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Overview of HiPerCap results so farSecond EU-Australian workshop, Lausanne, Switzerland, November 14th 2016

Hanne Kvamsdal & Richard Blom (SINTEF)

Hanne.Kvamsdal@sintef.no, Richard.blom@sintef.no

Outline

Project overview – facts and metrics

Project objectives

Technology development in the project – some

results

Technology assessment and benchmarking

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EU project HiPerCap – some metrics

• EU-Australia twinning project

• Coordinator: SINTEF MC (Dr. Hanne Kvamsdal)

• Partners: • 13 EU partners

• 1 from Australia (CSIRO)

• 1 from Russia (TIPS)

• Duration:• 4 years, Jan 2014 - Dec 2017

• Budget:• 7.7 M€ (4.9 M€ from EU)

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http://www.sintef.no/projectweb/hipercap/

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Project objectives

• Develop environmentally benign energy- and cost-efficient

technologies for post-combustion capture

• Develop a methodology for fair comparison and benchmarking

of the technologies

• Develop technology roadmap for the two most promising

technologies

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Key focus on potential of the capture technologies

Specific objectives• Reduction of 25% energy pentalty compared to the State-

of-the-Art

Post-Combustion capturetechnologies in HiPerCap

• Absorption

• Proof-of-concept of 4 solvent concepts

• Feasibility study of bio-mimicking concept

• Adsorption

• Testing of various sorbents including "green" sorbents

• Studying two reactor systems (fixed-bed and moving-bed)

• Membrane

• Hybrid (polymer + nanoparticles) membranes

• Supported ionic liquid membranes6

Images: www.co2crc.com.au

WP4 Assessment of new and emerging technologies and processes

WP 1 Absorption

Concepts

- Catalysed systems- Low temperature

regeneration

Chemicals/materials

- Enzyme activators- Strong bicarbonate

formers- Precipitating systems

WP5 Roadmap for demonstration of selected technologies

WP 3 Membranes

Concepts

- Module design

Materials- Mixed Matrix membranes- Ionic liquids

WP 2 Adsorption

Concepts

- Monoliths- Moving bed

Materials

- Sorbent development- Carbon based- others

Project overview

WP1 ABSORPTION (LED BY TNO)

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Enzyme catalysis of CO2 absorption (led by Procede)

• Enzymes in solvents can drastically accelerate the capture of CO2. It’s an environmentally friendly promotor.

Idea

• Testing of carbonic anhydrase and develop and test an optimized process in a pilot plant

Work in the project

• Enzyme stability throughout the process and separation of the enzymes prior to desorption due to the high temperature

Challenges for this technology

• 40 wt% DMMEA + enzymes best results so far, challenges with column heights to achieve 90% capture and some safety issues with DMMEA for testing

Results so far

WP1. Absorption technologiesaddressed in HiPerCap

• Enzyme catalysis of CO2 absorption (led by Procede)

• Precipitation solvent systems (led by TNO)

• Strong bicarbonate forming solvents (Led by NTNU)

• Integration of CO2 absorption with utilization (by algae) (Led by TNO)

• Study of bio-mimicking systems (Led by SINTEF)

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Algae Biomass

Nutrients

Light

Biomass

rod ts

Makeup water

-lean

as

-ri

as

Rich solvent

Bottom Tray

Top Tray

Lean solvent

N

N

N

N

Zn

H2

O

OH

N

N

N

N

Zn

N

N

N

N

Zn OH2

I II

HiPerCap solvent #1 (HS1)

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HiPerCap 30% MEA AMP/Pz

Environmental properties (color code according to OSPAR convention)

Cyclic capacity (mol-CO2/kg solvent)Similar to

CESARBetter than MEA

Heat of absorptionLower than

MEASimilar to MEA

Thermal degradation (amine loss) 18% 56% 6 / 9 %

Oxidative degradation (amine loss) 58% 10% 7 / 30 %

Corrosion (Fe concentration, mg/l) < 3 600-900Corr. rate half of

that of MEA

CO2 recovery (%) 90 % 90 % 90%

Hipercap 30% MEA CESAR1

Spesific Reboiler duty [MJ/kg CO2]

2.77 3.62 3.02

WP1 ABSORPTION (LED BY TNO)

WP1 ABSORPTION

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Precipitation solvent systems (led by TNO)

• Regeneration of only the CO2 containing part of the solvent. Minimization of emission by the use of amino acids.

Idea

• Develop an process with the focus optimization of the absorber packing.

Work in the project

• Process control with solids present and the handling of large scale slurries.

