KIT – Die Forschungsuniversität in der Helmholtz-Gemeinschaft

Institute of Catalysis Research and Technology

www.kit.edu

Strategies for biomass liquefaction,upgrading and utilizationNicolaus Dahmen

Advanced Biofuels Conference May, 17-19, 2017, Gothenburg

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Biomass liquefaction routes

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Bio-oil based fuels and chemicals

Biomass liquefaction

Biomass production

Direct thermal liquefaction

Synthetic fuels & chemicals

GasificationCO + H2

Indirect liquefaction

Biomass conditioning

Syngas cleaning & conditioningBio-oil upgrading & conditioning

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Biomass liquefaction routes

24.05.2017

Bio-oil based fuels and chemicals

Biomass liquefaction

Biomass production

Direct thermal liquefaction

Synthetic fuels & chemicals

GasificationCO + H2

Indirect liquefaction

Biomass conditioning

Syngas cleaning & conditioningBio-oil upgrading & conditioning

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Motivation

Find the best combination of bio-oil or bio-crude production and application oriented upgrading process

An attempt for systematizationBio-oil yields and propertiesUpgrading opportunitiesConcept examplesRecommendations

Upgrading Application

Bio-oilproduction

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Biochemical

Overview 1 Biomass de-polymerization principles

Chemical

Cellulases

Gluconases

Cellulosomes

Laccases

Alkaline

Acidic

Org. solvents

Ionic liquids

Carbohydrates and lignin

Thermal

Solid heat carriers

Thermo-fluids

Hydrothermal water

Cracking

Hydrotreating

Deoxygenation

Catalytical

Bio-oil, biocrude

+ aqueous phase, + solids, + gas

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Examples of bio-oil and biocrude yieldsProcess Conditions Yields / wt.%

KIT thermal fast pyrolysis (FP)

Straw, 500 °C, cy. 2 sec gas retention time 32 % bio-oil, 22 % aqueous phase, 24 % gas, 22 % solids

Catalytic fast pyrolysis (CFP)

Beech wood, 500 °C, Zeolite type catalyst 25 % bio-oil (20 % O), 40 % gas (CO, CO2), 25 % water, 20 % coke

LBL, 1984Albany, OR, US

Acid hydrolysis (H2SO4), 320-370°C, 200-280 bar, CO/H2, 20-60 min

30 % biocrude (waf), < 8.5 % H2O, 1-10 % solids

PERC, 1985 Wood in recycle oil, 320-370 °C, 200-280 bar, CO/H2, Na2CO3, 10-30 min

40 % biocrude (waf), 3 % H2O10 % solids

BFH, Hamburg,1984

Wood slurry in recycle oil, 380 °C, >100 bar H2, Pd/active carbon

36 % biocrude (waf), 25 % aqueous phase, 38 % gases, 5 % solids

Hydrosolvolysis,KIT

Lignin in tetralin, Mo, Fe/S catalyst, 300-500 °C, H2, 200-300 bar, 1 h

50 % biocrude, 30 % gas, 10 % solids10 % aqueous phase

HTU, 1990Apeldorn, NL

Wood in water, 300-350 °C, 120-180 bar, 5-20 min

45 % biocrude, 16 % gas, 25 % gas (>90 % CO2),30 % aqueous phase, 1% solids

PNNL, USA(genifuel)

Forest residue, corn stover, sewage sludge 32 % biocrude, 47 % water phase, 5 % solids

HTL (KIT, Gent) Microalgae (N. gaditana), 350 °C, 150 bar 60 % biocrude, 27 % water phase, 6 % gas phase, 1 % solids

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Different..number pf product phases,product yields,product composition and properties,

depending on…. feedstock,type of process,process conditions.

Hyd

roso

lvol

ysis

Fast

pyr

olys

isH

ydro

ther

mal

L.

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Composition of thermal fast pyrolysis oil

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!Multicomponent mixtureWater containing, low pHHigh viscosity, not distillable

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Upgrading

As little as possible, as much as required !

