Transcript PowerPoint-presentatie

From fast pyrolysis oil
to transportation fuel:
pathways
and
obstacles
1
Wolter Prins
and
Frederik Ronsse
2
Fast Pyrolysis Summary
dp < 3 mm / 500 oC / 1 atm.
pyr = 1 to 30 s
/
pyr < 2 s
15 wt.% gas
15 wt.% char
70 wt.% liquid
typical for pine wood
ga
acids, esters, aldehydes, ketones and hydroxy-carbonyls,
furans,
s
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
1 Oasmaa
et al, Energy & Fuels 2010, 24, 1380-1388
2Hoekstra
et al., AIChE Journal 2012, 8 (9) 2830-2842
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Fast Pyrolysis
EMPYRO
Hengelo NL
start: now
5 ton/hr wood waste
BTG technology
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bio-oil for Campina
steam 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
pyrolytic
lignin
pyrolysis oil
aqueous
phase
l
www.btgworld.com
organic
acids
sugar
phase
sugar phase can be fermented to
bioethanol, after acid hydrolysis,
detoxification, neutralization and
filtration
Jieni Lian et al., Bioresource Technology 101 (2010) 9688-9699
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2. Pyrolytic sugars to alkanes: APR
Pt, Ni-Sn alloys
reforming
H2 / CO2
dehydration
sorbitol
SiO2/Al2O3
225 oC
35 bar
hydrogenation
ga
intermediates
s
Pt, Pd
C1 to C6
n
?
aldol condensation
C7 to C15
G.W. Huber, R.D. Cortright and J.A. Dumesic, Angew. Chem. Int. Ed. 2004, 43, 1549-1551
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3. Bio-oil for marine engines
blending
fast
pyrolysis
bio-oil
stabilization
emulsificati
on
marine engine fuel is obtained after
stabilization (e.g. esterification) and either
1. blending with diesel and alcohols or
2. emulsification with diesel and surfactants
http://www.pfi.no/Biorefinery/Biorefinery-Projects/ReShip/
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4. Bio-oil gasification
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
Venderbosch and Prins, Handbook of Biomass Gasification, 2 nd edition,
H.A.M. Knoef (ed.), Ch. 8, pp 222 to 250
• 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
ga
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• energy efficiencies
> 80 %
• decoupling of bio-oil
production and (large-scale)
gasification is attractive
• bio-oil gasification has been
demonstrated at a
significant
scale
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4. Bio-oil gasification
bio-oil
gasifier
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
syngas
cleaning
fuel
synthesis
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
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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
examined
FCC
H-forms of zeolites: Beta, Y, ZSM-5
alumina and silica alumina
transition metal catalysts (Fe/Cr)
metal doped MCM-41 mesoporous
Yields
on
biomass basis
organic liquids:
water
gases
char
coke on catalyst
ga
s
15 to 20 wt.%
30
30
15
5 to 10
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5. Catalytic Fast Pyrolysis
Critical issues are
hydrogen deficiency in feed
low hydrocarbon yield
increased coke on catalyst
catalyst regeneration procedure
catalyst poisoning (minerals)
Research should focus on
understanding catalyst
performance, and on
experimentation in mini-plants
enabling full mass and elemental
balances plus a proper product
analysis
Ex-situ catalysis
seems 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.
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Complete deoxygenation can be achieved, but oxygens removal is not
always the ultimate goal; the oil should be made non-acid, stable and
distillable.
hydrogen:
pressures:
temperatures:
catalysts:
up to 600 L/kg bio-oil
up to 200 bar
up to 275 oC in a first stabilization step (mild HDO)
up to 400 oC in a second finishing step (full HDO)
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
H
O
% w/w
% w/w
% 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
diesel
17.2
82.4
10.7
gasoil
30.3
84.6
10.4
5.3
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
0.4 wt.%
ga
s
11.9
7.5
Christensen et al., Energy Fuels 2011, 25, 5462-5471
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5/6. CFP and HDO
100 % iso-energy line
ga
s
bio-butanol
bio-ethanol
Venderbosch, ChemSusChem 2015
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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
bio-oil entrained flow gasification
co-processing of bio-oil in FCC
catalytic fast pyrolysis and HDO
fuel for marine engines
autocatalytic reforming of bio-oil
fermentation of pyrolytic sugars
aqueous phase reforming of pyrolytic sugars
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THE END
Wolter Prins and Frederik Ronsse
Laboratory for Thermochemical Conversion of Biomass
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University of Ghent, Belgium
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http://www.ugent.be/bw/biosysteemtechniek/en
[email protected]
[email protected]