Challenges for this technology

• Models for vapour-liquid-solid equilibria and several other thermodynamic properties developed based on experiments

• Preliminary flowsheet calculations shows thermal heat requirement of 2.4-2.5 GJ/ton CO2 (benchmark solvent is 2.8-2.9), 15% improvement

Results so far

WP1 ABSORPTION

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Strong bicarbonate forming solvents (Led by NTNU)

• Bicarbonate forming solvents with high pKa will accelerate reaction kinetics and allow for lower regeneration temperature.

Idea

• Screening activity to find promising candidates for detailed studies.

Work in the project

• There are many candidates. Low absorption rates might require a promotor (investigate connection with the enzyme task)

Challenges for this technology

• Two solvents identified, extra tests with a promoter shows promising results energetically

• The best one has some stability and environmental issues

Results so far

WP1 ABSORPTION

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Integration of CO2 absorption with utilization (by algae) (Led by TNO)

• Use al ae to “eat” t e from t e solvent loaded by t e fl e as. reate biomass as a prod t.

Idea

• Process development (algae strain, solvent, operation conditions). Test proof of concept with real flue gas.

Work in the project

• Solvent selection, optimize process conditions, resistance against impurities in flue gas.

Challenges for this technology

• Concept developed and experimentally proven

• Process model is developed for scale-up studies

Results so far

Algae Biomass

Nutrients

Light

Biomass

rod ts

Makeup water

-lean

as

-ri

as

Rich solvent

Bottom Tray

Top Tray

Lean solvent

WP1 ABSORPTION

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Study of bio-mimicking systems ( Led by SINTEF)

• Perform a fundamental study of CO2 binding mechanism in nature an determine processes for the utilization industry.

Idea

• Review and assessment of potential candidates. Perform screening experiments.

Work in the project

• Define some possible systems.

Goal

• 2 zinc complexes (bio-mimicking catalysts) synthesized and tested

• Increase in absorption rate (MDEA reference), but small compared to carbonic anhydrase (biocatalyst)

Results so far

WP2 ADSORPTION (LED BY CSIC)

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Sorbent development ( Led by CSIC)

• Development of low temperature solid sorbents, low cost and with a high surface area. Integrate them in a process.

Idea

• Production and characterization of possible candidates.

Work in the project

• Identification of materials suitable for the targeted process environment.

Challenges

• Low-temperature carbon-based solid sorbents (both particulates and structured) developed, characterized and tested

• Targeted adsorption capacities reached, experimental facilities and materials have been set up, characterization tests completed

• Exchange of two samples between CSIRO and CSIC

Results so far

MAST Carbon monolith

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 10 20 30 40 50 60 70 80 90 100

Am

ou

nt

of

CO

2ad

sorb

ed (

mm

ol g

-1)

Pressure (kPa)

0 ˚ 30 ˚ 50 ˚ 70 ˚ Toth

CO2 isot erms on MAST’s monolit

WP2 ADSORPTION (LED BY CSIC)

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Process development ( Led by CSIC)

• Develop temperature swing adsorption processes by means of fixed and circulating moving beds

Idea

• Tests in labs relevant for fixed bed and circulating bed conditions, but with real flue gas conditions at coal and NG fired power stations

• Tests in pilots with real flue gas from coal power station (TNO Maasvlakte pilot)

Work in the project

• Develop correlations describing kinetics and equilibrium relations for multi-component systems.

Challenges

• Breakthrough experiments in a lab-scale fixed bed unit with synthetic humid flue gas on carbon monoliths

• Process development based on simulation of fixed-bed cyclic process using Aspen Adsorption model parameters based on lab experiments

• Unit models for the different sections of the moving bed unit are being developed and implemented in gPROMS

Results so far

CO2 H2 N2

SCADA system

Extractor hood

Column

Activated carbon

Mix

er

Thermocouple

Back pressure regulator (BPR)

Micro-GCM

T

TC

P

Heating coil

PC

He

Gas feeding system Adsorption column Gas analysis

Fixed-bed experimental set-up

0.00

0.03

0.06

0.09

0.12

0.15

0 5 10 15 20 25 30

y CO

2

Time (min)

RN1

AD2

215SEP31

0.000

0.005

0.010

0.015

0.020

0 300 600 900 1200

y H2

O

Time (min)

RN1

AD2

215SEP31

Breakthrough curves: RN1 (granular-biomass), AD2 (monolith-biomass) and 215sep31 (monolith-resin)

WP2 ADSORPTION (LED BY CSIC)

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Process modeling ( Led by SINTEF)

• Develop process concepts for a full scale adsorption plant including the thermo-process integration with the power-plant

Idea

• Simulations to determine optimal design for integration with the power-plant

Work in the project

• High uncertainty level in the models as data from relevant pilot plant are very limited .

