Production of Drop-In Hydrocarbon Fuels from Cellulosic Biomass Track 3: Advanced Biofuels and Biorefinery Platforms Session 2: Monday, December 9 - 10:30 AM - 12:00 PM Moderator: Thomas Foust, National Renewable Energy Laboratory Thomas Foust, National Renewable Energy Laboratory Jesse Q. Bond, Syracuse University Charles Cai, University of California Riverside Brittany Syz, Oberon Fuels
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Production of Drop-In Hydrocarbon Fuels from Cellulosic ... BIO... · Continuous Furfural Production from Bagasse in Belle Glade, Florida - 1997 . ... Simultaneous Solvent Extraction
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Production of Drop-In Hydrocarbon Fuels from Cellulosic
Biomass
Track 3: Advanced Biofuels and Biorefinery Platforms
Session 2: Monday, December 9 - 10:30 AM - 12:00 PM
Moderator: Thomas Foust, National Renewable Energy
Laboratory
Thomas Foust, National Renewable Energy Laboratory
Jesse Q. Bond, Syracuse University
Charles Cai, University of California Riverside
Brittany Syz, Oberon Fuels
Aqueous Platforms for Conversion of Cellulosic Biomass Into “DropIn”
Hydrocarbon Fuel Precursors
Charles Cai*, Taiying Zhang, Rajeev Kumar, and Charles E. Wyman
Chemical and Environmental Engineering Department and
Center for Environmental Research and Technology (CE-CERT) University of California Riverside
Riverside, California 92507
2013 Pacific Rim Summit on Biotechnology and Bioenergy
San Diego, California December 9, 2013
• Sun Grant Initiative (NO. T0013G-H/11W-DOT-021)
• Fellowship from University of California Transportation Center (UCTC)
• DARPA through University of Massachusetts
• Ford Motor Company
• Center for Environmental Research & Technology (CE-CERT), University of California, Riverside for facilities
Acknowledgments 3
• Motivation for fuel production from biomass
• Chemistries of fuel precursor (FP) formation
• Opportunities and limitations of aqueous biomass conversion
• Our research thrusts to enhance FP production
1. Biphasic solvent system enhanced furfural and 5-HMF production
2. Single phase co-solvent enhanced furfural and levulinic acid production
• Closing thoughts
Presentation Outline 4
Aqueous Processing of Cellulosic Biomass to Fuel Precursors
5
• A renewable alternative for liquid transportation fuel is needed to reduce greenhouse gas emissions and long term sustainability of the transportation sector
• Lignocellulosic biomass is the only sustainable platform for low-cost liquid fuel production
Figure from EERE: <http://www1.eere.energy.gov/biomass/m/biochemical_processes.html>
Fuel precursors: Sugars
and dehydration products
Distribution of Lignocellulosic Biomass Cell Wall Components
6
• Cellulose – ~35-50% by weight
– Primarily composed of glucan
• Hemicellulose – Heterogeneous structure
– ~15-30% by weight
– Often predominately xylan
• Lignin/other – ~15-30% by weight
– The acid insoluble portion is commonly termed Klason lignin
Overall C5 sugar and products yield in liquid phase = 88.4 %
Overall C6 sugar and products yield in liquid phase = 52.4 %
Organic phase:
41.2% 5-HMF &
24.5% LA
Pure lignin
residue
14.95%
Aqueous phase:
acidic
Organic solvent
T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3, 9809-9819
• Miscible with water
• Low boiling point (66˚C) facilitates recovery/recycle
– 4.6% azeotrope with water
• High affinity for furfural and 5-HMF
– 21.5 partition coefficient in water
• High thermal efficiency from a single phase process
• Dissolves lignin
• Can be produced from furfural and levulinic acid as co-product
