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Workpackage: Liquid biofuels
Michael Studer, BFH; Jeremy Luterbacher, EPFL
Towards diesel and jet-fuel production from lignocellulosic biomass through biological and chemical processing
11.09.16 1 [email protected]
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Subsequent biochemical and catalytic conversion of lignocellulosic biomass to diesel and jet-fuel
[email protected] 11.09.16 2
Ligno-‐cellulosic feedstock
Conversion to carboxylic acids
Conversion to alkanes and α-
olefins
Market
Cataly(c conversion
Biochemical conversion
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Bioprocessing of beech wood to lactic acid
[email protected] 11.09.16 4
Product
(Steam) pretreatment
Solids washing
Cellulose hydrolyse
Liquid detoxification
Pentose fermentation
(Intermediate) product separation
Hexose fermentation
Enzym production
Ligno-cellulose
Solid/liquid separation
Product
(Steam) pretreatment
Consolidated bioprocessing
(Intermediate) product separation
Ligno-cellulose
• Loosens-‐up cellulose lignin entanglement • Releases C5 sugars
Enzymes break solid cellulose down into glucose monomers
C5 and C6 sugars are fermented to desired product
1) Adapted from: A. Aden et al. 2002, Lignocellulosic Biomass to Ethanol Process Design and Economics U7lizing Co-‐Current Dilute Acid Prehydrolysis and Enzyma7c Hydrolysis for Corn Stover, NREL, Golden CO
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Steam pretreatment – Commercial relevance
Advantages[1,2]: § No chemicals § Particle size reduction by explosion § Simplified downstream processing
§ Moderate energy requirements; Low Capex § 11 out of 14 commercial plants (cellulosic) use steam-ex
[email protected] 11.09.16 5
[1] E Tomás-‐Pejó, M Ballesteros, MJ Negro, Bioresour Technol, 2010. [2] S Brethauer, M Studer, Chimia, 2015. [3] Biochemtex Biorefinery, Crescen(no, Italy.
[3]
[3]
[1] E Tomás-‐Pejó, M Ballesteros, MJ Negro, Bioresour Technol, 2010. [2] S Brethauer, M Studer, Chimia, 2015. [3] Biochemtex Biorefinery, Crescen(no, Italy.
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Two-stage steam pretreatment
[email protected] 11.09.16 6 [1] Balan, R. et al. , 36th Symposium on Biotechnology for Fuels and Chemicals, Bal(more USA, 2016
first stage (high xylan yield)
liquid separa(on
second stage (high glucan yield)
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Consolidated bioprocessing of carboxylic acids
7 [email protected] 11.09.16
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Consolidated bioprocessing of pretreated beech to lactic acid
[email protected] 11.09.16 8
O2
oxygen conc.
y-positionCe
llulo
lytic
en
zym
es
Released sugar
Lact
ic
acid
pretreated biomass slurry
fungal biofilm(aerobic)
yeast/bacterial biofilm (anaerobic)
dense membrane
[1] Brethauer, S. and Studer, M. Energy Environ. Sci., 2014, 7 1446
§ Integration of
§ Cellulase production § Hydrolysis § Fermentation
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Lactic acid production from pure cellulose
§ Trichoderma reesei as celluloytic enzyme producer
§ Lactobacillus pentosus as lactic acid forming microorganism
[email protected] 11.09.16 9
40
30
20
10
0
lact
ic a
cid
conc
. /gL
-1
216192168144120967248240
time /h
Cellulose concentration: 17.5g/L 35g/L 50g/L
0.64 g/g
0.58 g/g
0.54 g/g
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Lactic acid production from pretreated beech wood
§ Beech wood
§ Pretreatment § 1-stage § 230°C, 15Min § Explosive discharge § Washed § 53% w/w cellulose
§ Trichoderma reesei as celluloytic enzyme producer
§ Lactobacillus pentosus as lactic acid forming microorganism
[email protected] 11.09.16 10
20
15
10
5
0
lact
ic a
cid
conc
. /gL
-1
144120967248240
time /h
Solids loading: 1.9% 2.2% 3.9%
0.73 g/g
0.87 g/g
0.83 g/g
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Co-fermentation of cellulose and xylose to lactic acid
§ L. pentosus facultative heterofermentative microorganism
[email protected] 11.09.16 11
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Co-fermentation of 2-stage pretreated beech with continuous feed of hydrolyzate
[email protected] 11.09.16 12
§ Beech wood § 2-stage pretreatment
§ Stage 1: 180°C, § Stage 2: 230°C, 15Min § Explosive discharge
§ 2.2% w/w solids loading § Continuous feeding of
hydrolyzate § Over 100h
§ Trichoderma reesei as celluloytic enzyme producer
§ Lactobacillus pentosus as lactic acid forming microorganism
10
8
6
4
2
0
conc
entra
tion
/gL-1
216192168144120967248240
time /h
lactic acid acetic acid ethanol xylose
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Catalytic upgrading Tandem hydrogenation/dehydration of carboxylic acids to α-olefins
