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
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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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
24.05.2017
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
24.05.2017
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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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.
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