same commercial catalyst provided by JM. Using the abovementioned protocol, more than 220 samples were tested and were categorised according to their efficiency. Several materials, with partial or complete replacement of PGMs, exhibited significant catalytic efficiency to all the tested components of the gas mixture. The partners, using the abovementioned ranking, selected the most promising materials to be up-scaled for the development of the prototypes. Based on the ranking of the materials, a large batch (~2 kg) of the most promising material was synthesised and used for the preparation of the first prototype. Furthermore, the consortium investigated the regeneration of the novel catalyst, after deactivation and the recovery of the transition metals contained in the novel catalysts’ substrate, starting from the recovery of metals from the spent catalytic converters. Dismantling of commercial spent catalytic converters as well as milling of the ceramic honeycombs was also performed. The obtained samples were used for metal recovery studies either by hydrometallurgical or pyrometallurgical treatment. Additionally, Life cycle Analysis (LCA) studies


78

were performed in order to compare the impacts and determine the environmental benefit of replacing the conventional three-way catalyst by the innovative one. Finally, studies on spent catalysts were also performed. On the other hand, the consortium contributed towards the Dissemination/Exploitation of the expected results, by participating to various events, conferences, by presenting scientific posters, papers etc. (http://www.nextgencat.eu/index.php/journal-publications). Key point of the dissemination plan was the launch and the maintenance of the projects’ website. Furthermore the plan for the training activities was defined and initial actions were implemented (exchange of personnel). Finally the consortium identified the communication tools that will enable the effective interaction between the partners as well as the management structures for the smooth implementation of the project.

7. Expected impact

At present, the three-way-catalyst (TWC) is the state-of-the-art technology. Indeed, the latter are capable of simultaneous removal of NOx, CO and residual hydrocarbons CxHy. The current exhaust system includes an oxygen probe dedicated to the regulation of the air/fuel ratio. This also allows the system to alternate quickly between a slightly lean mixture and a very slightly rich mixture. In this manner, the two functions of the catalytic convertor can operate simultaneously, i.e. oxidation of CO and HC into CO2 and water and the reduction of NOx into nitrogen. NEXT-GEN-CAT aims at pushing further the development of high efficiency three way catalysts. By applying a broad spectrum strategy including the preparation and characterisation of several types of nanostructured materials as well as simulation (modelling) and engineering tools, NEXT-GEN-CAT is expected to play active role in the efforts towards minimising polluting car emissions by proposing a

complete family of ready to use, well defined original catalysts. The developed composite materials exhibit a variety of desired properties for catalytic applications, including low cost, excellent dispersion of the metal nanoparticles, tunable size and metal loading, thermal stability and durability. Therefore these materials are perfect candidates to replace partial or complete the RGMs in autocatalysts, depending on their catalytic activity. Their preparation is based on novel, eco-friendly processes minimizing the environmental and health impact of the traditional catalysts. The produced materials can potentially be up-scaled and based on their final properties can be adopted in automotive catalysis sector in short time. It is expected to overcome the current limitations on the applicability of nanomaterials in industry and lead to “smart” innovative industrial processes and contributing to sustainable development and competitiveness of the EU industry. The effective replacement of noble metals with low cost transition metals in the automotive catalysts, will secure the undisturbed supply of the European industry with critical resources, eliminating problems that can be faced in future, due to overexploitation or trade and political restrictions. The presence of copper, cobalt, nickel, iron and zinc in Europe even at small quantities as well as their worldwide occurrence, enable the secure flow of raw materials in our continent, strengthening the leadership of European companies in automotive sector. The proposed innovative materials and processes are expected to contribute to the improvement of the quality of life, especially in the environmental issues. Finally, positive impact is expected on employment (strong need for hiring specialized personnel) and job security in the industrial sectors addressed which happen to be of significant importance for EU.



Fotios Katsaros NCSRD Terma Patriarchou Gregoriou& Neapoleos, Athens, 15310, Greece

[email protected]

Elise Berrier CNRS Unite de Catalyse et de Chimie du Solide (UCCS), Laboratoire de Physique des Lasers, Atomes et Molecules (PhLAM), Université Lille 1, Cité Scientifique, Bâtiment C3 59650 Villeneuve d'Ascq Cedex France

[email protected]

Iakovos Yakoumis MONO 83, Vrilissou Str. 11476 Polygono, Athens, Greece

[email protected]

Tamara Oroz LURE Área Industrial "Perguita", Calle A, nº 1 | 31210 Los Arcos, Spain

[email protected]

http://www.nextgencat.eu/index.php/journal-publications

http://www.nextgencat.eu/index.php/journal-publications






79

Paul Stubbs TP Blythe Park Sandon Road Cresswell, Stoke-on-Trent Staffordshire, UK ST11 9RD

[email protected]

Nikos Papayannakos NTUA School of Chemical Engineering, Iroon Politechniou 9, 157 80, Athens, Greece

[email protected]

Andrzej Puchalski JMJ Kotowiecko - ul. Kościelna 6, 63-460 Nowe Skalmierzyce, Poland

[email protected]

Claudio Fernandez TECNAN Área Industrial "Perguita", Calle A, nº 1 | 31210 Los Arcos, Spain

[email protected]

Antonella Glisenti UNIPD Dipartimento di Scienze Chimiche, Via Marzolo 1 - 35131 Padova, Italy

[email protected]

Pegie Cool UA Laboratory of Adsorption and Catalysis, Department of Chemistry Campus Drie Eiken, Gebouw B, B2.15, Universiteitsplein 1, B-2610 Wilrijk, Belgium

[email protected]

David Thompsett JM Technology Centre, Blounts Court Sonning Common, Reading RG4 9NH, United Kingdom

[email protected]

9. References

1. B. Harrison, A.F. Diwell and C. Hallet, Plat. Met. Rev. 32 (2) (1988) 73

2. M. Funabiki, T. Yamada, and K. Kayano, Catal. Today, 10 (1991) 33 3. T. Wang and L. D. Schmidt, J. Catal., 70 (1981) 187 4. H. C. Yao, H. K. Stepien, H. S. Gandhi, J. Catal., 61 (1980) 547 5. C. Meguerian, E. Hirschberg, F. Rakovsky, US Patent 4,006,103

6. Y.-K. Lui, J.C. Dettling, Society of Automotive Engineers, Paper No. 930249 (1993)

7. A. Gupta, U.V. Waghmare, M.S. Hegde, Chem. Mater., 22 (18)(2010) 5184 8 G. Li, Q. Wang, B. Zhao, R. Zhou, Catal. Today, 158 (3-4) (2010) 38510.


© 2015, NCSRD, Institute of Nanoscience and Nanotechnology, Terma Patriarchou Gregoriou& Neapoleos, Athens, 15310, Greece, on behalf of the NEXT-GEN-CAT consortium. NEXT-GEN-CAT is a Small Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




NEXT-GEN-CAT and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;













80

Innovative Catalytic Technologies & Materials for Next Gas to Liquid Processes

Proposal full Name: Innovative Catalytic Technologies & Materials for Next Gas to Liquid Processes

Acronym: NEXT-GTL Call identifier: FP7-NMP-2008-LARGE-2 NMP-2008-4.0-2 - Catalysts and sustainable

processes to produce liquid fuels from coal and natural gas Duration: 48 months Start date: 01/11/2009 End date: 31/10/2013 Grant Agreement n°: 229183 Total budget: 12.214.925,87 € Coordinator: Prof.Gabriele Centi Website: http://www.next-gtl.eu/

Consortium List

Benef. no. * Beneficiary name and acronym Country

1

(coord.)

CONSORZIO INTERUNIVERSITARIO NAZIONALE PER LA SCIENZA E TECNOLOGIA

DEI MATERIALI (INSTM) (UdR Messina, Bologna) Italy

2 DECHEMA GESELLSCHAFT FUER CHEMISCHE TECHNIK UND BIOTECHNOLOGIE

E.V. (DECHEMA) Germany

3 L'AIR LIQUIDE S.A A DIRECTOIRE ET CONSEIL DE SURVEILLANCE (AIR LIQ) France

4 BASF SE (BASF) Germany

5 BAYER TECHNOLOGY SERVICES GMBH (BAYER) Germany

6 ENI S.p.A. (ENI) Italy

7 ACKTAR LTD. (AKTAR) Israel

8 TECHNIP KTI SPA (TP-KTI) Italy

9 ECOTECH Ltd (ECOTECH) Greece

10 IPEL S.A. (IPEL) Greece

11 Parametric Optimization Solutions Limited (PAROS) U.K.

12 STIFTELSEN SINTEF (SINTEF) Norwey

13 CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS) France

14 CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS (CSIC) Spain

15 J. HEYROVSKY INSTITUTE OF PHYSICAL CHEMISTRY - ACADEMY OF SCIENCES OF

THE CZECH REPUBLIC PUBLIC RESEARCH INSTITUTION (HIPC) Czech Rep.

16 UNIVERSITAET STUTTGART (UNIST) Germany

17 INSTYTUT KATALIZY FIZYKOCHEMII POWIERZCHNI, POLSKA AKADEMIA NAUK

(ICSC) Poland

18 GOTTFRIED WILHELM LEIBNIZ UNIVERSITAET HANNOVER (LUH) Germany


81

19 NATIONAL CENTER FOR SCIENTIFIC RESEARCH "DEMOKRITOS" (NCSRD) Greece

20 TECHNISCHE UNIVERSITEIT EINDHOVEN (TUe) Netherlands

21 TECHNISCHE UNIVERSITAET MUENCHEN (TUM) Germany

22 UNIVERSITEIT GENT (UG-CPTC) Belgium

23 TECHNISCHE UNIVERSITEIT DELFT (TUDelf) Netherlands

Contents 1. Summary .................................................................................................................................................. 81 2. Keywords ................................................................................................................................................. 81 3. Objectives ................................................................................................................................................ 81 4. Ambition .................................................................................................................................................. 82 5. Expected impact ...................................................................................................................................... 82 6. Contact informations ............................................................................................................................... 82 7. Copyright statement ................................................................................................................................ 83

1. Summary

NEXT-GTL addresses main cost drivers and technical barriers of the conventional gas-to-liquid (GTL) process. The main objectives are to: - reduce the cost and energy consumption of syngas

production, and overcome the stability related barriers in using catalysts in this process;

- develop GTL technologies suitable for small-medium scale productions in remote NG areas;

- develop processes for producing liquid fuels which can be blended in both gasoline and diesel pools, or which may be used for chemical purposes.

Accordingly, three development lines are followed in this project: - Line 1: Advanced, low temperature route for catalytic

syngas formation from natural gas, in which reaction steps are integrated with different types of membranes for O2, H2 and CO2 separation.

- Line 2: Direct low temperature catalytic conversion of methane to methanol / DME, utilising several innovative concepts to overcome the drawbacks of previous approaches.

- Line 3: Direct catalytic conversion of methane to aromatics under non-oxidative conditions followed by upgrading of the products by alkylation with ethane / propane.

Line 1 aims at the improvement of the current GTL conversion chain by developing an improved technology for the most costly and energy-intensive step of syngas production.

Lines 2 and 3 address alternative direct routes (i.e. not via syngas) of methane to liquid conversion to

transportable fuels, suitable for both gasoline and diesel pools, and potentially for chemical uses; both oxidative and non-oxidative routes for methane conversion are explored to compare the two alternatives.

The consortium partners comprise leading companies and research groups, with core competences in catalysis, membranes and reaction engineering, to ensure strong interdisciplinary work at the different stages of theory / modelling, material development and characterisation, testing, material / reactor engineering, and process development.

2. Keywords

Nanoreactor H2O2, synthesis and use Safer chemical processes Catalyst design for process intensification

3. Objectives

INCAS general objective is to provide new tools for process intensification and enhanced selectivity by catalysis. In addition, the methodologies facilitate safer and more energy-efficient production routes.

Higher-yield, cleaner and more resource-efficient synthesis of large volumes of chemicals will be a benefit not only to the process routes highlighted but also to applications including fine chemical production and environmental clean-up or remediation.

Finally, the project will provide a much-needed framework to analyse the sustainability of various manufacturing processes.

INCAS project concept to promote a sustainable chemistry and more eco-efficient chemical syntheses is to integrate nanoreactor, membrane and advanced catalytic concepts. These concepts are applied to two


82

reactions:

- line 1: the direct synthesis of H2O2 and its in-situ use in propene oxide synthesis;

- line 2: the safer synthesis of diphenylcarbonate (DPC).

4. Ambition

INCAS aim is to increase efficiency with a reduced number of unit operations via process integration.

The concept goes beyond state-of-the-art microreactors that employ microchannels to confine chemical reactions and enhance speed, yield and safety. It exploits nano-size channels and an ordered sequence of catalytic sites along the axial direction of those channels in a membrane providing a vectorial pathway for multi-site catalytic reactions.

The concept applies to reactions (as those indicated above), where cascade processes are not possible. The use of nano-designed catalytic membrane for transient generation of risky intermediates will go beyond the on-site/on-demand production concept for safer operations. Toxic reactants produced as a result of transformations are immediately converted into harmless entities to completely eliminate storage, which is minimised but not eliminated in on-site/on-demand microreactor production concepts.

5. Expected impact

The project final expected impacts are to develop:

i. new approaches in process intensification through a novel concept of multiphase nanoreactor design,

ii. new approaches in multifunctional catalyst design by integrating catalyst and membrane functionalities in an approach aimed at process intensification,

iii. new approaches for intrinsically safer design for reactions involving risky reagents.

The expected final result of the project is to verify the applicability and scalability of new concepts in catalysis related to the development of novel nanoreactors and

related catalysts for the two listed target reactions and how they can improve (in these industrially-relevant multistage reactions) process intensification, sustainability (in terms of resource and energy efficiency) and safety of operations.

Functional to this general objective are the development of catalytic nanomembranes, and of the associated novel reactor concepts. Due to challenging objective of developing novel nanoreactor concepts, the demonstration activities in the project are limited to the proof-of-the-concepts.

In line 2 the expected impacts are achieved, with a new type for scaled reactor for intrinsically safer design, new more active and stable catalysts developed, relevant knowledge/catalysts for alternative processes. Further research, however, is needed to exploit these results.

In line 1 the integration between the two stages, even if many different configurations have been explored, has been not proven successfully. However, project results in this line showed new concept of ceramic hollow fiber reactor which are relevant and innovative for a new process of direct H2O2 synthesis, solving potentially issues of current approaches – autoclave, fixed bed, microreactors – that have inhibited commercial direct H2O2 synthesis. In the integrated process approach, progresses and new advances have been made in membrane reactor modelling, in preparing multicomponent membranes and in understanding role of gradients on performances. These results indicate the need to extend current extimations and consider further alternatives in process design, in particular regarding alternative heat removal solutions, membrane optimization from modeling, alternative reactors as hollow fiber, etc. Some of the results development within the project may also be exploited outside the project specific field. In addition, the research was proven quite successful in having a decisive impact to SMEs involved in the project to overcome general crisis and open new markets. Therefore, research in this line has generated new knowledge and concepts which translate (later) to innovation.


Scientific coordination (INSTM – UdR Messina) Prof. Gabriele Centi initial, from 01/01/2012 prof. Siglinda Perathoner (project coordinator) University of Messina (http://ww2.unime.it/catalysis/) V.le F. Stagno D’Alcontres , 31 Messina 98166, Italy Tel: +39-090-6765609 Fax: +39-090-391518 E-mail: [email protected]



83

Management coordination - ERIC aisbl (operative office in Florence & legal office in Brussels): Dr. Stefano Vannuzzi INSTM (www.instm.it) ERIC (www.eric-aisbl.eu) Via G. Giusti, 9 50121 Firenze, Italy Tel: +39-055-233-8713 (direct line) Fax: +39-055-2480111 E-mail: [email protected] Skype: [email protected] Dr. Serena Orsi ICCOM-CNR (www.iccom.cnr.it) ERIC (www.eric-aisbl.eu) Via Madonna del Piano,10 50019 Sesto Fiorentino (Firenze), Italy Tel: +39-055-5225279 Fax: +39-055-5225203 E-mail: [email protected] Skype: serewinnie


© 2015, CONSORZIO INTERUNIVERSITARIO NAZIONALE PER LA SCIENZA E TECNOLOGIA DEI MATERIALI (INSTM) (UdR Messina, Bologna),Italy, on behalf of the NEXT-GTL consortium. NEXT-GTL is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




NEXT-GTL and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;






84

NOVACAM NOVel cheap and Abundant Materials for

catalytic biomass conversion

Proposal full Name: NOVel cheap and Abundant Materials for catalytic biomass conversion Acronym: NOVACAM Call Identifier: FP7-NMP-2013-EU-Japan: NMP.2013.4.1-1 - Development of new

materials for the substitution of critical metals Duration: 01/09/2013 - 28/02/2017 Grant Agreement No: 604319 Total Budget: 2,415,573.20 € Coordinator: Prof. dr. ir. Emiel Hensen Website: www.novacam.eu

Consortium List


1 Technische Universiteit Eindhoven TU/e Netherlands 2 Cardiff University CU UK 3 Agencia Estatal Consejo Superior De Investigaciones

Cientificas CSIC Spain

4 Chemistry Innovation Limited/ Knowledge Transfer Network CIKTN/KTN UK 5 Hokkaido University/Kanagawa University CRC/KAN Japan 6 Tokyo Institute of Technology TIT Japan 7 Chiba University CHU Japan

Partners 5-7 are associated with the Japanese consortium funded by the Japan Science and Technology Agency.