13 [email protected] 11.09.16
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Catalytic upgrading of lactic acid to transportation fuels
§ Requirements for α-olefin production: § Aqueous phase § Linear § No double bond migration
[email protected] 11.09.16 14
C9+ transportation fuels
Oligomerization1
Amberlyst 70
1Bond et al. Science. 2010
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Tandem hydrogenation/dehydration
§ 5% Cu/SiO2-Al2O3 (70% SiO2)
§ Flow reactor
§ Conditions: § 1.2% lactic acid in water § 240 & 270°C § H2 atmosphere § Flow rates of 10 and 100ml/Min
[email protected] 11.09.16 15
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Challenges
[email protected] 11.09.16 16
Side reactions
overhydrogenation
esterification Isomerization
double bond migration
structural rearrangement
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Catalytic upgrading of lactic acid in aqueous solvent
[email protected] 11.09.16 17
Aqueous feed: lower dehydra(on ac(vity
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Catalytic upgrading Condensation reactions of carboxylic acids to aromatics
18
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Condensation reactions of carboxylic acids
19
Ketonization:
Advantage: high selectivity Disadvantage: single condensation possible
Aldol condensation:
Advantage: multiple condensation possible no carbon loss (deoxygenation without hydrogen)
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Reaction conditions
• Catalyst 2% Cu/ZrO2
• Similar low dispersion ~5%
• ZrO2 prepared by precipitation method
• Deposition of Cu by impregnation
• Conditions 400 °C
• 10 bar H2 pressure
• Flow 0.01 ml/min
• Gas flow 20 ml/min
[email protected] 11.09.16 24
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Products
[email protected] 11.09.16 25
olefins
Aroma(c hydrocarbons
water
H2O
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Carbon balance – total carbon
[email protected] 11.09.16 26
0
5
10
15
20
25
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17
C mol (%
)
Carbon number
Carbon balance
liquid hydrocarbons gas olefins oxygenates 69.6
25.9
4.5 0
20
40
60
80
organic gas water
C mol (%
)
phase
Carbon balance
carbon distribu(on
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Cross ketonization
14
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Summary
§ SCCER enabled cross discipline project
§ Two-stage steam pretreatment was developed
§ Consolidated bioprocessing of wood to lactic acid § Up-scaled the process to 3L
§ Tandem hydrogenation/dehydration of lactic acid to α-olefins in aqueous phase
§ Aldol condensation of aceton derived from acetic acid yields jet-fuel components
[email protected] 11.09.16 28
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Acknowledgement
11.09.16 29
- Robert Balan
- Robert Shahab
- Charilaos Xiros
- Jher Hau Yeap
- Bartosz Rozmyslowicz
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Biochemical production of carboxylic acids from lignocellulosic biomass
§ Corn stover, mixed grasses, beech wood chips
§ Lactic acid, butyric acid, mixed C2 to C6 carboxylic acids
§ Optimized mixture of carboxylic acids for catalytic conversion to alkanes and olefins
§ Simple, robust, highly integrated process
[email protected] 11.09.16 30
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Catalytic upgrading of lactic acid to transportation fuels
§ Requirements for α-olefin production: § Aqueous phase § Linear § No double bond migration
[email protected] 11.09.16 31
C9+ transportation fuels
Oligomerization1
Amberlyst 70
1Bond et al. Science. 2010
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0
5
10
15
20
25
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17
C mol (%
)
Carbon number
Carbon balance
hydrocarbons oxygentates 1
0.33
0.02 0
0.2
0.4
0.6
0.8
1
1.2
ace(c acid acetone oil
O/C ra
(o
O/C ra(o
10
Carbon balance – organic phase
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Carbon balance – gas phase
11
0
5
10
15
20
25
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17
C mol (%
)
Carbon number
Carbon balance
gas olefins acetone
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Carbon balance – water phase
0
5
10
15
20
25
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17
C mol (%
)
Carbon number
Carbon balance
acetone
12
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78 80 82 84 86 88 90 92
0 2 4 6 8 10 12
Conversion
of a
cetone
(mol %)
Time (days)
Conversion Regenera(on
Conversion of acetone
-‐10 -‐9 -‐8 -‐7 -‐6 -‐5 -‐4 -‐3 -‐2 -‐1 0
0 1 2 3 4 5 6 7 8
carbon
mol (%
)
Time (days)
conversion decrease propylene yield decrease
13