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From fast pyrolysis oilto transportation fuel:
pathwaysand
obstacles
Wolter Prinsand
Frederik Ronsse
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Fast Pyrolysis Summary
dp < 3 mm / 500 oC / 1 atm.
pyr = 1 to 30 s / pyr < 2 s
15 wt.% gas15 wt.% char70 wt.% liquid typical for pine wood
acids, esters, aldehydes, ketones and hydroxy-carbonyls, furans, sugars and anydrosugars, phenols and substituted aromatics
acidic, unstable, oxygenated, aqueous, particulates, 50 % unknown, immiscible with HC’s, 50 % vac. distill. residue
regarding the oil yield and quality, critical issues are the biomass ash content1 and the vapor residence time2
2Hoekstra et al., AIChE Journal 2012, 8 (9) 2830-28421 Oasmaa et al, Energy & Fuels 2010, 24, 1380-1388
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Fast Pyrolysis
EMPYROHengelo NL
start: now5 ton/hr wood wasteBTG technology
bio-oil for Campinasteam for Akzo Nobel
other large units: Ensyn, Renfrew Ontario Canada Fortum / Valmet / VTT in Joensuu Finland
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1. Pyrolytic sugars to bioethanol: fermentation
sugar phase
organic acids
pyrolytic lignin
aqueous phase
l
pyrolysis oil
sugar phase can be fermented to bioethanol, after acid hydrolysis, detoxification, neutralization and filtration
Jieni Lian et al., Bioresource Technology 101 (2010) 9688-9699
www.btgworld.com
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2. Pyrolytic sugars to alkanes: APR
sorbitol
C7 to C15
H2 / CO2
intermediatesdehydration hydrogenation
SiO2/Al2O3 Pt, Pd
n
reforming
Pt, Ni-Sn alloys
aldol condensation?
C1 to C6
G.W. Huber, R.D. Cortright and J.A. Dumesic, Angew. Chem. Int. Ed. 2004, 43, 1549-1551
225 oC35 bar
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3. Bio-oil for marine engines
fast pyrolysis
bio-oil stabilizatio
n
emulsification
blending
marine engine fuel is obtained after stabilization (e.g. esterification) and either 1. blending with diesel and alcohols or2. emulsification with diesel and surfactantshttp://www.pfi.no/Biorefinery/Biorefinery-Projects/
ReShip/
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4. Bio-oil gasification
• fast pyrolysis is a cheap pretreatment method
• bio-oil is easy to handle• problems due to feedstock
variations are avoided• pressurization of bio-oil is
easy• bio-oil contains no ash• energy efficiencies > 80 %• decoupling of bio-oil
production and (large-scale) gasification is attractive
• bio-oil gasification has been demonstrated at a significant scale
Venderbosch and Prins, Handbook of Biomass Gasification, 2nd edition, H.A.M. Knoef (ed.), Ch. 8, pp 222 to 250
Gas composition from wood-derived bio-oil gasification in ECT’s 0.4 MW pilot plant in Sweden.
Leijenhorst et al. , Biomass & Bioenergy 2014, special issue of the European Biomass Conference held in Hamburg, June 2014
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4. Bio-oil gasification
bio-oil gasifiersyngas
cleaningfuel
synthesis
Entrained Flow Gasification• non-slagging or• slagging for bio-oil char
slurries• 40 to 60 bar; 1250 to 1450 oC• co-feeding possible
Auto-thermal Catalytic Reforming• 1 bar; 850 oC• metal catalyst• low minerals content required
Fischer Tropsch diesel• iron or cobalt as catalysts• 10 to 60 bar; 200 to 300 oC
DME • diesel substitute• further synthesis to gasoline
Alcohols• methanol, ethanol, butanol • gasoline substitute
5. Catalytic Fast Pyrolysis
The purpose of CFP is to produce a stable, largely de-oxygenated liquid, enabling the co-processing in a petrochemical refinery.At severe conditions, BTX is produced at low mass yields
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5. Catalytic Fast Pyrolysis
Reactions dehydration, decarboxylation, decarbonylation isomerization, cracking, oligomerization
Products light alkanes, furans, phenols, (poly)aromatics + coke + CO + CO2 + H2O
Catalysts FCCexamined H-forms of zeolites: Beta, Y, ZSM-5
alumina and silica aluminatransition metal catalysts (Fe/Cr)metal doped MCM-41 mesoporous
Yields organic liquids: 15 to 20 wt.% on water 30biomass basis gases 30
char 15coke on catalyst 5 to 10
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5. Catalytic Fast Pyrolysis
Critical issues arehydrogen deficiency in feedlow hydrocarbon yieldincreased coke on catalystcatalyst regeneration procedurecatalyst poisoning (minerals)
Research should focus on understanding catalystperformance, and onexperimentation in mini-plantsenabling full mass and elementalbalances plus a proper productanalysis
Ex-situ catalysisseems more appropriate
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6. Catalytic hydrodeoxygenation
Purpose: removing oxygen, reducing average molecular weight, and increasing H/C
Conditions are much more severe than in catalytic fast pyrolysis.
Naphta like product, obtained by H20 rather than by CO2 rejection.
Complete deoxygenation can be achieved, but oxygen removal is not always the ultimate goal; the oil should be made non-acid, stable and distillable.
hydrogen: up to 600 L/kg bio-oil pressures: up to 200 bartemperatures: up to 275 oC in a first stabilization step (mild HDO)
up to 400 oC in a second finishing step (full HDO)catalysts: Ru/C, CuNi/δ-Al2O3 in the first step
CoMo, NiMo on γ-alumina in the 2nd step
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6. Catalytic hydrodeoxygenation
oxygen content
type of fraction
distillate fraction% w/w
C
% w/w
H
% w/w
O
% w/w
8 wt.% lights 5.3 72.8 11.9 14.2
naphtha 19.7 73.7 11.5 14.4
jet 18.7 77.8 11.0 11.9
diesel 17.2 82.4 10.7 7.5
gasoil 30.3 84.6 10.4 5.3
0.4 wt.% lights 13.9 85.9 14.6 0.3
naphtha 30.2 86.3 13.3 0.3
jet 22.0 87.0 12.3 0.7
diesel 20.6 88.4 11.4 0.5
gasoil 13.5 88.6 11.5 0.4
Christensen et al., Energy Fuels 2011, 25, 5462-5471
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5/6. CFP and HDO
Venderbosch, ChemSusChem 2015
bio-butanol
bio-ethanol
100 % iso-energy line
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7. FCC co-processing
• Petrobras-Six 200 kg/hr FCC demo unit in São Mateus do Sul, Brazil• Co-processing 3 ton of pine derived, crude pyrolysis oil from BTG• 10/90 and 20/80 bio-oil-VGO mixtures; 400 hrs. of total testing time
• Good quality gasoline/diesel with more phenols• Coke on catalyst increased with no more than15 %• 30 % renewable carbon in the liquid product• Co-production of renewable fuel gas and LPG
Presented by Marlon Almeida at the Empyro Symposium, May 2015
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Technology Readiness Levels
fast pyrolysis
fermentation of pyrolytic sugars
autocatalytic reforming of bio-oil
bio-oil entrained flow gasification
fuel for marine engines
catalytic fast pyrolysis and HDO
aqueous phase reforming of pyrolytic sugars
co-processing of bio-oil in FCC
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THE END
Wolter Prins and Frederik Ronsse
Laboratory for Thermochemical Conversion of BiomassUniversity of Ghent, Belgiumhttp://www.ugent.be/bw/biosysteemtechniek/en
[email protected]@UGent.be