Contents

1. Summary .......................................................................................................................................... 84 2. Keywords ......................................................................................................................................... 85 3. Background – Current state of the art ............................................................................................. 85 4. Scientific and technological challenges ........................................................................................... 85 5. Objectives ........................................................................................................................................ 87 6. Expected impact .............................................................................................................................. 87 7. People involved in the project ......................................................................................................... 88 8. Copyright statement ........................................................................................................................ 89

1. Summary

NOVACAM addresses the development of novel technology to enable the substitution of critical metals inindustrial catalysts (call objective). The project will aim to develop catalysts using non-critical elements for the conversion of biomass to chemicals and fuels. Catalysts are one of the six major uses of critical metals that are produced as byproducts of mining of primary metals, e.g. platinum group metals and lanthanides. Many industrial

heterogeneous catalysts have been developed empirically, such that the role of these critical metals in affecting catalyst performance is not clearly understood. NOVACAM will develop innovative catalysts by applying a “catalysis by design” approach, integrating the complete chain of knowledge from fundamental research to proof of concept. The prototype catalysts will be benchmarked against current catalyst technology. Industrial use of biomass is at an early stage and presents an opportunity to develop the next generation


85

of cheap and abundant catalysts. The main objectives of the project are (i) to understand by a “catalysis by design” approach the requirements for inorganic catalyst systems to speed up elementary reaction steps and valorise biomass with a focus on conversion of cellulose into fuels and chemicals; (ii) using these nanoscale insights to develop novel catalysts based on abundant elements for the conversion of biomass and (iii) to develop three proof of concept studies at laboratory scale to convert cellulose/sugar feedstock into fuels and chemicals - specific attention will be paid to catalyst robustness. In this way, the extensive knowledge base acquired in catalysis research will be employed to design novel inorganic catalytic systems. The project will be carried out with a partner consortium in Japan with complementary expertise in the field of innovative catalyst research. An industrial advisory committee will be integrated into the project in order to maximise exploitability of the project results.

2. Keywords

Replacement Critical Metals, Catalysis, Chemical Industry, Biomass, Cellulose, Nanoscience, Design, Synthesis, Characterisation, Reactions.


NOVACAM addresses the development of novel technology to enable the substitution of critical metals in industrial catalysts. The project will aim to develop catalysts using non-critical elements for the conversion of biomass to chemicals and fuels. Catalysts for petrochemical processing are one of the six major uses of critical metals that are produced as by-products of mining of other primary metals, e.g. platinum group metals and lanthanides. The upcoming change in feedstock will require new catalysts, and the project aims to take advantage of this change to introduce new catalyst technology which is risk free as far as metal supply is concerned.

The overarching objective of the project is to construct an innovative science base of novel catalytic technologies to enable the conversion of lignocellulosic biomass to useful and valuable organic chemicals, polymers, transportation and heating fuels. The novel catalytic technologies would completely eliminate the use of critical raw materials for these processes, and would have low environmental impacts. The underlying science will develop and demonstrate new principles for achieving excellent catalytic properties by control and manipulation of the composition and structure of solid catalysts made from abundant materials.

These objectives follow from consideration of the technical challenges posed by important societal needs. First is the necessity of identifying technologies which permit the replacement of fossil sources (oil, natural gas,

coal) as feedstocks for chemicals and fuels is a consequence of concerns about greenhouse cases and about depletion of resources.

Currently, about 200 million tons of fossil materials are converted annually into chemicals: this figure is based on the annual production of basic chemicals. They are converted through a group of basic chemicals and key intermediates into the 40,000 to 100,000 useful chemicals and materials, which meet the everyday needs of people all over the world. The scale of petrochemical industries is not that different from the scale of the industries producing sugar and sugar derivatives. In volume terms, then, the challenge is smaller than might be expected.

While biomass in all its forms is potentially available as a renewable feedstock for chemicals, NOVACAM focuses in this project on the use of lignocellulose. Potentially this can be converted into a whole range of existing useful chemicals and fuels, and also into new and different chemicals as better alternatives. It has the great benefit that starting from lignocellulose it will be possible to supply chemicals without adversely impacting land and other resources which are needed for food production.

The generic molecular challenge of switching to biomass is that of reducing the proportion of oxygen atoms in the product molecules below the C(H2O)n composition of carbohydrates. This is completely different from the chemistry needed for hydrocarbon feedstocks. Novel catalytic technologies will be key innovation in addressing this task, not just for the chemistry but also because the spectrum of impurities in the feeds will be very different from those found in petrochemical processing, changing for example catalyst poisoning problems.


NOVACAM takes on the challenge of creating new catalytic technologies for biomass conversion without relying on critical metals. This is a real opportunity for step change innovation. The rare earths and platinum group metals, which in the EU report on Critical Raw Materials were found to have the highest concern over security of supply, are widely used in many types of catalytic processes in petrochemical production and downstream conversion to high value products: in many cases they are the default option for catalyst design. The purpose of NOVACAM is to establish the basis for a knowledge based catalytic technology which can introduce a catalytic technology based on carefully designed oxides and base metals. While the specific process options researched by NOVACAM will be important, it is the contribution to a change in thinking about what materials can be used as catalysts that may produce the biggest impact.


86

Since industrial use of biomass for chemicals production is at an early stage, it is an ideal situation for innovative new technology to be taken up. It is much easier to introduce a new technology to meet a new need than it is to replace an existing process option. The proposed research to develop novel catalysts for these applications based on a sound fundamental footing is thus very timely. NOVACAM seeks to create a first specially designed generation of catalysts to power the uptake of technology for converting biomass to chemicals.

The overarching research objective described above

contains within it three subsidiary objectives:

• To understand, by a “catalysis by design” approach, the requirements for inorganic catalyst systems to accelerate the elementary reaction steps needed to depolymerize, deoxygenate, isomerise and couple biomass constituents with a focus on cellulose conversion into fuels and chemicals

• To develop based on these nanoscale insights novel functional materials composed of cheap and abundant elements for the catalytic upgrading of biomass

• To develop three proofs of concepts at the laboratory scale to upgrade cellulose/sugar feedstocks to fuels and chemicals using catalysts based on non-critical elements with specific attention for catalyst robustness

The catalysis by design approach NOVACAM shall employ to address these challenging and exciting objectives will integrate the complete chain of knowledge from fundamental concepts (theoretical studies of reaction mechanism and in-situ spectroscopic studies), via advanced synthesis protocols involving self-assembly approaches to complete laboratory proof of concept. In this way, the extensive knowledge base acquired in the last decades in catalysis research including tools and techniques will be employed to design novel inorganic catalytic systems.

The research work program in NOVACAM is divided in two phases. In the first phase covering the first half of the project, fundamental studies will be employed to study the mechanistic and active site requirements for the underlying chemistry to valorise biomass. NOVACAM focuses on transformations by highly selective catalysts in order to retain as much of the functionalities which Nature has built into the final product molecules. To this purpose, modern tools such as advanced materials characterisation, quantum-chemical modeling of the surface reaction processes and modern synthesis approaches will be employed.

The second phase of the project covers the use of these insights to develop three proofs of concept at the laboratory scale: Given its size and the goal to arrive at proof of concept on the laboratory scale, NOVACAM will

focus on the valorisation of cellulose and carbohydrates, which are the dominant part of lignocellulosic (2nd generation) biomass. It is envisaged at this time of writing the application that the three systems will be as follows:

• The valeric platform – this work comprises the development of novel catalytic routes from cellulose to γ-valerolactone, which is a platform for the production of transportation fuels. The objective is to replace state of the art precious metal based catalysts by cheaper metals and to decrease the number of steps in the upgrading process of cellulose by introducing novel chemistry.

• Chemocatalytic glycolysis – to replace the conventional acid-catalyzed cellulose depolymerization and glucose dehydration approaches and the more promising ones using a critical (and toxic) metal as chromium, novel approaches based on cheap metal oxides and well-defined Lewis acid sites in nanostrucured porous zeolites will be the target. The target product is lactic acid, the monomer for the biodegradable polymer PLA, and a possible intermediate to useful chemicals such as acrylic acids. A high risk, high reward task will be to develop decarboxylation chemistry (lactic acid to ethanol), by which a synthetic chemocatalytic glycolysis route would become available which can potentially replace the slow enzymatic process and create a possibility for the direct ethanol synthesis from cellulosic biomass.

• Aqueous phase reforming – This process produces hydrogen from biomass-derived oxygenated compounds such as glycerol and sugars. It is unique in that the reforming is done in the liquid phase, so there is no need to vaporize water representing energy savings and the possibility to convert sugars. The state of the art catalysts are precious metal nanoparticles. In this project, NOVACAM targets their replacement by cheaper metals, whose chemical state and nanoparticle size will be optimized to maximize hydrogen production.

Catalyst activity, stability and recyclability are critical issues to be addressed as well in NOVACAM. The process routes will be benchmarked against state of the art technologies, which are often the easy choice but involve the use of critical metals.

The consortium partners comprise leading catalysis research groups in the EU, with core competences in catalyst synthesis, mechanistic research involving theoretical/modeling studies, advanced characterisation and catalyst performance evaluation in biomass conversion. The project will be carried out with a partner consortium of Japanese scientists experienced in the field of catalytic biomass conversion and also following the innovative “catalysis by design” approach.

The project is structured in core activities (two main work packages, one exploring the basic chemistry using


87

novel catalysts based on non-critical metals and one developing the proofs of concept), a set of complementary activities related to dissemination of the results, networking, training and education and awareness building for young researchers involved in the project is embedded in a third work package, and the project management and coordination activities are included in the fourth work package. An Industrial Advisory Committee will act as a sounding board to the cooperation and advise on progress of the activities and their exploitability, the industrial relevance and impact of the research effort and where needed also to test successful proven laboratory concept at a larger scale.

Effective and timely dissemination constitutes a second broad objective for the project, so that it can inform and influence the individuals and organisations for whom this area of technology is important. In KTN NOVACAM has a partner specializing in technology strategy and technology translation in this particular area. It is leading the EU CRM_InnoNet project, and is very well connected with leading EU and international players

A key aspect of the NOVACAM concept is recruitment of bright young researchers, and how the project will add to their training to develop their skills and personal qualities. They will receive excellent research training by participating in a project which will move rapidly from exploratory research to proof of concept. Intercontinental collaboration will provide a multicultural experience. Each researcher will take part in two international exchange visits for research work, one to another local partner, and one intercontinental. They will participate in project events, including the final dissemination conference involving leaders from industry and government. Beyond this the project will establish a specific training program based on the principles of the Marie Curie Initial Training Networks; much of this will be delivered through webinars.

5. Objectives

The project concept shows several challenges, but consistent with the ambitious request of the call for a scientific and technological breakthrough: (1) Development of highly performing products (“catalysts”) by rational design methods. (2) The use of combinations of theoretical and experimental methods to come to design rules for the next generation of functional materials for catalytic biomass conversion. (3) Synthesis of structured catalysts, e.g. zeolites, nanostructured or with novel pore topologies and functionalised with well-defined isolated reaction sites and also metal oxides with metal cations in well-defined reaction environments.

(4) Define the necessary combination of catalytic functionalities in one material to control the reaction direction for the upgrading of highly complex biomass. (5) Exploration how the designed nanoscopic reactivity affects the behavior at the macroscopic scale by test reactions and development of proofs of concept at the laboratory scale and through interaction with industry to explore viability for novel processes. The chosen reactions are of great industrial relevance (all on a projected multi-million tons scale) and a relevant example of innovative pathways for sustainable chemicals and fuels production. The developed catalysts will also have potential use in a broader range of industrial applications. The very nature of NOVACAM will also lead to further deepening of the “catalysis by design” approach. In accordance with the call, the project has a strong coordination to a Japanese consortium. The collaborative actions are evident from the work package descriptions in this proposal. The NOVACAM project also educates and trains researchers at the early stages of their career by hiring PhD students and young postdoctoral research fellows and giving them the best possible training in the field of catalysis.

6. Expected impact

NOVACAM occupies a strong position linking two of the key industrial sectors underpinning any future sustainable society, namely energy and chemicals. They meet in the biorefinery, the vehicle which will convert biomass into fuels, energy, and a mix of added value chemical products. Many different types of biorefinery are being postulated and explored as possible components of the future sustainable society, but they share the common features that the production of added value chemicals is essential for successful biorefinery economics, and that catalytic technologies are essential to provide conversion processes that are efficient in terms of energy consumption and use of materials. Since this is a field where technology development is in its infancy, NOVACAM is positioned not just to provide alternatives to existing technology but to facilitate de novo a whole technology area based on abundant raw materials.

The new knowledge gained in this project will provide the basis for the design of novel and innovative catalytic technologies which do not require critical raw materials to generate catalytic properties, and which will provide a basis for an essential part of biorefinery operations. The adoption of these technologies will provide future-proofing for the biorefineries using them, reducing the risk to their operations of changes due to interruption of supply of essential process components, or escalations in price. The new knowledge about key process concepts which NOVACAM provides should therefore facilitate the more rapid take-up of technologies for converting biomass to chemicals.


88

The second aspect of the impact deriving from the knowledge generated in this project will be on catalytic technology itself. By establishing a basis in structure and mechanism for the predicting catalytic properties and designing catalysts, NOVACAM will help to generate a catalyst industry which is much less reliant on critical raw materials such as rare earths and platinum group metals, and which makes far better use of abundant materials. It will also make a significant contribution to the strategic thinking about rational design of catalysts, which will work its way through the industry into improved performance of chemical manufacturing processes and shorter development lead times.

While the specific process options researched by NOVACAM will be important, it is the contribution to a change in thinking about what materials can be used as catalysts that may produce the biggest impact. The development of this rational, knowledge based approach to catalyst design using abundant materials marks a significant change for the research process of discovering new catalysts. Catalytic technology is about 200 years old, and throughout its history there has been a reliance on empiricism to find new catalysts. The platinum group metals in particular are known to have good catalytic activity and selectivity, and in many investigations the material of first resort will be a platinum group metal: this was for instance Fritz Haber’s approach in 1909 to prove the concept of the ammonia fixation process, and it took an intensive empirical study by Karl Mittasch, ultimately involving 20,000 candidate materials, to find by serendipity a cost-effective alternative.

The adoption of a rational approach to catalyst design and discovery using abundant materials marks a significant cultural change for the catalyst industry. The

catalyst market is relatively small (~ 10 billion €), catalysts enable the production of ~85% of chemical processes (~ 1500 billion €). Outside the specific world of chemicals, it has been estimated that catalytic technologies are essential for the processes, products and services which contribute over 40% of GDP. NOVACAM aims to make a significant impact by helping to increase the raw material security for this essential underpinning technology. Thus, higher prices of critical elements in catalysts may have a very strong negative impact on prices of nearly all products used in modern society. Catalysts represent a small proportion of the total sales of critical metals, and are therefore very much at risk of disproportionately large price increases in periods of shortage.

The practical and economic importance of the project for its immediately target technologies for making chemicals from biomass can be judged from the expected development of biorefineries, which by 2050 will be processing annually some 25 billion tons of biomass, 3 million tons of which will be transformed into basic and speciality chemicals. NOVACAM’s impact is potentially amplified by being involved at the very start of these developments.

The change to a catalytic technology which uses metals widely available within Europe rather than imported metals will only have positive benefits for European industry. It will not affect catalyst makers, since their businesses will adapt easily to supplying the new technology. Moreover, it will put European catalyst makers at the forefront of this new sustainable technology, at a time when US businesses are preoccupied with catalyst technology for converting natural gas into chemicals.



Emiel Hensen TU/e Eindhoven University of Technology Het Kranenveld 14, Helix STW 3.35, 5612 AP Eindhoven, The Netherlands

[email protected]

Graham Hutchings CU Cardiff University Cardiff CF10 3XQ, UK

[email protected]

Avelino Corma Canos CSIC CSIC Av. de los Naranjos, s/n 46022, Valencia, Spain

[email protected]

Claire Claessen KTN The Knowledge Transfer Network Bailey House, 4 – 10 Barttelot Road Horsham,West Sussex, RH12 1DQ, UK

[email protected]

Wataru Ueda CRC/KAN Kanagawa University 3-27-1, Rokkakubashi, Kanagawa-ku, Yokohama-shi, Kanagawa, 221-8686, Japan

[email protected]

Michikazu Hara TIT Tokyo Institute of Technology [email protected]


89

4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8502, JAPAN

Satoshi Sato CHU Chiba University Yayoi, Inage, Chiba 263-8522, Japan

[email protected]


© 2015, TU/e, Eindhoven University of Technology Het Kranenveld 14, Helix STW 3.35, 5612 AP Eindhoven, The Netherlands, on behalf of the NOVACAM consortium. NOVACAM is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




NOVACAM and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




90

OCMOL Oxidative Coupling of Methane

followed by Oligomerization to Liquids

Proposal full Name: Oxidative Coupling of Methane followed by Oligomerization to Liquids Acronym: OCMOL Call Identifier: NMP.2008.4.0-2 – Catalysts and sustainable processes to produce liquid

fuels from coal and natural gas Duration: 01/09/2009 – 31/08/2014 Grant Agreement No: 228953 Total Budget: 11 312 472 € Coordinator: Prof. dr. ir. Guy B. Marin Website: www.ocmol.eu

Consortium List


1 Ghent University UGENT Belgium 2 Ruhr-Universität Bochum RUB Germany 3 Universitetet i Oslo UiO Norway 4 University of Cambridge CAM United

Kingdom 5 CNRS, Institut de Recherches sur la Catalyse et

l’Environnement IRCE France

6 STIFTELSEN SINTEF SINTEF Norway 7 Instituto de Tecnologia Quimica CSIC-ITQ Spain 8 Institut für Mikrotechnik Mainz GmbH IMM Germany 9 Boreskov Institute of Catalysis BIC Russia 10 Bayer Technology Services GmbH BTS Germany 11 Johnson Matthey plc JM United

Kingdom 12 LINDE AG LE Germany 13 Compañía Española de Petróleos S.A. CEPSA Spain 14 Haldor Topsoe A/S HTAS Denmark 15 INEOS N.V. INEOS Belgium 16 ENI S.p.A ENI Italy 17 ALMA Consulting Group SAS ALMA France


http://www.ocmol.eu/


91

1. Summary

The OCMOL project addressed several key challenges in catalysis and chemical engineering, such as oxidative coupling of methane, ethylene oligomerization to liquids, membrane/PSA separation, methane dry reforming, oxygenate synthesis and oxygenate to liquids conversion. For this purpose, OCMOL has developed and implemented high throughput methodologies to accelerate the discovery of new materials, such as catalysts, adsorbents and membranes, and to propose a green integrated chemical process with near zero CO2 emissions.