Challenges

• A two-stage approach for the fixed-bed is established in order to meet the recovery (85%) and purity specifications (95% dry basis) for the CO2

Results so far

MBTSA process

Task 3.1 Hybrid membrane development (NTNU, SINTEF, TNO)

Objectives

• Develop a high flux mixed matrix membrane based on incorporation of nanoparticles in a polymer and supported ionic liquid membranes.

Target: CO2 permeance of 2.5 m3(STP)/ m2 h bar

selectivity CO2/N2 above 100.

Membrane fabrication and study on transport phenomena.

Research Activities

• Study of the transport mechanism and role of the nano-sized particles.

• Tailoring nanoparticles to tune the desired membrane properties such as selectivity and flux.

Nanosized particles prepared and characterized (SINTEF & TNO)

Hybrid membranes prepared and performance tested at NTNU

• Optimization in different iteration steps for the hybrid membrane.

Expected outcome

• Hybrid membranes with targeted performance

• Dedicated permeability model based on experimental flux data over a wide range of operating conditions

WP3 MEMBRANES (LED BY NTNU)

Task 3.1 Hybrid membrane development (NTNU, SINTEF, TNO)

WP3: Membrane based technologies

SO2 durability of the HAPS-PVA/PSf membrane

• Membrane PVA:HAPS ratio equal to 1:0.4. Experiment performed over a period of 1500 hours under varying SO2 levels up to 400 ppm at atmospheric pressure at 25 °C.

• Introduction of SO2 results in a decreasing permeance behavior for all gases at a constant CO2/N2 selectivity.

• The decrease in permeance during the SO2 exposure is explained by the decrease in humidity of the feed gas mixture occurring during the SO2 exposure.

• SO2 does not have a permanent negative effect on the membrane performance under the conditions investigated

More information at: GHGT-13 POSTER SESSION A 41:"Influence of functionalised nanoparticles on CO2/ N2 separation properties of FSC gas separation membranes" Davide Venturi, University of Bologna; Thijs Peters, Nicolas Rival, Christian Simon, SINTEF; Sikander Rafiq, May-Britt Hägg*, NTNU

WP4 BENCHMARKING (LED BY DNVGL)

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Develop and apply an assessment methodology for emerging

technologies on different TRL-level

•Develop a KPI based methodology with a consistent way of scaling up to a representative scale of application.

Idea

•Define a clear base case, use defined system boundaries, modeling approach and comparison criteria. Select the two most promising technologies.

Work in the project

•Develop a fair methodology for comparison of immature and technologies at different TRL levels.

Challenges

•Methodology developed based on two stage selection process

•Reference case established and the integrated process simulated

•Starting collecting available data especially from WP1

Results so far

WP4 Approach and Workflow

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WP4 Approach and Workflow

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Capture Process

Scope 1

T ConditioningPre-

treatmentCompression

ReferencePower Plant(modified)

Scope 4

Scope 5

flue gas

Treatedflue gas

CapturedCO2Coal

Power(kWe)

Scope 2

Capture technology

Scope 0

Scope 3 Scope 3

treatedflue gas

steam

condensate

CoolingWater

WP5 ROADMAP DEVELOPMENT (LED BY UNIPER, FORMER E.ON)

• Develop a technological roadmap for the industrial demonstration of two chosen technologies. Furthermore, we also aim to identify any gaps in knowledge required for implementing the technologies at industrial pilot units.

• A plan will be made for demonstrating the technologies at an

industrial pilot plant.

• Depending on the specific technologies to be further studied,

additional activities such as experimental lab activities for improved

models and further process optimization are foreseen in order to

reduce the uncertainty in the performance data prior to the final

benchmarking.

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ACKNOWLEDGEMENTS

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Thanks to co-authors:Inna Kim1, Peter van Os2, Covadonga Pevida3, May-Britt Hägg4, Jock Brown5, Robin Irons6, and Paul Feron7

1. SINTEF Materials and Chemistry, Norway2. TNO, Netherlands3. CSIC, Spain4. NTNU, Norway5. DNVGL Oil and Gas, Norway6. UNIPER, U.K.7. CSIRO, Australia

This work is performed within the HiPerCap project. The project receives funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 608555. The industrial partners who also financially support the project are also gratefully acknowledged.

Thank you for your attention!