Tightening marine emissions legislation shakes up bunker fuel demand from 2020 With the International Maritime Organisation (IMO) confirming its proposed January 2020 start-up for the global limitation on marine sulphur oxide emissions, to 0.5% from its current 3.5% threshold, significant changes in the makeup of marine demand are anticipated. …... Hence, a combination of switching to marine diesel, blended products, low-sulphur fuel oil and/or liquefied natural gas (LNG) will be seen, along with some use of high-sulphur fuel oil.Oil Market Report 2017 (Analysis and Forecasts to 2022)

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Overview 2: Upgrading/conditioning

Physical

Downstream conditioning

Filtration

Chemical

CO2 addition*•Reduce viscosity

•Increase H2 solubility•Improve atomization

*W. Olbrich, C. Boscagli, K. Raffelt, H. Zang, N. Dahmen, J. Sauer, Catalytic HDO of pyrolysis oil over Ni-catalysts under H2 /CO2 atmosphere, Sustainable Chemical Processes 4 (2016) 1-8

Dilution by solvents

Modification by e.g. esterification

Catalytic

Zeolite Cracking

Catalytic Hydrotreating

H2 transfer solvents

Downstream and in-situ/integrated upgrading

Dehydration

Decarbonyl.

Decarboxyl.

Hydrogenation

Demethylation

Deoxygenation

Hydrogenolysis

Hydrocracking

Solvent cycle (tetralin)

Solvent reforming

Fractionation

Emulsification

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R&D workUse of model compounds

Phenol, anisole, guaiacol, sugars,“ligninic” dimers, furans, acids

Application of bio-oils/bio-crudein different process configurations

Parameters: Deoxygenation degree, H2-consumption, temperature, pressure, C-efficiency, heating value

Stabilization

H2, catalyst175-250 °C, 20

MPa, min.

Hydrodexoygenation

H2, catalyst>250 °C, 20 MPa

min.-hour

Hydrocracking

H2, catalyst>250 °C, 35 MPa

hour

Stable fragments soluble in

water

Non-polar fragments insoluble in water

> 1.0 g cm-3

Non-polar fragments

insoluble in water

< 1.0 g cm-3

Pyrolysis oil

CxHy CxHy

Methanation Methanation

Fig. adapted from: R. Venderbosch et al., Stabilization of biomass-derived pyrolysis oils, Chem. Technol. Biotechnol. 85 (2010) 674

Improve thermal and chemical stabilityIncrease heating valueImprove miscibility with hydrocarbonsReduce viscosity…….

Release of H2O, CO2

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Hydrodeoxygenation

Stabilisation

Mild HDO

Deep HDO

Figure adapted from S. Kersten et al., Options for Catalysisin the Thermochemical Conversion of Biomass into Fuels, pp. 119145

H/C molar ratio

HDO of beechwood thermalpyrolysis oilwith NiCu/Al2O3

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Available catalysts

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The classic: Transition metal sulfide catalysts: Mo with Co, Ni, and sulfur:MoS, CoMoS, NiS, NiMoS/Al2O3…Better, but expensive: Noble metal catalysts: Pt/TiO2, Ru/C, RhPt/ZrO2… Promising: non noble metal catalystsmetal bases and oxides, carbides, phosphides: NiFe/Beta, NiCu/Al2O3,MoP/Al-SBA-15, Mo2C, Mo2N…..

Mild hydrotreatment of the light fraction of fast-pyrolysis oil produced from straw over nickel-based catalystsC. Boscagli, K. Raffelt, W. Olbricht, T. Otto, J. Sauer, J.-D. Grunwaldt, Biomass and Bioenergy 87 (2015) 525

Hydrogen consumptionby mild hydrodeoxygenation

About the same HDO degreeMore hydrogenated productswith Ru/C

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Catalyst performance in HDO

340 °CD.O.D.=67-70%HHV=34-37 MJ/kgR.C. ~60%

250 °CD.O.D.=40-53%HHV=30-32 MJ/kgR.C. ~50%

C. Boscagli, Dissertation, KIT 2017

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Model substance vs. Mixtures

Mild hydrotreatment of the light fraction of fast-pyrolysis oil produced from straw over nickel-based catalystsC. Boscagli, K. Raffelt, W. Olbricht, T. Otto, J. Sauer, J.-D. Grunwaldt, Biomass and Bioenergy 87 (2015) 525

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Influence of bio-oil compositionBetter understanding required!