A considerable number of breakthrough materials have been discovered, demonstrating reduced lab-to-pilot-to-process cycle times, with reduced environmental impact and cost. These achievements have been obtained by developing an advanced process simulation toolkit and high-tech micro-engineering technology as well. This toolkit was systematically applied by the OCMOL partners to the aforementioned chemical objectives.

The main process steps have been implemented in separate test units and were virtually integrated. An economic evaluation of the integrated process resulted into several recommendations for improving the competiveness of the OCMOL process, e.g., increasing the yield towards liquids via ethylene oligomerization. Life cycle analysis indicated that the carbon footprint ‘from cradle to gate’ is smaller compared to other natural gas-to-synthetic diesel processes. Additionally, some key remaining challenges have been identified, in particular the limited ethylene yield of the oxidative coupling of methane and capital expenditures for the separation section.

2. Keywords

gas-to-liquid technologies, methane oxidative coupling, methane dry reforming, membrane/PSA separation, ethylene oligomerization, process intensification, micro reactor technologies


As the global energy demand and crude oil price rise, alternative production routes for the same hydrocarbon products are becoming more and more economically attractive. In this respect, synthetic fuels created from natural gas offer now an alternative to the traditional fuel supply mix.

Unfortunately, approximately one third of the world’s natural gas reserves are considered stranded and, hence, remain unexploited so far. Today, the established processes for natural gas transformation into synthetic fuels, i.e., natural gas liquefaction and Fischer-Tropsch synthesis, require large investments which are

prohibitive for the exploitation of small natural gas reservoirs.

The OCMOL project aims at developing an innovative chemical route adapted to the exploitation of small gas reservoirs from both a technical and an economic point of view. The corresponding process is, among others, based on oxidative coupling of methane followed by its subsequent oligomerization to liquids.


Major challenges will have to be addressed in the fields of methane oxidative coupling, methane dry reforming, membrane/PSA separation and ethylene oligomerization. They will be met by:

process intensification to improve the energy efficiency of the whole process, such as integration between the exothermic methane oxidative coupling and the endothermic dry reforming, development of cutting edge materials to design effective catalysts/membranes which are of paramount importance to the innovative processes foreseen

using micro reactor technologies to investigate novel reactor designs necessary to ensure the efficiency and the cost effectiveness of the OCMOL solution

5. Objectives

The general objectives of OCMOL are twofold:

process intensification via cutting-edge micro reactor technologies. This will enable to skip the expensive scale-up stage to provide a proof of concept of the OCMOL liquefaction route and allow companies to make go/no go decisions.

to develop a fully integrated process, see figure 1, which will be self-sufficient through the reuse and the recycling of by-products, in particular CO2

Figure 3: schematic overview of the OCMOL process

Major technological challenges are addressed in the fields of methane oxidative coupling, ethylene oligomerization, membrane/PSA separation, methane dry reforming, oxygenate synthesis and oxygenate to liquids conversion.


92

The OCMOL route will be designed to offer 4 main advantages:

an economic operation at capacities of 100kT/year

an operation at more uniform pressure levels

the flexibility of product streams: linear α-olefins, fuels from gasoline to diesel range

low if not zero CO2 emission thus contributing to face global warming


Methane conversion (oxidative coupling and reforming) [1-3]

The first step in the OCMOL process is the exothermic OCM followed by the endothermic RM. The heat integration of these two steps augmented the process competiveness by reduced CO2 emissions and energy requirements.

Novel, innovative catalyst synthesis routes have been validated and catalysts have been optimized to exhibit desired activity and stability. Fundamental kinetic modelling technologies provided an unprecedented understanding of the reaction mechanism and proved to be essential in reaching the performance targets. The integration of both reactions has been established both using ‘conventional fixed bed reactor system’, the so-called multi-bed micro-structured reactor (MMR) as well as the catalytic wall micro-structured reactor (CWMR) technology. Autothermal operation was achieved and maintained at a time scale of 24h.

No new breakthrough catalyst formulations have been discovered, confirming the well-established intrinsic limitation in C2 yields for OCM. However, various formulas have been found adequate for being coated on micro-structured reactors as planned in OCMOL, and, hence fulfilling the stability performance required for demonstrating the autothermal concept proposed as key objective.

Separation processes [4, 5]

In the OCMOL process, several streams should be separated and/or purified before they can be sent to other units. For example, impurities from the OCM reactor can highly decrease the performance of the ethylene oligomerization reactor downstream. The preparation and screening of new adsorbent and membrane materials was planned.

An important criteria for the realization of the OCMOL process concept has been to address the need for efficient and selective separation processes at the interface of the core process steps. Two specific challenges have been under focus: 1) remove specific by-products that can impact or even "poison" the activity of the catalyst, 2) separate out key components for recycling in order to achieve the overall targets of the

OCMOL process. Technologies based on sorbent and membrane separation have been investigated, with the core of the research involving the developing and modifying materials with potential functionality and modelling the process to gauge simulate the potential for the process of the materials.

Syngas to liquids [6-8]

In the RM unit, syngas is produced which is fed to the syngas-to-liquids (STL) unit. In fact, this unit consisted out of two different subunits, i.e., STO and OTL.

Catalysts with improved selectivities for the production of oxygenates from syngas have been developed. Additionally, novel tailor-made zeolitic materials have been developed for the selective conversion of methanol/oxygenates to a hydrocarbon stream with a low aromatic content.

Fundamental understanding of the oxygenate-to-hydrocarbon synthesis over zeolites has been gained during the project. Improved catalysts for the production of alcohols and ether intermediates and novel tailor-made zeolite materials for the conversion of methanol/oxygenates to hydrocarbons with low aromatics selectivity have been tested. An integrated, two-step, syngas to low-aromatic fuel process scheme has been established.

Oligomerization [9-11]

The ethylene produced in the OCM unit is sent to an oligomerization unit. Current technologies for ethylene oligomerization rely on the use of homogeneous organometallic catalysts. Environmental issues, among other reasons, prompts to the replacement of the homogeneous system by more friendly heterogeneous catalysts.

A large catalyst library (±100 samples) has been tested from which the promising catalysts have been selected and optimized. From this selection, several catalyst achieved the targeted productivity of 5 mmol/(kgcat·s) and a lifetime of at least 60h time-on-stream. Using these optimized catalysts, an extensive experimental dataset has been acquired which has been used to develop a microkinetic model. This micro-kinetic model is capable to describe the effects of operating conditions and catalyst properties on the observed ethylene oligomerization kinetics. Additionally, an industrial oligomerization reactor based on these micro-kinetics has been designed ‘in-silico’. A pilot-plant has been used to investigate the possibilities op upscaling.

Process integration

Each subunit in the OCMOL process has been tested separately using the selected catalysts and reaction conditions in dedicated units:


93

OCM and RM unit: multi-bed reactor with structured heat-exchangers and micro-structured reactor

separation unit

syngas to liquids unit

oligomerization unit

These tests aimed at proving the objectives set for the reactions and the catalysts, i.e., selectivity, yield, conversion and lifetime. The results from these tests have been used as design basis for the virtual integration of the OCMOL process for the economic evaluation and lifecycle analysis.

Toolkit for material and reactor design

The design and building of a number of different reactors for testing of OCM catalysts, testing of ethylene oligomerization catalysts and the measuring of reaction kinetics, including a novel NMR reactor, were achieved.

The formation of microkinetic models to aid the other technical SP’s was included. Selection of standard catalysts for other SP’s, as well as their large scale preparation and forming by innovative coating methods was incorporated into this area of the project. It also includes the realisation of two microstructured laboratory prototype reactors allowing the combination of the exothermic OCM and endothermic dry reforming reactions at a quasi auto-thermal regime with staged oxygen dosing. Investigations in to separation materials were also involved.

Process engineering and economic evaluation

A process simulation was performed integrating the different process steps and further developed along the project to reach the most sustainable design considering different aspects such as economic constraints and achieved performances during the experimental phase of the project.

An economic study was performed and was based on the calculation of fixed capital investment as well as cost of production defined by the process simulation. Two cases were considered:

the first case represented the results obtained during the OCMOL project from the laboratory phase

the second case represented results which could be possibly achieved with additional R&D efforts.

Both cases show that the project could be economic.

The following recommendations were made to improve the competitiveness of OCMOL:

the investment has to be as low as possible by economizing expensive separation steps.

the production of liquids via methane coupling and ethylene oligomerization has to be very effective in order to compensate the additional capital cost due

to the recovery of ethylene and its further oligomerization.

the process has to be economic at much lower capacities of 100 kTon/year, which is currently not possible by using state of the art technologies.

the product stream should present several alternatives allowing maximum profitability by adapting the outcome (gasoline/diesel fuels and/or petrochemicals) to fluctuations of the market demand.

A life-cycle analysis was performed and based on the carbon footprint associated with the OCMOL process. A cradle-to-gate approach was taken and a partial product life cycle from resource extraction (cradle) to the factory gate (i.e., before it is transported to the consumer) was performed. The emissions related to the transport and the usage of the final synthetic fuels produced by the OCMOL process, were considered not to be different from other conventional fuels.

Three impact categories were identified where the OCMOL process may contribute to the improvement of the environmental impact:

1. Energy consumption 2. Emissions 3. Transportation.

Emissions related to energy consumption from the OCMOL process are inherently low because of its heat integration. Since oxidative coupling is generating heat that can be used for reforming no extra furnace needs to be installed. The only emissions that are related to energy are due to the consumption of electricity.

The OCMOL process has been designed to be CO2 neutral. Apart from fugitive emission no other emissions were expected. CO2 emissions will also be considerably reduced with the recycling of produced CO2 from the OCM into the RM step. With a carbon efficiency of 92% obtained, the corresponding CO2 emissions were estimated around between 578 and 606 kg CO2/ton of final product and slightly lower than the value of 823 kg CO2/ton found for a natural gas-to-synthetic diesel process.

The impact of logistics, which depends on the distance between a gas field and the OCMOL plant, was low when the process is build close to the gas field. Gas transport could be avoided and replaced by a much more efficient transport of liquid. It has been estimated that each extra kilometer of gas transport corresponds to 0,1 kg CO2/ton of final product. Of course it is not always possible to construct an OCMOL plant close to a remote gas field due its deep-sea location or due to extreme climate conditions. In these cases OCMOL still can reduce the carbon footprint when the plant is constructed in the neighborhood of the nearest gas storage terminal. In all cases the carbon footprint will be lower than bringing


94

the feedstock via pipelines over a large distance to the market.

7. Expected impact

The innovative OCMOL process will allow the conversion of natural gas into

Energy market (gasoline, kerosene, diesel, heating oil, additives…)

Petrochemical/polymer market (ethylene and linear α-olefins)

Environmental market (sulphur free fuels)



Guy Marin UGENT Technologiepark 914, B-9052 Zwijnaarde, Belgium

[email protected]

Martin Muhler RUB Universitätsstraße 150, 44801 Bochum, Germany

[email protected]

Unni Olsbye UiO Boks 1072 Blindern 0316 Oslo, Norway

[email protected]

Mick Mantle CAM The Old Schools, Trinity Lane, Cambridge CB2 1TN, United Kingdom

[email protected]

Claude Mirodatos IRCE 43 Boulevard du 11 Novembre 1918 69100 Villeurbanne, France

[email protected]

Anna Lind SINTEF Strindveien 4, NO-7465 Trondheim, Norway

[email protected]

Agustín Martinze CSIC-ITQ Av. de los Naranjos, s/n 46022, Valencia, Spain

[email protected]

Helmut Penneman IMM Carl-Zeiss-Str. 18-20 55129 Mainz, Germany

[email protected]

Vladislav Sadykov BIC Boreskov Institute of Catalysis pr. Lavrentieva 5, Novosibirsk, Russia, 630090

[email protected]

Rainer Bellinghausen BTS Bayer Technology Services GmbH 51368 Leverkusen, Germany

[email protected]

Stephen Poulston JM 5th Floor 25 Farringdon Street London, EC4A 4AB United Kingdom

[email protected]

Mariane Ponceau LE Dr.-Carl-von-Linde-Straße 6-14 82049 Pullach im Isartal, Germany

[email protected]

Jesus Lazaro CEPSA Torre Cepsa Paseo de la Castellana, 259 A, 28046, Madrid, Spain

[email protected]

Pablo Beato HTAS Haldor Topsøes Allé 1 2800 Kgs. Lyngby, Denmark

[email protected]

Johan Corthouts INEOS Zone Industriëlle, Zone C, 7181 Feluy, Belgium

[email protected]

Vincenzo Calemna ENI Piazza Ezio Vanoni, 1, 20097 San Donato Milanese (MI), Italy

[email protected]

Fabienne Brutin ALMA 55 avenue René Cassin - CP 418 - 69338 Lyon, France

[email protected]

9. References

1. T. Serres, L. Dreibine, Y. Schuurman, Chem. Eng. J. 213 (2012) 31-40 2. V.A. Sadykov, E.L. Gubanova, N.N. Sazonova, S.A. Pokrovskaya, N.A. Chumakova, N.V. Mezentseva, A.S. Bobin, R.V.

Gulyaev, A.V. Ishchenko, T.A. Krieger, C. Mirodatos, Catal. Today 171 (2011) 140-149 3. P.N. Kechagiopoulos, J.W. Thybaut, G.B. Marin, Ind. Eng. Chem. Res. 53 (2014) 1825-1840 4. S. Aguado, G. Bergeret, C. Daniel, D. Farrusseng, J. Am. Chem. Soc. 134 (2012) 14635-14637 5. V.A. Sadykov, V. Zarubina, S. Pavlova, T. Krieger, G. Alikina, A. Lukashevich, V. Muzykantov, E. Sadivskaya, N.

Mezentseva, E. Zevak, V. Belyaev, O. Smorygo, Catal. Today 156 (2010) 173-180 6. P. Kumar, J.W. Thybaut, S. Svelle, U. Olsbye, G.B. Marin, Ind. Eng. Chem. Res. 52 (2013) 1491-1507 7. T.V.W. Janssens, S. Svelle, U. Olsbye, J. Catal. 308 (2013) 122-130





















95

8. S. Teketel, W. Skistad, S. Benard, U. Olsbye, K.P. Lillerud, . P. Beato, S. Svelle, ACS Catal. 2 (2012) 26-37 9. J. Canivet, S. Aguado, Y. Schuurman, D. Farrusseng, J. Am. Chem. Soc. 135 (2013) 4195-4198 10. A. Martinez, M.A. Arribas, P. Concepción, S. Moussa, Appl. Cat., A. 467 (2013) 509-518 11. S.T. Roberts, M.P. Renshaw, M. Lutecki, K. McGregor, A.J. Sederman, M.D. Mantle, L.F. Gladden, Chem. Commun.

49 (2013) 10519-10521


© 2015, UGENT, Technologiepark 914, B-9052 Zwijnaarde, Belgium, on behalf of the OCMOL consortium. OCMOL is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




OCMOL and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




96

PCATDES Photo-catalytic materials for the

destruction of recalcitrant organic industrial waste

Proposal full Name: Photo-catalytic materials for the destruction of recalcitrant organic

industrial waste Acronym: PCATDES Call Identifier: NMP.2012.2.2-6 Photo-catalytic materials for depollution (SICA) Duration: 01/02/2013 – 01/02/2017 Grant Agreement No: Total Budget: 5,615,292 € Coordinator: Prof. Philip R. Davies, Cardiff University Website: www.pcatdes.eu

Consortium List

No Organisation name Short name Country

1 Cardiff University CU UK 2 Sampas Nanotechnology SNANO Turkey 3 University College London UCL UK 4 Universität Rostock UROS Germany 5 Universidad Rey Juan Carlos URJC Spain 6 University of Bath UoB UK 7 National Metal and Materials Technology Center MTEC Thailand 8 SIRIM Berhad SIRIM Malaysia

9 Vietnam Academy of Science and Technology (VAST) Institute of Chemical Technology

VAST-ICT Vietnam

10 VAST-Institute Materials Sciences VAST-IMS Vietnam 11 Aston University AU UK

Contents 1. Summary .......................................................................................................................................... 96 2. Keywords ......................................................................................................................................... 97 3. Background – Current state of the art ............................................................................................. 97 4. Scientific and technological challenges ........................................................................................... 98 5. Objectives ........................................................................................................................................ 98 6. Significant results / exploitable results ........................................................................................... 99 7. Expected impact .............................................................................................................................. 99 8. People involved in the project ....................................................................................................... 100 9. Copyright ....................................................................................................................................... 100

1. Summary

Whilst power is often scarce in the remote sites where small oil producing industries are located they do benefit

from abundant sunlight. The central concept of the PCATDES project is to utilize this resource via


97

photocatalysis to achieve cost effective remediation of low concentrations of organic pollutants in waste-water. Photocatalysis has huge potential for the remediation of low concentrations of organic pollutants in water and offers a cost effective and inherently “clean” solution to this issue. However, practical exploitation of photocatalysis for water cleanup has not yet been achieved and the PCATDES project has been designed to address some of the practical challenges that have hindered this development including:

Poor wavelength range over which current photocatalytic materials operate

Requirement for robust, cost effective high surface area catalytic materials capable of withstanding operation in the field

Design of efficient reactors with optimized performance in real-world applications.

A key strategy to be explored by the project is the use of smart reactors employing UV LEDs to illuminate the catalyst and close the gap between the wavelength range of sunlight and the optimum operating range of the photocatalysts.

In this, the first reporting stage of the PCATDES project, the development of novel materials for testing against real applications was planned together with investigations into suitable LED light sources for use in the reactor. An essential element in the project was the development of a standard lab scale photocatalytic reactor together with standard reaction protocols; this would ensure that materials from different laboratories are tested under reproducible and common conditions and thus decisions on the new materials to be taken forward into subsequent stages are based on firm foundations..

2. Keywords

Photocatalysis; solar; UV irradiation;TiO2 ;catalysts; LED;anatase; sunlight; photoexcitation; semiconductor quantum efficiency; waste water; POME; Olive oil; Palm oil;


Typically, contaminated wastewater is first treated by particulate matter separation and subsequent biological degradation. These cheap and effective methods reduce the contaminants by approximately 95%. However, removing the final 5% of organic pollutants is challenging. Current methods employ a variety of approaches of which ozonation, membrane bioreactors and electrocatalytic treatment are the most common. All of these approaches are characterized by very high capital and energy costs and not affordable to small scale producers. Photo-catalytic water depollution is an emerging technology, which has significant advantages over all of the alternative methods currently employed. Using solar power is inherently more environmentally benign, eliminating the need for toxic oxidants, reducing overall energy usage and associated CO2 emissions, while also enabling deployment in areas where power is not readily available. Applications could range from providing clean drinking water in remote areas of developing nations or for deployment after emergency situations (e.g. earthquake or tsunami). The TiO2 based catalysts are relatively inexpensive and robust and therefore catalytic units can be constructed that are cost effective for small scale producers. TiO2 photo-catalysts operate via the light induced formation of active oxidising species, such as OH

●, H2O2

and O2¯ from water. The efficiency of TiO2 for producing these oxidants is related to the band gap and defect density in the structure, thus development of TiO2 based photo-catalysts often centres on methods to tune the band structure such that photo-excitation can be achieved at lower energies (i.e. higher wavelengths). Particular approaches include:

Incorporation of donor or acceptor energy levels into the TiO2 band gap.

Increasing the life time of charge carriers using charge trapping agents to decrease e

- - h

+

recombination rates.

Tuning particle size and morphology of TiO2: Previous investigations of photo-catalytic reactors have predominantly utilised fluidized systems rather than fixed bed configurations and often use high catalyst/pollutant ratios where catalytic properties will be different. In practical applications, slurry and fluidizing systems suffer from leaching and expensive downstream processing to remove the catalysts from the solution. These are not issues with fixed bed systems which also have the advantage of being able to operate in both batch and continuous flow conditions. Fixed bed systems do suffer from limitations including optimal illumination of the entire support containing the catalyst and mass transfer limitations affected by catalyst thickness and low porosity.

Fig. 2. Overview of the PCATDES strategy


98

A significant challenge to photo-catalyst development is improving the quantum efficiency. Only 5% of the solar spectrum incident on the Earth’s surface is sufficiently energetic to excite an electron across the TiO2 band gap. The effective use of photo-catalysis in purifying waste water is expected to need a significant extension of the usable wavelength into the visible range if sunlight alone is to be used. Furthermore, whilst visible light absorption in pure water is very low (~0.0100 ± 0.0006 m-1 at 320 nm for pure water) it increases rapidly at lower wavelengths and also with contamination of the water; even low percentages of effluent will require innovative design and high power light sources if the reactors are to be effective. An approach that addresses the large TiO2 band gap indirectly has been the introduction of photo-reactors based upon UV light emitting diodes (UV-LED). UV LEDs based on InAlGaN can operate across the entire UV-A (400–320 nm), UV-B (320–280 nm) and even UV-C (280–200 nm) spectral ranges. UV-LED reactors have been employed for direct water purification using 200 - 300 nm photons to destroy micro-organisms. However, the volume of water treatable is quite small and first generation UV LED sources suffer from relatively low external quantum efficiencies (EQE) and emission power. More recently a UV-LED array source that emits light at 385nm with >10mW at 20mA was deployed in a thin film recirculating reactor. Studies with this system have so far only focused on commercial P25 TiO2


Our aim is to design and optimise TiO2 catalysts to operate at these wavelengths to take advantage of both the greater intensity of sunlight available in the violet-blue part of the spectrum compared with the UV and the new technology of high-brightness blue LEDs. A relatively small decrease in TiO2 band gap would allow us to utilise these systems to full effect (Fig 4) and bring together technological advances in the two fields.

Fig. 4. Absorption spectrum undoped TiO2 compared to the

solar spectrum, showing limited overlap (~5%). Power output of commercial LEDs are also shown (dotted line) indicating that

a relatively small change in TiO2 bandgap allows the higher power of violet-blue LEDs to be utilised

The development of an efficient UV-A or HB-BV-LED driven photo-catalytic reactor for water pollution requires tandem development of catalyst, LED array and reactor technology driven with a knowledge of the site of operation and pollutants to be targeted for wastewater treatment technologies. The choice of treatment method usually depends upon the composition of the wastewater engineering design and modelling, in particular for the most efficient operation of the UV-A LED array will be critical for successful scale up of laboratory tests to large-scale operation. Improved fundamental understanding is required, of the impact of preparation conditions and impurities derived from anodisation on the resulting TiO2 band structure, as is an assessment of the optimum reactor configurations to optimise energy efficiency and irradiation uniformity of LED arrays.

5. Objectives

PCATDES focuses on the following objectives:

Optimise Catalyst Formulation for operation under UV-A and HB-BV LED operation: The impact of morphology of TiO2 based photo-catalysts will be explored using nanotubes prepared via anodisation of Ti films, wires and meshes to provide high surface area rigid structures for use in flow reactors. The introduction of dopants to tune performance of anodised TiO2 nanostructures will also be explored. In addition methods to prepare coated films of high surface area nanoparticulate forms of photo-catalyst via dip or sol-gel coating will also be explored to utilise materials having more advanced/complex formulations.

Improved fundamental knowledge: As outlined above, the impact of dopants may serve to alter the electronic structure of the photo-catalyst (e.g. shifting absorption into the visible), or have an impact on the lifetime of the activated electron-hole pair. Fundamental understanding of structure reactivity relationships via time resolved in-situ spectroscopy and band structure measurements of different TiO2 is thus critical to aiding catalyst design. In addition it is also important to determine whether poisons present in authentic waste streams may have a detrimental impact on photo-catalyst lifetime.

Reactor optimisation: Reaction conditions and reactor design will be guided through modelling of laboratory scale kinetic studies to determine optimum catalyst concentration, presentation, flow rates, film thickness, photon irradiation and potential for pulse operation. Methods to minimise unfavourable light scattering by the catalyst and optimise light penetration into the solution will be assessed with the impact of light intensity and pulsed


99

mode irradiation by UV-A LEDs will be included in the model.

Optimise LED array technology: Efficient photo-catalysis requires incident light of photon energy greater than the optical band gap of the active material. In the case of TiO2 the emission wavelength of any UV-LEDs used to boost the incident optical intensity will need to be < ~350 nm.

Integration of a sustainable environmentally benign process: There are few studies of photo-catalytic treatment of authentic waste water streams. We are focussing on the recalcitrant component, however while work on model systems can guide models, the presence of potential catalyst poisons may require pre-treatment steps or more robust catalyst systems. Systematic spectroscopic and kinetic studies will be used to guide catalyst development and highlight problems associated with real feeds (e.g. poisons etc).


A site survey was conducted aimed at determining the sites where photocatalytic reactor would be most effective; this included an analysis of the water pollution problem based on countries and industries. Several target markets were identified:

Olive oil (Olive Oil Mill Effluent OOME);

Palm oil (biologically treated palm oil mill effluent BT-POME)

Seafood industries. Based on this site survey a market survey was conducted in which the views of industries and experts in the field were sought across the regions likely to be most interested in the photocatalytic reactor. Analysis of the results of the survey will feed into the eventual business plan for the consortium and inform the development pf the reactor itself. Cost is a major limiting factor. The PCATDES web site (http://www.pcatdes.eu) contains full details of the project and is an ideal platform to share news of the advances made. Presentations, posters and papers as well as all reports are loaded into a private area for consortium members. The site has developed a good hit rate for the early stage of the project. A project information leaflet was developed. The leaflet introduces the PCATDES consortium and its ambitions. It was distributed at a number of events including WICS 2013, and the ASEAN-EU (STI) meeting in Bangkok, January 2014 Conference participation: World Intelligent Cities Summit and Exhibition” (WICS) 2013, Istanbul, Turkey “ASEAN-EU Science, Technology and Innovation” (STI), Bangkok, January 2014 Several PCATDES partner leaders also made presentations.

Development of a standard PCATDES test reactor

Reactor gives excellent illumination characteristics with a large area of consistent radiation that can be tuned using a 12 sensor calibration system.

Light intensity in the reactor can be much brighter than that obtained with alternative UV illumination sources and thus reaction kinetics were much faster.

Development of novel photocatalyst materials. A large range of materials have been investigated as replacements for the standard P25 TiO2 powder including:

TiO2 films doped with non-metal precursors using vapour deposition methods

Hierarchically-structured ZnO structures, Fig 5 & double layer Zn–Al–NO3– and Zn-Cr-NO3–layered double hydroxides.

Highly active carbon nitrides (CNs) & core-shell

CuS/ZnS and CuO/TiO2 materials.

7. Expected impact

The aim of the PCATDES project is to develop a prototype reactor capable of removing the final 5% of organic contaminants from the biologically treated effluent from vegetable oil and seafood processing industries using the power of the sun and a suitable catalyst. The reactor will be a benefit to the smaller scale industries and make a contribution to mitigating the impact of such industries on the natural environment. Other benefits from the project include the extensive cross fertilisation of ideas between the 11 centres of excellence situated throughout Europe and the South East Asia regions and the scientific collaborations that have developed between these different groups. We also expect to generate a great deal of new knowledge about photocatalysis, with new catalytic materials created, new understanding of catalytic mechanisms and new designs for the reactors

Fig 5. SEM images of 3D porous ZnO

http://www.pcatdes.eu/


100


Affiliation Name email

Cardiff University Prof Phil Davies Mr Nigel Pearson


Aston University Prof Karen Wilson [email protected]

Sampas Nanotechnology Mr Eser Karakaya Mr. Mehmet Mermutlu


University College, London Prof Ivan Parkin Dr Raul Quesada


Universitat Rostock Dr Hendrik Kosslick Prof Axel Schulz


Universidad Rey Juan Carlos Dr Javier Mauragan Dr Ruud Timmers


University of Bath

Prof Chris Bowen Dr Duncan Alsopp Dr Chris T. Clarke

[email protected] [email protected] [email protected]

National Metal & Materials Technology Centre

Dr Angkhana Jaroenworatuck [email protected]

SIRIM-Berhad

Isnazunita Ismail Mohamad Zahid Abdul Malek Dr Teng Wang Dung Tan Yong Nee

[email protected] [email protected] [email protected] [email protected]

Vietnam Academy of Science & Tech - ICT

Prof Dr Sc Cam loc Luu Dr Pham Thuy Phoung


Vietnam Academy of Science & Tech - IMS

Prof Nguyen Quang Liem Dr Ung Thi Dieu Thuy


9. Copyright

© 2015, Cardiff University, on behalf of the PCATDES consortium. PCATDES is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




PCATDES and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;


























101

4G-PHOTOCAT Fourth generation photocatalysts: nano-

engineered composites for water decontamination in low-cost paintable

photoreactors

Proposal full Name: Fourth generation photocatalysts: nano-engineered composites for water

decontamination in low-cost paintable photoreactors Acronym: 4G-PHOTOCAT Call Identifier: FP7-NMP-2012-SMALL-6- Photocatalytic materials for depollution Duration: 01/01/2013 – 31/12/2015 Grant Agreement No: 309636 Total Budget: 4,884,983 € Coordinator: Prof. Dr. Radim Beránek Website: www.4g-photocat.eu

Consortium List


1 Ruhr-Universität Bochum RUB Germany 2 University College London UCL UK 3 J. Heyrovský Institute of Physical Chemistry JHI Czech republic 4 Advanced Materials - JTJ sro AM Czech republic 6 Jagiellonian University Krakow JUK Poland 6 University of Helsinki UH Finland 7 Picosun Oy PS Finland 8 Universiti Teknologi Malaysia UTM Malaysia 9 Vietnam National University of Agriculture VNUA Vietnam 10 Q&A Ha Noi Ltd Q&A Vietnam

Contents

1. Summary ........................................................................................................................................ 101 2. Keywords ....................................................................................................................................... 102 3. Background – Current state of the art ........................................................................................... 102 4. Scientific and technological challenges ......................................................................................... 102 5. Objectives ...................................................................................................................................... 103 6. Significant results / exploitable results ......................................................................................... 103 7. Expected impact ............................................................................................................................ 104 8. People involved in the project ....................................................................................................... 105 9. References ..................................................................................................................................... 106 10. Copyright statement .................................................................................................................... 106

1. Summary

Heterogeneous photocatalysis is potentially one of the cheapest and most efficient methods for decontamination of water and air from toxic organic

pollutants since highly oxidizing conditions can be established without any further reagents needed – the only prerequisite is the supply of aerobic oxygen and sunlight irradiation. Nevertheless, real-life applications of photocatalysis are still rather scarce, particularly

http://www.4g-photocat.eu/


102

because the photocatalytic degradation rates are not high enough, and the costs associated with the photoreactor construction make the implementation economically unviable.

The project 4G-PHOTOCAT allies the expertise of 7 academic and 3 industrial partners from 5 EU countries (Germany, United Kingdom, Czech Republic, Poland, and Finland) and 2 ASEAN countries (Malaysia and Vietnam) for the development of a novel generation of low-cost nano-engineered photocatalysts for sunlight-driven water depollution. Through rational design of composites in which the solar light-absorbing semiconductors are coupled to nanostructured redox co-catalysts based on abundant elements, the recombination of photogenerated charges is suppressed and the rate of photocatalytic reactions is maximized. In order to achieve fabrication of optimal architectures, advanced chemical deposition techniques with a high degree of control over composition and morphology are being employed and further developed. Furthermore, novel protocols are being developed for the implementation of the photocatalysts into a liquid paint, allowing for the deposition of robust photoactive layers onto flat surfaces, without compromising the photoactivity of immobilized photocatalysts. Such paintable photoreactors are envisaged particularly as low-cost devices for detoxification of water from highly toxic persistent organic pollutants which represent a serious health issue in many remote rural areas of Vietnam and other countries. The 4G-PHOTOCAT project will provide novel scientific insights into the correlation between compositional/structural properties and photocatalytic reaction rates under sunlight irradiation, as well as improved fabrication methods and enhanced product portfolio for the industrial partners. Finally, 4G-PHOTOCAT will lead to intensified collaboration between scientists working at the cutting edge of synthetic chemistry, materials science, heterogeneous photocatalysis, theoretical modelling, and environmental analytics, as well as to unique reinforcement of cooperation between scientists and industry partners from EU and ASEAN countries.

2. Keywords

Photocatalysis, water depollution, titanium dioxide, transition metal oxides, solar detoxification, paintable coatings, persistent organic pollutants (POPs), herbicides.


People from many countries of the world extensively use pesticides which contaminate drinking and irrigation water with toxic organic compounds. For example, in rural areas of Vietnam, herbicides and dioxins, which are resistant to degradation, made their way into the water

cycle during the Vietnam war. Cancer and abnormalities in newborns can be the consequence. Heterogeneous photocatalysis utilizing low-cost materials like titanium dioxide (TiO2) is potentially one of the cheapest and most efficient methods for decontamination of water from toxic organic pollutants.

1

Sunlight and oxygen establish, at the photocatalyst surface, highly oxidizing conditions under which toxic organic compounds are easily degraded into non-harmful substances like water and carbon dioxide (Figure 1).

Figure 1. Principle of heterogeneous photocatalalysis: upon light absorption in semiconducting particles electron-hole pairs are generated; toxic organic pollutants are degraded (oxidized) either directly by photogenerated holes or by the action of hydroxyl radicals formed. Nevertheless, real-life applications of photocatalytic water treatment are still rather scarce, particularly because the photocatalytic degradation rates are very low. Moreover, the assembly of the needed photoreactors is often too expensive to make photocatalytic systems economically viable.


In the context of recent efforts to enhance the photoactivity of TiO2-based photocatalysts, our project goes beyond the paradigm of focusing chiefly on shifting the light absorption edge of pristine TiO2 (first generation photocatalysts) into the visible light range by doping with metals (second generation), or by non-metal-doping (third generation), which only rarely and in case of few pollutants led to activity enhancements, mainly due to enhanced recombination.