Nickel-based catalysts show low conversion of phenol and only cyclohexanone was detected

Nickel-based catalysts completely convert phenol to cyclohexanol

Phenol as model compound

Pyrolysis oil (straw based)

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Process related issues

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Catalyst stabilityCatalyst regeneration abilityImpuritiesCoke formationHydrogen provision and pressure requirementsProper process designLegislation aspects: Maximize transportation fuel fractionUse of by-products and residues

What now a processcould look like ?

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Concepts - Example 1

www.bioboost.eu, deliverables and final report

24.05.2017

Catalytic bio-oil upgrading by refining indedicated plants (by CERTH, NESTE)1. Catalytic fast pyrolysis2. Integrated Two-step upgrading process:

Stabilization @ 150-200°C and H2 pressures of 150-200 bar:Removal of water and acids present in CPO improving the possibility touse classic catalysts with low water tolerance and decreased corrosion riskHydrodeoxygenation and cracking 350-375 °C

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Catalytic fast pyrolysis

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5 10 15 20 25 30 35 40

Oil yield, wt%

Oil O2, wt%

Steamed ZSM‐5_newZSM‐5 w/ matrix 2468ZSM‐5 Alternative  matrix 2464Alumina  matrix 2465ZSM‐5 Based FCC 2467Alumina  Matrix CP3

Fast pyrolysis in circulated fluid bed reactor with in-situ catalytically active bed materialOxygen content is reduced on cost of bio-oil yieldCPO yield: Woody biomass > miscanthus > wheat strawGas phase mainly consist of CO2 and CO

www.bioboost.eu, deliverables and final report

Main CPO components

CERTH, Thessaloniki

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CPO upgrading

Upgraded oil product yield ca. 73 wt.%Hydrogen consumption ca. 6 wt.%Non-condensable gases 13 wt.% primarily paraffinic hydrocarbonsCP oil feed requires stabilization but even then catalyst coking is foundResults for 120 h test, Tav: 299 °C, 148 bar:

Temperature gradient tube reactor device at NESTE, Porvoo

CFP feedstock Upgraded bio-oilWater content 5 % < 0.1 %C 76.1 % 86.7 %H 7.1 % 11.1 %O 16.8 % 1.5 %HDO degree 86 %

www.bioboost.eu, deliverables and final report

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Preliminary process flow scheme

www.bioboost.eu, deliverables and final report

recycle hydrogen

water

C1-C5 gasessteam / hydrogenproduction

CO2

CPO feed

H2 productionCH4

C6-C10

C11-C20 200-280 C

80-180 bar

330-380 C150 – 200 bar

steam

steamsteam

light gases

HRSG

steam

SMR

SMR: Steam methane reformerHRSG: Heat recovery steam generatorHDO: HydrodeoxygenationHT: Hydrotreater

HT

HDO

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Acetic acid and phenols extractionintegrated upgrading from CPOProcess scheme set-up (DSM)

Acetic acid/short chain oxygenates removal Mild hydrotreatingPhenols recovery

Other relevant findingsUse of phenolic and acidic aqueous fractions havebeen proved for plywoodpanel production

Concepts – Example 2

www.bioboost.eu, deliverables and final report

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Preliminary process scheme

www.bioboost.eu, deliverables and final report

Distribution coefficientsfor acid separation:Phenol: < 0.1Cresol: > 0.03Acetic acid: 3-4

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StrategyDefine your application and product specification rangeSelect liquefaction, fractionation and upgrading scheme

Fit feedstock to catalyst requirementsFit catalyst to feedstock requirements

R&D demandBetter understanding of chemical reaction network in the complex bio-oil and biocrude mixturesAdapt and improve catalytic system to bio-based feedstockDevelop integrated process schemes and variantsComparative techno-economic studies required

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Acknowledgement

A European R&D project co-funded under contract 282873 within the Seventh Framework Programme by the European Commission.