2-4 Indeed, even

for pristine TiO2 photocatalysts the major challenge are the very low quantum yields (only few per cent), meaning that most of the photogenerated charges recombine before they are able to induce desired redox reactions. In this context it is important to realize that it is particularly the oxygen reduction by photogenerated electrons which is typically very slow and represents thus a kinetic bottleneck in photocatalytic applications.

5-

6 Therefore, the main scientific thrust of 4G-PHOTOCAT is that higher photocatalytic reaction rates can be achieved if the interfacial transfer of photogenerated electrons to oxygen molecules can be significantly improved through rational surface nano-engineering of the photocatalyst, e.g., by depositing a co-catalyst for


103

oxygen reduction (Figure 2). Indeed, it is well known that the deposition of small amounts of platinum particles can enhance photocatalytic degradation efficiencies of TiO2.

7 Obviously, for large-scale photocatalytic

applications an alternative to use of noble metals like platinum must be found.

Figure 2. The photocatalyst design concept of 4G-PHOTOCAT (a low-cost redox co-catalyst is deposited onto TiO2 photocatalyst to catalyze the reduction of oxygen by photogenerated electrons, and maximizing thus the charge separation and reaction rates) as compared to other strategies for enhancing the photocatalysis at pristine TiO2 (1st generation) by bulk-doping with transition metal ions (2nd generation) or main group elements (3rd generation) for visible light activity. In terms of photocatalyst immobilization a key challenge is to ensure high mechanic and chemical stability of the immobilized photocatalysts, without compromising the photocatalytic activity by using binder systems which would block the photocatalyst surface and hinder thus the photocatalytic reactions.

5. Objectives

4G-PHOTOCAT therefore focuses on the following objectives:

The main scientific objective of the 4G-PHOTOCAT project is to develop a novel generation of low-cost nanoengineered photocatalysts for sunlight-driven water depollution. The newly developed photocatalysts are TiO2 particles coupled to nanostructured redox co-catalysts based on cheap and abundant elements (Cu, Co, Fe). In the presence of the co-catalysts the rate of oxygen reduction reaction is enhanced, which suppresses the recombination of photogenerated charges, and leads to enhanced rates of photocatalytic reactions.

In order to achieve fabrication of optimal architectures, advanced chemical deposition techniques with a high degree of control over

composition and morphology (e.g., atomic layer deposition) are being employed and further developed.

Another important scientific objective of 4G-PHOTOCAT is to understand the correlation between compositional, structural and optical properties of immobilized photocatalyst layers, and the photocatalytic reaction rates and degradation mechanisms under sunlight irradiation. Detailed mechanistic investigations supported by theoretical modelling (DFT) play an essential role in 4G-PHOTOCAT in order to understand the influence of the photocatalyst and binder properties on the rate of the photocatalytic reactions and on the degradation mechanism. Protocols for a very careful analysis of degradation products are being developed in order to identify possible unreacted intermediates and optimize the photocatalyst performance for complete mine-ralization. Furthermore, detailed investigations of the energetics of the reactive photogenerated electrons and holes (positions of the band edges) and time-resolved studies of the reaction-recombination dynamics of photogenerated charges are performed.

The main technological objective of 4G-PHOTOCAT is to implement the photocatalysts into a liquid paint, allowing for the deposition of robust photoactive layers onto various surfaces. Such paintable photoreactors are being tested under real-life conditions as low-cost devices for sunlight-driven detoxification of irrigation as well as drinking water from highly toxic persistent organic pollutants (POPs) in remote rural areas of Vietnam and other countries.


• Precursor synthesis: Successful synthesis and delivery of novel precursors for atomic layer deposition (ALD) of transition metal oxide-based cocatalyst. • ALD processing: Fabrication of TiO2 films by ALD that have been successfully used in photocatalytic testing as model systems. These films serve also as well-defined model substrates for metal oxide cocatalyst depositions. • ALD reactor development: Development and optimization of up-flow (fluidized bed, PicoFloat®) and down-flow (powder cartridge, POCA) designs of Picosun’s ALD reactors has been started for TiO2 powders consisting of small-size particle agglomerates, and suitable sample holders for TiO2 powders have been found.


104

• Photocatalyst development: Large sets of commercially available TiO2 powders (used as benchmark starting materials) were modified with low-cost co-catalysts based on metal oxides and characterized. Model TiO2 films and co-catalyst-modified powders have been tested on their photocatalytic activity; enhanced photocatalytic degradation rates (as compared to conventional TiO2 photocatalysts) have been achieved.

8-10

• Photocatalyst paint: Protocols for painted photocatalyst coatings with a long-term adhesion to the support in aqueous media and on tuning of the binder surface properties have been developed.

Figure 3. Large-scale photocatalytic reactors for quasi-field testing have been developed and installed at the campus of Vietnam National University of Agriculture in Hanoi. • Theoretical calculations: Several different metal-oxide systems were studied. The bulk band structure of these materials was calculated, and experimental data were used to determine what the relative positions of the band edges are. The effects of sensitization of anatase TiO2 with Fe2O3 clusters on the reaction chemistry were studied (based on realistic low energy (Fe2O3)n clusters, particularly their reaction chemistry with the (101) surface and the mechanisms of charge transfer from the anatase TiO2 to the iron oxide material. • Quasi-field photoreactor testing: Proof-of-the-principle test reactors have been developed and installed at the campus of the Vietnam National University of Agriculture in Hanoi (Figure 3). Solar

decontamination of surface water by floating photocatalysts was successfully tested. • Dissemination: Several consortium meetings were organized; project has been promoted via press statements and TV programs; project and project results have been presented at international conferences (altogether more than 90 oral and poster presentations so far; e.g. at the EuroNanoForum 2013 in Dublin, and several conferences in ASEAN countries). Two best poster prizes for our posters have been awarded. A joint workshop on photocatalysis has been organized together with LIMPID and PCATDES consortia within the EU-ASEAN STI Days in Bangkok (21.-23.01.2014); project webpage (www.4g-photocat.eu) has been established and maintained.

7. Expected impact

The main scientific objective of 4G-PHOTOCAT is to develop novel composite photocatalysts with enhanced efficiency and to understand the correlation between compositional and structural properties of the nanostructured composite, and the photocatalytic reaction rates and degradation mechanisms under solar irradiation. The main technological objective of 4G-PHOTOCAT is to develop paintable photoreactors that will be utilized as low-cost devices for sunlight-driven detoxification of water from highly toxic persistent organic pollutants (POPs) in remote rural areas of Vietnam and other countries. The application of the low-cost painted photocatalytic reactors for water decontamination in remote rural areas of Vietnam and elsewhere will in middle and long term lead to improvement of health standards of poor and underprivileged people based in areas affected by the overuse of herbicides and other toxic organic substances. Moreover, the composite photocatalysts developed within 4G-PHOTOCAT might find use also in other photocatalytic applications including cleaning of air or solar fuel production. It should be noted that novel routes for synthesis of metal oxide nanomaterials, their advanced characterization and better understanding developed within 4G-PHOTOCAT are expected to have a major impact on nanotechnology in general, with possible repercussions on sectors of catalysis, health, environment, energy and transport. The 4G-PHOTOCAT consortium contains three industrial partners all of which are eager to pick up the technological progress of the project for future commercialisation. Picosun, a well-established developer of unique ALD reactors, is developing a novel fluidized bed ALD reactor. It should be noted that the development of such a

http://www.euronanoforum2013.eu/

http://www.4g-photocat.eu/


105

reactor would represent a significant breakthrough with technological and commercial significance reaching far beyond the scope of 4G-PHOTOCAT. Fast ALD processed deposition of metal oxide nanostructures onto highly porous substrates can be expected to open up the route to major technological developments in the broad, and commercially highly attractive, field of synthesis of heterogeneous catalysts and other porous nanostructured materials. Advanced Materials, the SME based in the Czech Republic running production of photocatalytic coatings has already established cooperation with Q&A Ha Noi, a small Vietnamese SME founded in order to introduce nanotechnologies to the Vietnamese market. Showing the feasibility of water remediation using paintable photoreactors achieved within 4G-PHOTOCAT will for both partners lead to enhancements of product portfolio (photocatalytic coating applicable in aqueous media) and increase of sales. Moreover, 4G-PHOTOCAT provides for AM and Q&A enhanced visibility on the highly important market segment of Asian region. This is crucially

important since, due to increasing environmental concerns, the market for photocatalytic environmental applications is expected to boom within the next 10 years. Apart from the above-mentioned synergy on the industrial level, the specific EU-ASEAN cooperation within 4G-PHOTOCAT offers unique opportunity of intensified collaboration and mutual scientific exchange between scientists from EU and ASEAN countries. Biannual meetings and short-term research exchange visits are practised in order to assure fast progress within the project. The cooperation networks established within 4G-PHOTOCAT represent a platform for a long-standing scientific exchange and cooperation. The project provides funding for ca. twenty young investigators in the early stage of their career (postdocs and PhD students) who have the opportunity to visit other partners’ labs and obtain valuable scientific and intercultural experiences. This intense exchange is expected to lead to further cooperation in further collaborative projects in the future.



Radim Beránek RUB Faculty of Chemistry and Bio-chemistry, Ruhr-Universität Bochum, Universitätsstr. 150, D-44780 Bochum, Germany

[email protected]

Roland A. Fischer RUB Faculty of Chemistry and Bio-chemistry, Ruhr-Universität Bochum, Universitätsstr. 150, D-44780 Bochum, Germany

[email protected]

Martin Muhler RUB Faculty of Chemistry and Bio-chemistry, Ruhr-Universität Bochum, Universitätsstr. 150, D-44780 Bochum, Germany

[email protected]

Jennifer Strunk RUB Faculty of Chemistry and Bio-chemistry, Ruhr-Universität Bochum, Universitätsstr. 150, D-44780 Bochum, Germany

[email protected]

Junwang Tang UCL 212A Roberts Building, Chemical Engineering, London, WC1E 7JE, UK

[email protected]

Z. Xiao Guo UCL Room 339, Department of Chemistry, UCL, London, UK

[email protected]

Jaromír Jirkovský JHI Department of Electrochemical Materials, J. Heyrovsky Institute of Physical Chemistry of the ASCR, v. v. i., Dolejškova 2155/3, 182 23 Prague 8, Czech Republic

[email protected]

Jan Procházka AM Advanced Materials-JTJ s. r.o., Kamenné Žehrovice 23, 273 01, Czech Republic

[email protected]

Wojciech Macyk JUK Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland

[email protected]











106

Markku Leskelä UH Department of Chemistry, PO Box 55 FI-00014, University of Helsinki, Finland

[email protected]

Satu Ek PS Picosun Oy, Masalantie 365, FI-02430 Masala, Finland

[email protected]

Leny Yuliati UTM Ibnu Sina Institute for Fundamental Science Studies, 81310 UTM Skudai, Skudai, Johor, Malaysia

[email protected]

Mustaffa Shamsuddin UTM Ibnu Sina Institute for Fundamental Science Studies, 81310 UTM Skudai, Skudai, Johor, Malaysia

[email protected]

Nguyen Truong

Son VNUA Vietnam National University of Agriculture, Trau Qui Gia Lam, 84, Hanoi, Vietnam

[email protected]

Nguyen Manh

Hung Q&A Q&A Ha Noi Ltd, Quynh Mai Street 119 / E7 Hai Ba Trung Dict, Hanoi, Vietnam

[email protected]

9. References

1. Kisch, H. Semiconductor Photocatalysis. Principles and Applications. Wiley-VCH, 2015. 2. Chen, X.; Mao, S. S. Chem. Rev. 2007, 107, 2891. 3. Ohtani, B. Rec. Pat. Eng. 2010, 4, 149. 4. Herrmann, J. M. SCIENCE CHINA Chemistry 2010, 53, 1831. 5. Gerischer, H.; Heller, A. J. Phys. Chem. 1991, 95, 5261. 6. Jing, L.; Cao, Y.; Cui, H.; Durrant, J. R.; Tang, J.; Liu, D.; Fu, H. Chem. Commun. 2012, 48, 10775. 7. Bahnemann, D. W.; Mönig, J.; Chapman, R. J. Phys. Chem. 1987, 91, 3782. 8. Neubert, S.; Pulisova, P.; Wiktor, C.; Weide, P.; Mei, B.; Guschin, D.A.; Fischer, R.A.; Muhler, M.; Beranek, R. Catal. Today 2014, 230, 97. 9. Moniz, S. J. A.; Shevlin, S. A .; An, X.; Guo, Z. X .; Tang, J. Chem. Eur. J. 2014, 20, 15571. 10. An, X.; Liu, H.; Qu, J.; Moniz, S. J. A.; Tang; J. New J. Chem. 2015, 39, 314.


© 2015, RUB, Faculty of Chemistry and Bio-chemistry, Ruhr-Universität Bochum, Universitätsstr. 150, D-44780 Bochum, Germany, on behalf of the PCATDES consortium. PCATDES is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




PCATDES and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;










107

SCOT Smart CO2 Transformation

Organzation full Name: Smart CO2 Transformation Acronym: SCOT Type of Organisation: FP7 Consortium

Address: N/A Country: Greenwin (BE), Axelera (FR), DECHEMA (GE), University of Sheffield (UK),

Trinomics (NL), DCMR (NL), Service Publique Wallonie (BE), Yorkshire Chemical Focus (UK), Leeds City Council (UK) + Other Affiliate Members

Employees: N/A President/Director: Youssef Travaly, Project Coordinator, [email protected] Website: www.scotproject.org

Contents 1. Summary ........................................................................................................................................ 107 2. Keywords ....................................................................................................................................... 107 3. Description of the Organisation .................................................................................................... 107 4. Scientific and technological challenges, objectives and scopes .................................................... 108 5. Activities and highlights ................................................................................................................. 108 6. Organogram (flow chart) ............................................................................................................... 108 7. Copyright statement ...................................................................................................................... 109

1. Summary

SCOT (Smart CO2 Transformation) is a collaborative European project (supported by the Seventh Framework programme) in the area of Carbon Dioxide Utilisation (CDU). The main objective of the project is to define a Strategic European Research and Innovation Agenda for CO2 recycling. Nowadays it groups 9 core partners from 5 European regions already involved in CO2 recycling (Belgium, France, Germany, The Netherlands and the

UK) and a growing number of affiliate regions.

2. Keywords

Strategic Research Agenda, Europe, CO2 Utilization, CCU, Catalysis, Photocatalysis, Green chemistry, Polymerization Catalysis, Renewable fuels, Mineral carbonation, Industrial competitiveness

3. Description of the Organisation

SCOT is a European project focused on 6 general objectives that have related work packages (WP):

Objective 1: Assess the capacity of regional clusters in structuring the CO2 recycling community and streamlining the value chain for CO2 recycling in synergy with the existing regional priorities and initiatives (WP1: Regional Assessment)

Objective 2: Address societal, economic, regulatory and legislative barriers which may affect the development of products and material based on recycled CO2 (WP2: Socio-economic analysis)

Objective 3: Define common research priorities and collaboration strategies in addressing the key challenges in a Vision document and a R&D agenda (WP3: European Research and Innovation Strategy)

Objective 4: Strengthen European knowledge skills, infrastructures and research driven clusters via tools sharing, knowledge exchange (WP4: Joint Action Plan and preparation for implementation)

Objective 5: Organize coherent and structured Regional


108

and European financial support to conduct research & networks in the CO2 industries to optimize an integrated value chain of CO2 recycling and to start its implementation (WP5: Financial Engineering)

Objective 6: Set-up a financial framework to enable the implementation of the Joint Action Plan (WP6: Mentoring and International Cooperation)

4. Scientific and technological challenges, objectives and scopes

The three key deliverables of the SCOT project are: A Strategic European Research Agenda (SERA) aimed at improving the techno-economic performance of emerging CO2 transformation technologies.

1. A Joint Action Plan (JAP) for Europe that includes structural policy measures to favor the transition to a new European society based on low carbon energy and the paradigm of “CO2-as-a-resource”.

2. An EU CCU newtrok (universities, research centres and industries), to structure multidisciplinary research programmes and other collaborative actions defined in the Join Action Plan (JAP).

SCOT focuses on CO2 transformation. The scope of the project does not cover CO2 capture or direct use of CO2 (EOR, carbonated drinks, etc.). Our research agenda will consider research and innovation needs on both chemical and biological transformations leading to three types of products: chemical building blocks, synthetic fuels, and building materials (mineral carbonation).

Figure 1 - CO2 Value Chain

5. Activities and highlights

In the past, the Consortium has produced and published a Regional Assessment and a Socio-economic analysis of CDU in Europe.

Recently, the SCOT Consortium has elaborated a Vision for the future of CO2 recycling in Europe that is available for public consultation on the website: www.scotproject.org.

The work on the Strategic European Research Agenda is well advanced and will be presented in the project’s mid-term conference on the 28

th of September in Essen.

Parallel to that, SCOT regularly organizes workshops on the potential of specific CDU technologies, brokerage sessions, trainings and networking events.

In June 2016, SCOT will organize the final project conference in Brussels gathering key European stakeholders to discuss about CO2 recycling policies.

Finally, SCOT is structuring an Affiliate network of organizations working on CDU in Europe. The network is still open so we invite interested partners to contact us should they wish to take part in this European network.

6. Organogram (flow chart)

SCOT is a European Consortum formed 9 core partners coordinated by the Belgian cluster Greenwin. A description of the partners can be found below:

GreenWin [GW] (Wallonia, Belgium). It is one of the six innovation-driven competitiveness clusters recognized by the Walloon government. GreenWin’s strategy is focused on clean technology innovation along the whole life-cycle of materials. It has accompanied the development of several collaborative R&D projects aimed at treating CO2 as a valuable resource rather than as a waste effluent.

Axelera [AXL] (Rhône Alpes, France). AXL is French competitiveness cluster aimed at promoting and accelerating the development of innovative chemical and environmental industries in Rhône Alpes and beyond. They have certified more than 180 R&D projects (securing an overall funding above 700 M€). Among those, they have worked ion CO2 recycling projects in France..

The University of Sheffield [TUOS] (Yorkshire, UK). TUOS is one of the UK's leading research-led Universities, being part of the elite Russell Group. It has expertise in energy technologies, process engineering, biological systems, chemical synthesis, carbon capture and the recycling of CO2 into value added products using chemical and biological techniques, electrochemistry, catalysis, hydrogen production and communication of science.

http://www.scotproject.org/


109

Yorkshire Chemical Focus [YCF] (Yorkshire, UK). YCF is an industry-led membership organisation which supports and promotes the chemicals sector in Yorkshire. The aims of YCF are to increase the competitiveness of the industry, encourage growth and to promote a better understanding and awareness of an industry that is crucial to the region’s economy.

Leeds City Council [LEP] (Yorkshire, UK). LEP is the local government organisation for the Leeds area which acts as the accountable body on behalf of the Leeds City Region Local Enterprise Partnership.

DCMR Environmental Protection Agency Rijnmond [DCMR] (Rotterdam area, Netherlands). It is the regional environmental agency of the local and regional authorities operating in Rijnmond, the larger 'Port of Rotterdam'-area in the Netherlands.

Trinomics [TEC] (formerly called Triple-E) (Netherlands). TEC is an economic consultancy giving advice to leading public sector clients on policy related to energy, environment and climate change. They provide

knowledge that allows decision-makers to make decisions based on facts, evidence and thorough analysis. They team up with experts from academia, business and consultancy to solve complex problems.

Service Public de Wallonie [SPW] (Wallonia, Belgium). SPW is the regional administration in charge of the overall supervision and funding of the competiveness clusters in Wallonia. Within SPW, the Directorate General Operational for Economy, Employment and Research (DGO6) is in charge of funding applied research for new technologies and innovation projects for industries, academia and research centers.

Society for Chemical Engineering and Biotechnology e.V [DECHEMA] (Germany). DECHEMA is an interdisciplinary scientific society with more than 5,800 personal and institutional members (including about 800 companies). It is dedicated to the support of R&D progress and implementation in various fields of chemical

engineering.


© 2015, GreenWin, on behalf of the SCOT consortium. SCOT is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




SCOT and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




110

SusFuelCat Sustainable fuel production by aqueous phase reforming – understanding catalysis and hydrothermal stability of carbon supported noble metals

Proposal full Name: Sustainable fuel production by aqueous phase reforming – understanding

catalysis and hydrothermal stability of carbon supported noble metals Acronym: SusFuelCat Call Identifier: NMP.2012.1.1-1 - Rational design of nano-catalysts for sustainable

energy production based on fundamental understanding Duration: 01/01/2013 – 31/12/2016 Grant Agreement No: 310490 Total Budget: 4,601,001.96 € Coordinator: Prof. Dr.-Ing. Dipl.-Kfm. Bastian J. M. Etzold Website: www.susfuelcat.eu

Consortium List

No Beneficiary Name Short name

Country

1 Friedrich-Alexander-University Erlangen- Nürnberg FAU Germany 2 Abo Akademi University AAU Finland

3 Bayerische Forschungsallianz GmbH BayFOR Germany 4 Boreskov Institute of Catalysis

BIC Russia

5 BTG Biomass Technology Group BTG Netherlands 6 Future Carbon GmbH FC Germany

7 Johnson Matthey PLC JM United Kingdom

8 Universidad Autónoma de Madrid UAM Spain 9 University of Palermo UNIPA Italy 10 University of Twente UT Netherlands

Contents 1. Summary ........................................................................................................................................ 111 2. Keywords ....................................................................................................................................... 111 3. Background – Current state-of-the-art .......................................................................................... 111 4. Scientific and technological challenges ......................................................................................... 111 5. Objectives ...................................................................................................................................... 112 6. Significant results / exploitable results ......................................................................................... 113 7. Expected impact ............................................................................................................................ 113 8. People involved in the project ....................................................................................................... 114 9. References ..................................................................................................................................... 114 10. Copyright statement .................................................................................................................... 114

http://www.susfuelcat.eu/


111

1. Summary

Biomass conversion is of high priority for sustainable fuel production to reduce the reliance of Europe on fossil fuel production and to provide environmentally friendly energy. Aqueous phase reforming (APR) is one of the most promising, competitive ways for the production of liquid and gaseous fuels from biomass, since it is low energy consuming. APR enables processing of wet biomass resources without energy intensive drying and additional hydrogen production from water by the water-gas-shift reaction. Hence, APR is one of the processes that allow fast industrialization of conversion systems suited for wet biomass resources. Catalysis is here the key technology. State-of-the-art catalysts used are a) not optimized and b) can lack hydrothermal stability. Regarding the latter, the paradigm shifts towards carbon supported catalysts, due to its superior hydrothermal stability. Within the project experts for multinational industry, SMEs and academia focus on the optimization of hydrothermally stable carbon supported catalysts for the APR to unleash the potential of catalysts. Methodology employed is not a trial and error optimization. By deduction of fundamental structure-property relationships from highly defined model catalysts a catalyst design capability is build up. This knowledge will be used for optimization with the objectives to increase catalyst activity, selectivity and hydrothermal stability. Cost efficient routes to produce these catalysts in a technical scale will be evaluated encompassing the synthesis and long term operation with technical feedstocks.

2. Keywords

Sustainable fuel, aqueous phase reforming, catalyst design, structure-property relationships, nano and macroscopic carbon support materials.

3. Background – Current state-of-the-art

Aqueous phase reforming (APR), introduced by Dumesic and co-workers in 2002 [1], is a promising technology for production of both hydrogen and/or liquid hydrocarbons from aqueous sustainable resources (see [2] and references cited therein). It opens up new paradigms in efficient and selective fuel (hydrogen, alkanes) production from renewables. The process was successfully applied to convert carbohydrates (and usually polyols) to hydrogen and hydrocarbons [1, 3, 4] and to produce fuel from model compounds such as ethylene glycol and glycerol. APR of polyols can be performed at approx. 225°C and 30 bar either in absence or presence of hydrogen [5]. It occurs at much lower temperatures compared to the conventional alkane steam reforming process (600°C), which, besides energy savings, also suppresses

unwanted decomposition reactions. More specifically, the water-gas shift reaction to H2 is thermo-dynamically favored at lower temperatures. The (liquid-phase) reforming catalyst anticipated must promote C-C bond cleavage and the water-gas shift reaction while suppressing C-O bond cleavage that may lead to further hydrogenation to CH4. Degradation of the polyols can occur via various routes. The number of possible processes involving metal and acid sites of the catalytic material, and thereby influencing the intermediate formation in case of C5 and C6 polyols, is significant. The activity and stability for the production of hydrogen and/or alkanes by APR and the composition of the products are significantly affected by the nature of the catalyst’s metal component, acidity, basicity and hydrothermal stability of the support. Group VIII metals generally show high activities in breaking C-C bonds, and thus can be effective catalysts here. Many studies have been conducted regarding APR of ethylene glycol and glycerol wherein supported precious metals (Pt, Pd, Ru, Rh, Ir) were applied. The nature of the support strongly affects the catalytic activity and product distribution via acidity and metal-support interactions. Furthermore it provides higher selectivity in APR by changing the heat of adsorption of intermediates [6]. In particular, a strong influence of the support nature was observed for Pt catalysts [7]. Studies with activated carbon or carbon nanomaterial supports indicate the notable superiority regarding the stabil i ty of carbon supported catalysts [7, 8].


Aqueous phase reforming The project combines fundamental insights for deriving catalyst material property relationships on the APR process and technical development of optimized carbon supported catalysts. Both will go hand in hand within SusFuelCat, and will enriche and guide each other. Hence, technical development for a rapid industrialization will reap maximum benefit from fundamental research, while, the fundamental research is streamlined towards the industrial needs. In the SusFuelCat approach, SMEs, multinational industry and academic partners will contribute a range of competences from theoretical studies to technical validation capabilities with the aim to identify and exploit synergistic effects leading to rapid industrialization. Using cutting edge techniques for both the carbon support and noble metal synthesis and by the integrative and interdisciplinary methodology, the outcome will be innovative carbon supported catalysts for the sustainable fuel production by APR processes.


112

Colloidal nanoparticle synthesis To synthesize controlled mono- and bimetallic nanoparticles and thus tune the catalytic center, colloidal synthesis and micro-emulsion techniques will be used in this project. These approaches can be used to study the metallic materials, both independently of and immobilized on the carbon support carbon. The control of the properties of the nanoparticles will make it possible to assess whether APR is a structure-sensitive reaction. Furthermore it will enable the optimization of the nanoparticles synthesis in order to achieve the performance demanded for the catalysts. Advanced physico-chemical techniques for in-situ and ex-situ investigations will be used at both the nanoparticle preparation stage and for characterization of the prepared catalysts and supports. A thorough insight into the structure of the active centers makes it possible to successfully resolve problems of synthesis, optimal distribution of the active component, optimization of the chemical composition and porous structure of a catalyst support. Analysis of factors determining the concentration profile of the deposited metal will allow the development of approaches to the controlled distribution of active components in catalyst grains.

Carbon materials and carbon nanomaterials The final catalytic properties also depend on the type of carbon support material. Maximizing the hydrothermal stability of carbon supports and tuning acidic functionality as well as morphology in parallel for optimal activity, selectivity and stability will go beyond state-of-the-art. The exploitation of existing knowledge on maximizing oxidation stability towards increasing hydrothermal stability, will allow for a rapid industrialization. The approach to use the novel class of porous carbons - carbide-derived carbons - as model materials for catalytic studies increases the possibility to tune the porous carbon support beyond state-of-the-art. In particular the conformal conversion process decoupling material properties from size of the precursor is advantageous.

Spectroscopy and theory In situ IR spectroscopy with attenuated total reflection (ATR) is unique in the sense that adsorbed species can be observed and characterized despite the presence of the solvent. To make this work under APR, i.e. at elevated pressures and temperatures, is a major technical challenge and successful implementation would constitute a significant breakthrough. Moreover, observation of relevant adsorbed species under these conditions would contribute vital information to the understanding of the mechanism of APR under practical conditions. The computational study of APR will go beyond state-of-the-art due to the harmonization with the

experimental work and model catalysts synthesized in the project. This will be achieved by a) the model catalysts synthesized, b) detailed characterization of the materials, c) the in situ and ex situ data from standardized experiments and d) strong coordination of all activities and alignment of experiments. In summary, the obtaining of a complete picture of the catalytic cycle and structure-performance relationships from an industrial, materials, theoretical and experimental chemistry and chemical engineering point of view will result in science-based catalyst design and optimization capabilities exceeding the current state-of-the-art and will provide a significant boost to industrialization of the APR for sustainable energy production.

5. Objectives

Energy production and supply is one of the most important requirements for a high quality of life, industrialization and civilization. Europe’s wealth and leading position in industry depends heavily on energy, for which fossil fuels remain the primary source. In addition to the huge dependency on (mainly non-European) fossil fuel exporting countries and unstable prices, fossil fuels are a limited resource whose use releases carbon dioxide, a major contributor to global warming, into the atmosphere. Hence, efficient and environmentally-friendly European based sustainable energy production will become even more pertinent in Europe. SusFuelCat aims to boost Europe’s expertise on catalysts for sustainable fuel production, especially hydrogen, by the process of aqueous phase reforming. APR is a technology that allows the catalytic conversion of low value biomass streams into biomass based fuels, with catalysts being the key stone in the process. This is the reason why SusFuelCat aims to gain fundamental material structure-property relationships for the catalyst using model supports and metal nanoparticles. In cooperation with the industrial partners a strategy will be developed to optimize APR catalysts based on this fundamental understanding and being closely related to market prices of materials and dependency on imports from outside of Europe. Hydrothermal stability will be addressed by carbon supports and studied in long-term tests. SusFuelCat focuses on the following two primary objectives:

To unleash the potential of carbon supported catalysts to establish APR as an energy efficient process to convert different biomass based streams to sustainable fuels and to decrease time to market for a commercial APR catalyst.

To generate data to allow the design and scale up of the APR process towards a further


113

demonstration level. The final target is to show the technical and economical viability of the global process, from synthesis to efficiency and durability of the nano-catalytic system.


Towards tuneable carbonaceous model material, the synthesis of porous carbons with variable pore structure (from microporous to mesoporous) was realized for powder sizes that can be employed in fixed bed experiments. This was done by using carbide-derived carbons (CDC). Furthermore, the degree of graphitization was varied from highly amorphous to pronounced graphitic crystals. A material with external surface area was prepared by establishing the synthesis and purification of platelet type carbon nano fibres (CNF-PL).

Regarding the metal model material, Pt, Pd, Re, Ru, Co and Ni nanoparticles were synthesized as colloids by various methods. Narrow particle size distributions could be achieved. Synthesis parameters to vary the sizes ranging from 0.9 to 13.7 nm were deduced. The range of particle sizes produced differ for each metal. For the most important methods the synthesis was scaled up and this resulted in only slight deviations in the properties of the nanomaterial. The stability of the colloids was tested for several weeks and proved to be excellent for Pt and Pd. Base metals showed a tendency to reoxidize.

First efforts to study the immobilization of these well-defined nanoparticles on the model supports of this project and reference carbon materials were carried out. These studies gave promising results and good stability. Furthermore, for the initial screening several variations of catalysts were prepared by classical methods on reference carbon material. To provide insight with calculations, the pathway to carry out simulation studies on the APR was paved. Therefore, exchange-correlation functionals were calibrated and tested for their accuracy for Ni, Ru, Pd, Re, Pt surfaces. It was assured that the structural features and adsorption energy for water monomer can be accurately described. The simulation was used to start a study on the nucleation of Pt, Pd and mixtures with Ni on graphene with and without vacancies. Furthermore, the adsorption of polyols (up to C4) on Ni, Ru, Pd and Re could be simulated, while for Pt challenges remain. To obtain feedback from catalytic experiments three continuous set-ups were reconfigured and set into operation to study the APR of i) C5 and C6 polyols in lab scale, ii) the APR of C1-C3 oxygenates in lab scale and iii) the long term APR of various feeds in validation scale. Technical scale sugar alcohols were prepared as feedstock for experiments. An initial screening of commercial and self-made catalysts was carried out and

specialized SusFuelCat catalysts were also tested. For xylitol, sorbitol and galactitol first structure property relationships could be deduced for Pt/C. It was proven that the carbon supports are well suited for tuning the hydrogen and alkane selectivity. Thereby materials with promising hydrogen selectivity could be identified. Furthermore, indications were found that for bulky polyols the reaction is structure sensitive and an optimum for the active metal size exists. The initial long term runs indicated a good stability of the carbon supported catalysts after a startup phase. To get first insights for hydrothermal stability the pure carbon materials were tested. For all SusFuelCat carbons an excellent stability was observed, while the stability increased even further with higher degree of graphitization.

7. Expected impact

It is expected that the project will achieve its objectives and establish fundamental structure-property relationships for carbon based APR catalysts. Important steps were carried out during the past period towards this aim. A good basis of model materials and for experimental and computational testing is set and the consortium is proven to operate efficiently in the proposed workflow. It is expected that this understanding will allow leveraging the potential of catalysts in APR. A concentration of the European expertise in industry and academia in this area, and more specifically the synthesis, production and optimization is envisaged. Through this, we believe that APR technology will enable efficient sustainable fuel production from biomass in Europe. Besides this direct impact of the project, further benefits have already become apparent for each partner. These benefits include the pronounced knowledge on well-controlled colloidal based catalysts and high quality carbonaceous materials progress on the simulation of systems and developed experimental protocols. These have the potential to be of great use in catalysis and neighbouring disciplines.


114



Bastian Etzold FAU Egerlandstrasse 3, D-91058 Erlangen, Germany

[email protected]

Dmitry Murzin AAU Domkyrkotorget 3, 20500 Abo, Finland

[email protected]

Panteleimon Panagiotou BayFOR Prinzregentenstrasse 52, D-80538 Munich, Germany

[email protected]

Irina Simakova BIC Prospect Akademika Lavrentieva 5, 630090 Novosibirsk, Russia

[email protected]

Venderbosch Robbie BTG Josink Esweg 34, 7545 PN Enschede, The Netherlands

[email protected]

Tim Schubert FC Ritter-von-Eitzenberger-Straße

24, D-95448 Bayreuth, Germany

[email protected]

Sonia Garcia JM JM Technology Centre Blount’s Court Sonning Common, RG4 9NH, UK

[email protected]

Miguel Gilarranz Redondo

UAM Calle Einstein 3, Ciudad Univ. Cantoblanco Rectorado, 28049 Madrid, Spain

[email protected]

Dario Duca UNIPA Piazza Marina 61, 90133 Palermo, Italy

[email protected]

Leon Lefferts UT Drienerlolaan 5, 7522 NB Enschede, The Netherlands

[email protected]

9. References

1. Cortright, R.D., Davda, R.R. and Dumesic, J.A., Nature, 418 (2002) 964-967. 2. Simonetti, D.A. and Dumesic, J.A., Catalysis Reviews, 51 (2009) 441-484. 3. Huber, G.W. et al., Science, 308 (2005) 1446-1450. 4. Huber, G.W., Shabaker, J.W. and Dumesic, J.A., Science, 300 (2003) 2075-2077. 5. Li, N. and Huber, G.W., Journal of Catalysis, 270 (2010) 48-59. 6. Reuel, R.C. and Bartholomew, C.H., Journal of Catalysis, 85 (1984) 63-77. 7. Wen, G. et al., International Journal of Hydrogen Energy, 33 (2008) 6657-6666. 8. Wang, X., et al., The Journal of Physical Chemistry C, 114 (2010) 16996-17002.


© 2015, FAU, Egerlandstrasse 3, D-91058 Erlangen, Germany, on behalf of the SusFuelCat consortium. SusFuelCat is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




SusFuelCat and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;














115

Tandem Electrocatalytic Reactor for energy/Resource efficiency And process intensification

Proposal full Name: Tandem electrocatalytic reactor for energy/resource efficiency and process intensification

Acronym: TERRA Call identifier: H2020-SPIRE-2014-2015/H2020-SPIRE 2015 Duration: 48 months Start date: 15/09/2015 End date: 14/09/2019 Grant Agreement n°: 677471 Total budget: 4.424.785 € Coordinator: Prof.Gabriele Centi Website: www.terraproject.it

Consortium List

Contents 1. Summary ................................................................................................................................................ 115 2. Keywords ............................................................................................................................................... 116 3. Objectives .............................................................................................................................................. 116 4. Ambition ................................................................................................................................................ 116 5. Expected impact .................................................................................................................................... 117 6. Contact informations ............................................................................................................................. 117 7. Copyright statement .............................................................................................................................. 118

1. Summary

TERRA aims to develop, from TRL 3 to 5, a tandem electrocatalytic reactor (TER) coupling an oxidation reaction to a reduction one, with thus the great potential advantage of i) saving resources and energy (needed to

produce the oxidant and reductants for the two separate reactions), and ii) intensify the process (reduce the nr. of steps, coupling two synthesis processes and especially eliminating those to prepare the oxidation and reduction agents). The proposal addresses one of SPIRE Roadmap Key Actions “New ways of targeting energy input via electrochemical”.

Partip. No Participant organisation name /Acronym Country Type

1 (Coord.) European research Institute of Catalysis aisbl / ERIC Belgium RES 2 Avantium Chemicals BV / AV Netherlands IND (SME) 3 Magneto Special Anodes BV / MAGNETO Netherlands IND (SME) 4 Gensoric GmbH / GENS Germany IND (SME) 5 HYSYTECH S.R.L. / HYS Italy IND (SME) 6 Politecnico di Torino / POLITO Italy HES 7 Centre Tecnologic de la Quimica de Catalunya / CTQC Spain RES 8 Technical University of Denmark / DTU Denmark HES



116

The TER unit may be used in a large field of applications, but will be developed for a specific relevant case: the synthesis of PEF (PolyEthylene Furanoate), a next generation plastic produced from furan di carboxylic acid (FDCA) and mono ethylene glycol (MEG). The TERRA project aims to make a step forward in this process by coupling the FDCA and MEG synthesis in a single novel TER reactor, with relevant process intensification. Between the elements of innovation of the approach are: i) operation at higher T,P than "conventional" electrochemical devices for chemical manufacturing, ii) use of noble-metal-free electrocatalysts, iii) use of novel 3D-type electrodes to increase productivity, iv) use of electrode with modulation of activity based on independent temperature control, v) possibility to utilize an external bias (from unused electrical renewable energy) to enhance flexibility of operations. In addition, in order to scale-up reactor and test under environmental relevant conditions (TRL 5), the approach in the TERRA project is to address the critical elements to pass from lab-scale experimentation to industrial prototype with intensified productivity. These developments are critical for a wider use of electrochemical manufacturing in chemical and process industries.

2. Keywords

Electrocatalysis Electrocatalytic reactor HMF oxidation Sugar hydrogenolysis

3. Objectives

The objective of this project is to develop, from TRL 3 to

5, a tandem electrocatalytic reactor coupling an

oxidation reaction to a reduction reaction, with the great

potential advantages of

- saving resources and energy (elsehow required to produce the oxidant and reductant for the two separate reactions),

- process intensification (by reduction of the number of process steps, via the coupling two synthesis processes and especially the elimination

of those related to the preparation of the oxidation and reduction reactants, namely oxygen and hydrogen, as well as the avoidance of reactant recovery and recycle process loops).

Many production sites may benefit from coupling

oxidation & reduction processes:

- bio-refineries/-factories: production of valuable chemicals or biofuels from intermediates by selective oxidation and/or reduction;

- production of fine/specialty chemicals: generally entailing many oxidation and reduction steps in the synthesis procedures;

- in the frame of industrial symbiosis and reduction of environmental impact: coupling reduction and oxidation production processes, where the latter can be the (total) oxidation of pollutants in aqueous streams to purify wastewaters.

4. Ambition

The TERRA project has a ground-breaking and innovative nature for the following main characteristics: - Tandem operations in chemical synthesis, to allow

process intensification and better use of resources and energy.

- Operation at higher temperatures (and pressure) than "conventional" electrochemical cells and use of OH

--type membranes. This allows process

intensification, operating under different (non-conventional) pH conditions, and reducing the kinetic limitations.

- Development of advanced catalytic electrodes (noble-metals-free) with a 3D-type structure to intensify the process.

- Partially decoupling the two anodic and cathodic syntheses, by introducing the possibility of temperature modulation of one of the electrodes thereby coping with localised catalyst deactivation or change of the feed conditions. Evaluation of the impact of this approach on production flexibility.

There are thus many innovative and ground-breaking elements introduced in the design of TER reactor, which is applied to a relevant industrial innovation case: intensification of the industrial PEF production. As mentioned above, the novel adaptable reactor concept may be applied also to a broader relevant industrial area, such as that of combining chemical syntheses to wastewater treatment, either oxidation of waste alternative to other AOP technologies or reduction of waste (to reduce toxicity for example by hydrodehalogenation, or to reduce nitrates). Although TERRA focuses on a specific innovation case, it has a potential broader impact on increasing sustainability of chemical production.


117

5. Expected impact

The expected impacts are:

- Reduction of at least 15% in process energy intensity and material resource use for relevant large volume industrial processes.

- Reduction of at least 15% in emissions compared to the present state of the art. Significant improvements in the flexibility and productivity of industrial processes.

Policy priorities of the Europe 2020 strategy reflect the

need to address the major concerns shared by citizens in

Europe and elsewhere. Between these, moving to a low-

carbon economy, reduce impact on environment,

improve competiveness through novel technologies and

increase resource/energy efficiency are between some

of the relevant targets, between the challenges indicated

by the SPIRE roadmap. TERRA project has a significant

impact on:

i) Environmental impact reduction (low-carbon economy, reduce impact on environment, reduce GHG emissions);

ii) Competiveness improvement; iii) Increase of resource/energy efficiency.


Scientific coordination (ERIC – UdR Messina) Prof. Gabriele Centi (project coordinator) President of ERIC University of Messina (http://ww2.unime.it/catalysis/) Salita Sperone, 31 Messina 98122, Italy Tel: +39-090-6765609 Fax: +39-090-391518 E-mail: [email protected] Skype: merlinowiz Prof. Siglinda Perathoner University of Messina (http://ww2.unime.it/catalysis/) Salita Sperone, 31 Messina 98122, Italy Tel: +39-090-6765609 Fax: +39-090-391518 E-mail: [email protected]

Management coordination (operative office in Florence & legal office in Brussels): Dr. Stefano Vannuzzi INSTM (www.instm.it) ERIC (www.eric-aisbl.eu) Via G. Giusti, 9 50121 Firenze, Italy Tel: +39-055-233-8713 (direct line) Fax: +39-055-2480111 E-mail: [email protected] Skype: [email protected] Dr. Serena Orsi ICCOM-CNR (www.iccom.cnr.it) ERIC (www.eric-aisbl.eu) Via Madonna del Piano,10 50019 Sesto Fiorentino (Firenze), Italy






118

Tel: +39-055-5225279 Fax: +39-055-5225203 E-mail: [email protected] Skype: serewinnie


© 2015, European research Institute of Catalysis aisbl / ERIC , Belgium, on behalf of the TERRA consortium. TERRA is a Collaborative project under the European Commission's 7th Framework Programme. This is an Open Access document distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Anyone is free:




TERRA and the European Commission's 7th Framework Programme must be given credit, but not in any way that suggests that they endorse you or your use of the work;




119

B. Institutions


120

Organzation full Name: Cefic asbl Acronym: CEFIC Type of Organisation: Non-profit Industry Organization Address: Ave E. Van Nieuwenhuyse 4 B1160 Brussels Country: Belgium Employees: President/Director: Hubert Mandery Website: www.cefic.org

Contents

1. Summary ................................................................................................................................................ 120 2. Keywords ............................................................................................................................................... 120 3. Description of the Organisation ............................................................................................................ 120 4. Activities and highlights in Innovation................................................................................................... 120 5. Organization (flow chart) ....................................................................................................................... 121

1. Summary

Cefic is a committed partner to EU policymakers, facilitating dialogue with industry and sharing our broad-based expertise. We represent 29,000 large, medium and small chemical companies in Europe, which directly provide 1.2 million jobs and account for 17% of world chemical production. Based in Brussels since our founding in 1972, we interact every day on behalf of our members with international and EU institutions, non-governmental organizations, the international media, and other stakeholders

2. Keywords

European Chemical Industry

Sustainable Chemistry


Our 650 members and affiliates form one of the most active networks of the business community, complemented by partnerships with industry associations representing various sectors in the value chain. Representing the entire range of chemicals production, Cefic is organised around 6 programs covering:

Energy & HSE

Industrial Policy

Legislation & Institutional Affairs

Product Stewardship

Research & Innovation

Public Affairs

Sustainability

and also around industry sectors, which look after specific issues related to individual substances or groups of substances.

The Cefic International Chemicals Management unit strengthens and coordinates European input to International Chemicals Management across Cefic programmes and its membership, and integrates it in Cefic's main activities.

Cefic is an active member of the International Council of Chemical Associations (ICCA) which represents chemical manufacturers and producers all over the world and seeks to strengthen existing cooperation with global organisations such as UNEP and the OECD to improve chemicals management worldwide.

Read More on CEFIC

4. Activities and highlights in Innovation

The Cefic Research and Innovation Program addresses innovation policy and new technologies. It also addresses research and emerging science issues such as

http://www.ce/

http://www.cefic.org/About-us/Our-Members/

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes/

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes/

http://www.icca-chem.org/

http://www.icca-chem.org/

http://www.cefic.org/About-us/Cefic/

http://www.cefic.org/About-us/Cefic/


121

endocrine disruptors, indoor air quality and human bio-monitoring.

Cefic works with other academic and industry stakeholders under the umbrella of SusChem which stands for the Sustainable Chemistry European Technology Platform which was started in 2004 between CEFIC, the Royal Society of Chemistry, Dechema, GdCh, EuropaBio and ESAB. representing the chemical and biotech industry and scientific community.

SusChem has established a Strategic Innovation and Research Agenda (SIRA) which spells out the priority topics to carry-out at a European level. The main fields are:

- Raw materials an feed-stocks: access to more renewable feed-tocks either from bio-mass or from CO2 utilization linked to development of biotechnologies, recycling of raw materials, substitution of critical raw materials.

- Resources efficiency in chemical processes through process intensification, better catalysts, industrial symbiosis, waste to resources concepts.

- Materials technologies to meet the main societal challenges for clean renewable energy sources, better energy efficiency in construction, transportation, innovative production technologies (like 3D printing) to give a few examples

Catalysts development plays a central role in many of the innovations that SusChem promotes.

SusChem consults and mobilizes its stakeholders through yearly stakeholders events (for strategy discussion) and brokerage vents (for participation to European research and innovation calls). Read More on SusChem

5. Organization (flow chart)

General Assembly

The Board and Executive Committee

National Associations Board

Cefic Leadership Team

Industry Sectors Board

Energy & HSE

Industrial Policy

Legislation & Institutional Affairs

Product Stewardship

Research and Innovation

Sustainability

Read more

http://www.suschem.org/

http://www.cefic.org/About-us/Our-Members/

http://www.cefic.org/About-us/How-Cefic-is-organised/Executive-Committee--Board/

http://www.cefic.org/About-us/How-Cefic-is-organised/The-National-Associations-Board/

http://www.cefic.org/About-us/How-Cefic-is-organised/Leadership-Team-/

http://www.cefic.org/About-us/How-Cefic-is-organised/Industry-Sectors-Board/

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#HSE

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#Industrial

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#Legis

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#Product

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#RD

http://www.cefic.org/About-us/How-Cefic-is-organised/The-Programmes#SD

http://www.cefic.org/About-us/How-Cefic-is-organised/


122

Organzation full Name: Consiglio Nazionale delle Ricerche Acronym: CNR Type of Organisation: Public Research Organization Address: Piazzale Aldo Moro, 7 - 00185, Roma Country: Italy Employees: People, their skills and ideas represent the main capital resource of the

CNR. With its huge patrimony of human resources (more than 8200 employees among researchers, technicians and administrative and more than 3000 young scientists completing their scientific training at the institution), CNR ranks in terms of scientific production, among the major contributors in Italy, with a prominent and well-consolidated scientific reputation on an international level. On this ground a significant contribution also comes from its research associates: researchers, from Universities or private firms, who take part in CNR’s research activities.

President: General Director: ECC CNR referent:

Prof. Luigi Nicolais Dr. Paolo Annunziato Dr. Giuliano Giambastiani

Website: www.cnr.it

Contents 1. Summary ................................................................................................................................................ 122 2. Keywords ............................................................................................................................................... 122 3. Description of the Organisation ............................................................................................................ 123 4. Scientific and technological challenges, objectives and scopes ............................................................ 123 5. Activities and highlights ......................................................................................................................... 123

1. Summary

The National Research Council (CNR) is the greatest research public body in Italy whose main priority is to foster, promote, spread, transfer and improve research activities in the main sectors of knowledge. By this way, CNR aims at growing and strenghtning the scientific, technological, economic and social development of the Country.

Its activity, divided into macro areas, covers all main research areas always with a highly interdisciplinary approach. Main macro areas are: chemistry, physics, biotechnology, medicine, materials, environment and land, information and communications, advanced systems of production, judicial and socio-economic sciences, classical studies and arts.

CNR is distributed all over Italy through a network of about one hundred institutes aiming at promoting a wide diffusion of its competences throughout the national

territory and at facilitating contacts and cooperation activities with local firms and organizations.

From the financial point of view, the main resources come from the central government with a relatively high percentage of its balance sheet (more than 30%) coming from: i) external contracts for studies and activities of technical advice; ii) agreements with private companies; iii) contracts with the European Union and iv) contracts with other national and international funding organizations.

2. Keywords

Keywords meet with the areas of technological and scientific research of the institution:

Chemical Sciences and Material Technologies

Earth Sciences and Environmental Technologies

Engineering and Technologies for Energy and Transport

Humanities, Social Sciences and Cultural Heritage

http://www.cnr.it/


123

Physical Sciences and Technologies of Matter

Agri-food and Biosciences

Biomedical Sciences


CNR is the largest public research institution in Italy, the only one under the Research Ministry performing multidisciplinary activities. It is structured in 7 areas of technological and scientific research (Departments) which plan, coordinate and monitor research activities of 109 Institutes located throughout the Italian territory. The Institutes are not dependent on the Departments but are autonomously responsible for their scientific research and duties. The widespread distribution of the Institutes throughout the territory, their interdisciplinary and multidisciplinary character, allow them to strongly contribute to the scientific and technological growth of each region.

The CNR Research infrastructures are mainly located within the Research Parks, grouping together institutes with related scientific tasks and allowing them to share common services. The use of some large research infrastructures is also made available to researchers coming from other scientific institutions in Italy and abroad in order to promote and foster international cooperation on specific topics of high priority as the research activity at the heart of renewable energy resources and environmental protection.

The main CNR resource is represented by its employees, their skills, commitment and ideas. This huge human capital comprises more than 8.000 people, of whom more than half are researchers and technologists. At the same time, about 3000 young researchers are engaged in postgraduate studies and research training at CNR within top-priority areas of interest.


CNR is strongly committed to strengthen the results deriving from its research activities by protecting them and promoting their transfer and their implementation in both national and international productive and social contexts.

In order to pursue these goals, CNR operates as follow:

strengthens the awareness of its researchers on intellectual property

promotes the industrial and commercial exploitation of the innovative scientific results

translates research results into technology and products while supporting patenting activities and fostering the creation of start up and spin-off entrepreneurial activities

attracts investments and participations aimed at fostering high-tech capital companies

encourages contacts between the research community and the national/international entrepreneurial organizations

promotes the dissemination of innovation favoring the creation of networks grouping together CNR, companies, industry associations and financial organizations.

Within this activity, the development of international cooperation actions by taking part to large research programs aimed at stressing its international competitiveness along with its collaboration with foreign research institutions, represent other priority issues within the CNR strategy.

Its scientific and technological cooperation activity on an international ground is performed in the following ways:

participating in the European Framework Programs for Research and Technological Development including other EU initiatives

participating in Science Europe and ESF and their international initiatives and programs

representing Italian science in international non-governmental Organizations

ensuring national participation in management and use of large international scientific facilities

fostering cooperation by means of bilateral Agreements and Memoranda with similar organizations in other countries, enhancing the exchange of researchers

Supporting visits of young researchers in labs abroad through the "Short Term Mobility" Program.


The CNR aims to enhance the entire life cycle of ideas, according to research excellence and results achieved within the seven Scientific Departments. In this framework CNR looks to the productive system, intensifying its activities in the field of technological development. It also maintains the role of national hub for Flagship Programs supported by Institutional funds. These aspects taken all together, along with other fundamental links with the current scientific and technological external landscape, build up the huge portfolio of CNR.


124

European Materials Research Society (E-MRS)

Organization full Name: European Materials Research Society Acronym: E-MRS Type of Organization: Non-profit Research Organization Address: 23 Rue du Loess - BP 20 - 67037 Strasbourg Cedex 02 Country: France Employees: 3 permanent staff, 1 General Secretary, 30 members of the Executive

Committee, 30 members of the Board of Delegates, 15 members of the Senate, over 3000 members (industry, government, academia and research laboratories)

President/Director: Paul Siffert, General Secretary Thomas Lippert, Running President until 2015 Luisa Torsi, President from January 2016

Website: www.european-mrs.com

Contents

1. Summary ................................................................................................................................................ 124 2. Keywords ............................................................................................................................................... 124 3. Description of the Organization ............................................................................................................ 124 4. Scientific and technological challenges, objectives and scopes ............................................................ 125 5. Activities and highlights ......................................................................................................................... 125 6. Organogram (flow chart) ....................................................................................................................... 125

1. Summary

Founded in 1983, the European Materials Research Society (E-MRS) now has more than 3,200 members from industry, government, academia and research laboratories, who meet regularly to debate recent technological developments of functional materials.

2. Keywords

Materials Science and Technology

3. Description of the Organization

The E-MRS differs from many single-discipline professional societies by encouraging scientists, engineers and research managers to exchange information on an interdisciplinary platform, and by recognizing professional and technical excellence by promoting awards for achievement from

student to senior scientist level. As an adhering body of the International Union of Materials Research Societies (IUMRS), the E-MRS enjoys and benefits from very close

relationships with other Materials Research organizations elsewhere in Europe and around the world.

Each year, E-MRS organizes, co-organizes, sponsors or co-sponsors numerous scientific events and meetings. The major society conference, the E-MRS Spring Meeting, is organized every year in May or June and offers on average 25 topical symposia. It is widely recognized as being of the highest international significance and is the greatest of its kind in Europe with about 3000 attendees every year. Each symposium publishes its own proceedings that document the latest experimental and theoretical understanding of material growth and properties, the exploitation of new advanced processes, and the development of electronic devices that can benefit best from the outstanding physical properties of functional materials.

In addition, a significant number of workshops towards scientists, policy makers, industrial and the general public, as well as and educational activities (e.g. Summer schools, tutorials) are organized by the society.

http://www.european-mrs.com/


125


Topics of the 2015 conferences: - Materials for energy and environment - Materials for optics and optoelectronics - Multifunctional oxides - Organic and bio-materials - Materials for advanced electronics - Advanced materials synthesis, processing and

characterization - Materials and devices for energy and

environment applications - Materials for electronics and optoelectronic

applications away from silicon - Nanomaterials, nanostructures and nano-

devices - Characterization of materials by experiments

and computing


Each year, E-MRS organizes, co-organizes, sponsors or co-sponsors numerous scientific events and meetings.

The major society conferences are:

- the E-MRS Spring Meeting, organized every year in May or June in France and offers on average 25 topical symposia. It is widely recognized as being of the highest international significance and is the greatest of its kind in Europe with about 3000 attendees every year. Each symposium publishes its own proceedings that document the latest experimental and theoretical understanding of material growth and properties, the exploitation of new advanced processes, and the development of electronic devices that can benefit best from the outstanding physical properties of functional materials.

- the E-MRS Fall Meeting, organized every year in September in Poland and offers on average 20 topical symposia, with around 1100 participants every year. The Fall Meeting provides another opportunity to get involved to scientists of Central and Eastern Europe and offers the same high quality scientific platform as the Spring Meeting.

Apart from these 2 conferences, the E-MRS has been involved in numerous STOA workshops and the organization of the World Materials Summit.

E-MRS made efforts to remedy the fragmentation of the Materials community by taking part in the initiatives EMF and MatSEEC and has also in this sense been recently involved in numerous INTERREG IV Upper Rhine, FP7 and H2020 projects on Materials (Nano@matrix, InnoMatNet, MatVal, CRMInnoNet, CEOPS, Stimulate, Eurosunmed, I-Flexis, MATCH).

In 2014, E-MRS has been granted, together with the Strasbourg University, the UNESCO Chair in Materials Sciences and Engineering.


The E-MRS is directed by the Executive Committee, a veritable "Members' House" comprising representatives from institutions all over Europe. It is this Governing Council that deliberates on the scientific activities, the use of its financial means, and elects its President and 2 vice-presidents.

The President is elected for a one year renewable mandate.

All past presidents become automatically member of the Senate.

The Board of Delegates includes Chairs of past-conferences.


126

European Research Institute of Catalysis a.i.s.b.l. (ERIC)

Organzation full Name: European Research Institute of Catalysis a.i.s.b.l. Acronym: ERIC Type of Organisation: Non-profit Research Organisation Address: Ron Point Schuman, 14 – 1040 Bruxelles Country: Belgium Employees: 13 temporary staff President/Director: Gabriele Centi , President and Legal Representative

Stefano Vannuzzi, Chief Executive Officer Website: www.eric-aisbl.eu

Contents

1. Summary ................................................................................................................................................ 126 2. Keywords ............................................................................................................................................... 127 3. Description of the Organisation ............................................................................................................ 127 4. Scientific and technological challenges, objectives and scopes ........................................................ 127 5. Activities and highlights ......................................................................................................................... 128 6. Organogram (flow chart) ....................................................................................................................... 128

1. Summary

The “European Research Institute of Catalysis A.I.S.B.L.” (ERIC) is a non-profit association founded in Belgium on November 13th, 2008 to provide long-term continuity to the Network of Excellence (NoE) IDECAT (Integrated Design of Catalytic Nanomaterials for a Sustainable Production) by creating a Durable Integration Structure.

ERIC thus shares the original aims of the NoE from which it derives, e.g. to support and foster the collaboration between the partners, but goes beyond this objective, also in terms of partnership, to become a reference center for activities in catalysis in Europe in order to create the critical mass and partnership to address the Grand Challenges of catalysis.

ERIC aims to promote all aspects of cutting edge catalysis and serve as an interface between academic, industrial and societal needs in the field.

ERIC will build a stronger link between catalysis communities to foster interdisciplinary approaches. It aims to: - bridge and facilitate interactions between Industries

and ERIC partners; - help in manage projects and intellectual property right; - be a common platform for sharing equipment and

infrastructures, knowledge and competences for

research, training and educational objectives; - be a forum for brainstorm-type activities to identify

long-term research directions and opportunities; - manage as single entity multidisciplinary and

multipartner activities to be more effective in relations with companies and international Institutions; - help in manage training and educational activities, such

as company-sponsored PhD studentships and post-doctoral research projects, or training networks; - increase visibility of catalysis as enabling science within

the scientific community and at governmental and international levels;

- act as lobby center to promote catalysis and related activities within scientific, institutional and governmental organizations.

ERIC aims to provide also services for the members, companies and catalysis community, between which: - prepare strategic white papers and scouting studies as

well as be interface for consultancy capacity; - help in the definition of strategies and actions to

protect and exploit research results; - assist companies, particularly SME’s, to expedite their

technology development and protect IP; - organize events, activities and focused training on

catalysis; - realize activities for the valorization of research results

and brokerage events;


127

- help in the preparation of research projects in the area of catalysis and related activities, as well as transform project ideas to specific applications; - be the interface for international activities, such as

participation in SPIRE initiatives, and promote lobbying activities at EU level.

ERIC seeks to be recognized as the leading expert resource in Europe for innovative research on nanotech-based catalytic materials and, through its Europe wide network of partners a single reference point of expertise and know-how for Industry. ERIC is already involved in several EU funded projects with industrial leaders such as Air Liquide, BASF, Bayertech, eni, Repsol, Sasol, Shell.

2. Keywords

- Asymmetric catalysis

- Biocatalysis

- Catalysis by coordination compounds

- Catalytic material and nanomaterials

- Catalytic reactions in organic synthesis

- Environmental catalysis

- Green and sustainable chemistry

- Sustainable energy

- Homogeneous catalysis

- Heterogeneous catalysis

- Industrial catalytic processes

- Organocatalysis

- Photocatalysis

- Polymerization catalysis

- Renewable and solar fuels

- Carbon dioxide and greenhouse gas emissions

- Sustainable production


The Network of Excellence was a funding instrument designed by the European Commission in the context of the Sixth Framework Programme for Research and Technological Development. The experience has confirmed the validity of the concept in mobilising transnational research collaborations between partners sharing a commitment to long-term integration. A key feature that differentiates this instrument from previous initiatives was the requirement to plan for perpetuation and development of the cooperation in the form of a self-sustaining Durable Integration Structure (DIS). ERIC encompasses these efforts and is the DIS in the area of

Catalysis, grouping all the key research centres in Europe in the field.

From the original 13 Founding Members, ERIC counts nowadays 21 partners, all Universities or Research centres. Although new members have to be approved by existing members and in general a pro-active strategy of expansion of the partnership is present, ERIC is an open association to all which will promote catalysis in Europe and bring new competences and expertise to the association.

The registered office for IDECAT is in Rond-Point Schuman, 14: 5° floor – Bruxelles (Belgium). The Operational Office is instead at Consorzio INSTM-Via G. Giusti, 9 –50121 Firenze (Italy).

Through the creation of a “critical mass” of knowledge, ERIC competes at the highest levels, with innovative, pure and applied research projects in order to satisfy the needs and quality standards of national, international and industrial research.

The main goals of ERIC are:

- Providing a single reference point for international partnerships and collaborations, offering the full spectrum of the best European research and facilities in the field of catalysis

- Promoting, developing and valorising interactions between academia and industries, by the implementation joint activities;

- Increasing the societal awareness on the importance of chemistry and catalysis in the future challenges, from CO2 decrease to energy saving, from public health to renewable energies by means of congresses, publications, and conferences.


ERIC scientific network is organized along the main catalysis areas: homogeneous, heterogeneous, organo- and bio-catalysis. ERIC sustainability is realized through the involvement in various internationally financed research projects of the utmost quality and the realization of specific activities for catalysis community and members. Between these, it should be remembered that ERIC will organized the Europacat 2017 event in Florence (Italy), a main bi-annual conference on catalysis.

Since its foundation, ERIC has increased the number of its members, promoting research and securing funds and financing. ERIC’s success is due to the flexibility and quality of the service provided by its personnel, which supports all research activities in the field, among its Members. Its efficiency in bringing together and


128

managing Partner’s expertise creates a virtuous circle and effectively increases their critical mass at European level.


ERIC is active in all areas of catalysis, such as homogeneous and heterogeneous catalysis, organo- and bio-catalysis, industrial catalysis, environmental catalysis, polymerization catalysis, catalysis by coordination compounds and catalytic material and nanomaterials.

All these areas are of paramount importance for a sustainable future and to grant a friendly environment for the future generations. In this respect, ERIC activities try also to create a different interaction with industry capable of narrowing the gap between academia and companies.


ERIC is governed by the General Assembly, comprising one representative from each of the 21 members, with equal voting rights. The General Assembly deliberates on the scientific activities, the use of its financial means, the approval of new members and elects its Board of Directors (BoD), President and Chief Executive Officer. The BoD is formed by 7 elected members and the CEO, and is the body in charge of putting in practice the guidelines approved by the General Assembly

The General Assembly and the BoD are convened and chaired by the President, who oversees the implementation of the General Assembly’s and BoD’s resolutions. The Director is responsible for ensuring that these resolutions are acted upon and oversees the Association's activities.


129

Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM)

Organzation full Name: Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei

Materiali Acronym: INSTM Type of Organisation: Non-profit Research Organisation Address: Via Giuseppe Giusti n. 9 – I50121 Florence Country: Italy Employees: 13 permanent staff, 6 temporary staff and over 2500 affiliated

researchers (tenured professors, research fellows, holders of research and scholarship grants and doctorate students)

President/Director: Teodoro Valente, President and Legal Representative Andrea Caneschi, Managing Director

Website: www.instm.it

Contents

1. Summary ................................................................................................................................................ 129 2. Keywords ............................................................................................................................................... 129 3. Description of the Organisation ............................................................................................................ 129 4. Scientific and technological challenges, objectives and scopes ............................................................ 130 5. Activities and highlights ......................................................................................................................... 130 6. Organogram (flow chart) ....................................................................................................................... 130

1. Summary

INSTM - Consortium of Italian Universities for the Science and Technology of Materials was established in September 1992 as a Consortium of Italian Universities with the goal to promote research activities in the field of chemistry of materials. Later it was joined by other similar institutions and expanded its interests to the science and technology of materials. Nowadays it groups 48 Italian universities, which basically represents all the universities where research on materials is carried out.

2. Keywords

Materials Science and Technology

Asymmetric catalysis

Biocatalysis

Catalysis by coordination compounds

Catalytic material and nanomaterials

Catalytic reactions in organic synthesis Environmental catalysis

Green chemistry

Homogeneous catalysis

Heterogeneous catalysis

Industrial catalytic processes

Organocatalysis

Photocatalysis

Polymerization Catalysis

Renewable fuels

Sustainable production

Ziegler-Natta catalysis


INSTM is involved in all the strategic areas of materials science and technology and promotes the research activities of its members in this field through organizational, technical and financial support.

Through the creation of a “critical mass” of knowledge, INSTM competes at the highest levels, with innovative, pure and applied research projects in order to satisfied the needs and quality standards of national, international and industrial research.

The main goals of INSTM are:



130

- to promote, coordinate and perform research, education, technological advancement in the area of material science in Italy, particularly in connection with chemistry, engineering and nanotechnology, optimising the efforts of the partner universities and supporting PhD and post doctorate activities;

- to promote the formation of centres of excellence and of the national level facilities needed to perform research and development in materials science at the highest level;

- to provide a single reference point for international partnerships and collaborations, offering the full spectrum of the best Italian research and facilities in the above areas;

- to develop and valorise exchanges between universities and industries, by supporting joint activities in order to develop solutions to industrial problems and to study new scenarios related to materials and science technology;

- to support technological transfer, spin-off activities and training for enterprises;

- to help the Italian society in understanding the topics dealing with Materials Science and Technology and underlining their important role in public health, security, energy resources and the preservation of cultural heritage, by means of congresses, publications, and conferences.


The INSTM scientific network is organized in four scientific sections (High mechanics, construction and transport; Energy and environment; Healthcare and food; Systems for processing, transmission and storage of information) and two ad hoc committees (Conservation and valorisation of cultural heritage; Computational calculus).

INSTM research groups are involved in a large number of nationally and internationally financed research projects of the ulmost quality.

Since 2004, the INSTM has internally promoted the creation of Reference Centres, establishing well-equipped laboratories, skilled research and development, which can be certified as National Reference Centres.

INSTM's charge is to unite and concentrate the efforts of its affiliates to help them become more competitive both in Italy and abroad in securing funds and financing. And it is here that INSTM excels, providing the organisational, technical and financial support necessary to promote research activities in science and technology

within its affiliate universities. Its efficiency in bringing together and managing their considerable talents creates an effective critical mass that renders them highly competitive in taking on innovative research projects. Such projects may benefit Italy's business community, or may support initiatives in the development of technology transfer, providing significant opportunities for the academic and industrial spheres to benefit from their mutual interaction.


The Consortium is active in all areas where Materials Science and Technology is of strategic importance. This includes molecular materials for electronics; photonics; polymers; composites; metals and ceramics for structural and functional applications; nanomaterials; biomaterials; protective coatings; and catalysis (homogeneous and heterogeneous catalysis; industrial catalysis; environmental catalysis; polymerization catalysis; catalysis by coordination compounds; and catalytic material and nanomaterials).

In all of these sectors, the Consortium's aim is to develop a greater knowledge base and the advanced technologies that will contribute to a better quality of life in Italy.

To date, the Consortium has participated in 5 European projects in catalysis (IDECAT, NEXT-GTL, INCAS, CARINHYPH, SOLAROGENIX). Among these projects are Integrated Design of Catalytic Nanomaterials for a Sustainable Production (IDECAT), a Networks of Excellence in catalysis coordinated by INSTM, the only Italian organisation to have been selected for this role.

INSTM's management of this network led to the formation of a structure, the European Institute of Catalysis (ERIC), with the aim of integrating this European-wide joint scientific research for the longer term.

The research initiatives in catalysis are run from approximately 39 INSTM’s Research Units in the 48 affiliated universities.

It looks forward to achieving this through its growing interaction with industry as together with its affiliates and industrial partners, it faces all of the challenges that are inherent in the development, engineering and manufacture of new products based on these new materials.


The INSTM is directed by the Governing Council, a veritable "Members' House" comprising representatives from each of the 48 member universities, each of whom holds equal voting rights. It is this Governing Council that


131

deliberates on the Consortium's scientific activities, the use of its financial means, and elects its Executive Board, President and Director. The Board, made up of 4 elected members and the Director, is INSTM's Executive Body.

The Governing Council, Executive Board and the Scientific Council are convened and chaired by the President, who also nominates the Director and oversees the implementation of the Governing Council's and Executive Board's resolutions. The Director is responsible for ensuring that these resolutions are acted upon and oversees the Consortium's activities.

The research initiatives are run from the Research Units (UdRs) in the Universities, as are the INSTM's Centres of Reference. The UdRs report to the INSTM's Fields of Research under which the Consortium's scientific network is organised. The Directors of the Fields of Research together form the Scientific Council, which

decides on the Consortium's research priorities.

compendium of the european cluster on catalysis · (water splitting, co 2 reduction, pollutant...

Documents