2. Use of Tetrahydrofuran (THF) as Unique Single Phase Co-Solvent
25
THF solution Water solution
5 wt% maple wood loading
26 THF Promotes Sugar Dehydration and Enhances FP Production from Maple Wood
With THF
No THF With THF
With THF
With THF
With THF
No THF
No THF
No THF
No THF
Glu
cose
, g/L
Furf
ura
l, g
/L
Lev
uli
nic
, g/L
Glu
cose
+
Xylo
se, g/L
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
Conditions: 170C
1% H2SO4, 1:1 THF:Water
11 13
87
8 2
62
0
25
50
75
100
Levulinicacid
5-HMF Furfural
% Y
ield
of
theo
reti
cal
Maple wood
12 17
82
11 3
59
0
25
50
75
100
Levulinicacid
5-HMF Furfural
Corn stover
With THFNo THF
THF is Highly Selective for Furfural and 5-HMF from Different Feedstocks
27
40% 39%
550% 466%
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
Conditions: 170C 1% H2SO4, 1:1 THF:Water
8.3 4.9
76
11 13
87
29
20
87
0
10
20
30
40
50
60
70
80
90
100
Levulinic acid 5-HMF Furfural
% Y
ield
of
theo
reti
cal
1:3 THF:Water
1:1 THF:Water
3:1 THF:Water
Increasing Solvent:Water Ratio Can Enhance Co-Production Potential and Biomass
Solubilization
28
Conditions: 170C
1% H2SO4, 1:1 THF:Water
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
0 10 20 30 40 50 60 70 80 90 100 110 120 130
0
10
20
30
40
50
60
70
80
2% H2SO
44.9 % H
2SO
4
1% H2SO
4
1.5% H2SO
4
0.5% H2SO
4
1% H2SO
4
1.5% H2SO
4
2% H2SO
4
4.9% H2SO
4LA
yie
ld(%
)
reaction time (min)
0.5% H2SO
4
1% H2SO
4
1.5% H2SO
4
2% H2SO
4
4.9% H2SO
4
0.5% H2SO
4
High Levulinic Acid Production from Hexose-Rich Pretreated Maple Wood Residue
29
75% LA yield
Reaction conditions:
• 10 wt% pretreated maple
wood (hydrothermal)
• 200 C reaction
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
Substantial Lignin Removal by Co-Solvent System
30
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
Conditions: 170C 1% H2SO4, 1:1 THF:Water
Material Balance: High Overall Recovery of FPs with THF Co-Solvent Reaction
31
C.M. Cai, T. Zhang, R. Kumar, C.E. Wyman. Green Chem., 2013,15, 3140-3145
32 THF and MIBK Enhance Furfural Yields and Allow for Unique Co-production Strategies
Process Process Type Operating
Temperat
ure (˚C)
Catalyst Substrate Furfural
Yield (%
theoretical)
Co-products
Quaker Oats Batch/Aqueou
s
153 H2SO4 Oat Hulls <50% N/A
Quaker Oats Continuous/A
queous
N/A H2SO4 Bagasse 55% N/A
Huaxia/Westp
ro
Continuous/A
queous
160-165 H2SO4 Corn Cobs 35-50% Methyl alcohol,
acetone, acetic
acid, levulinic
acid
Vedernikovs Continuous/A
queous
188 H2SO4 Wood chips 75% Acetic acid,
ethanol
Zeitsch/Supra
Yield®
Continuous/A
queous
240 H2SO4 N/A 50-70% N/A
MIBK
extraction
Batch/Aqueou
s organic
160-180 H2SO4 Corn stover
Hard woods
>85% 5-HMF, glucose,
lignin
THF co-
solvent
Batch/Aqueou
s organic
160-180 H2SO4 Corn stover
Hard woods
>85% Levulinic acid, 5-
HMF, glucose,
lignin
CM Cai, T Zhang, R Kumar, CE Wyman. 2013. Journal of Chemical
Technology and Biotechnology. 89 (1) 2-10
Closing Thoughts
• Traditional aqueous catalytic conversion of lignocellulose is limited by low yields and inefficient production
• Viable catalytic pathways for production of gasoline, jet, and diesel range fuels from biomass-derived sugars enable advancement of integrated production of fuel precursors (FPs) from biomass
• Complexity of biomass and kinetics of sugar breakdown provide interesting limitations to achieving integrated co-production of FPs.
• Our high-yield biomass-to-FP strategies: – Biphasic extraction of furfural and 5-HMF using MIBK in two stages
– Single phase co-solvent reaction using THF to produce furfural and LA in two stages
• Future modifications: – Exploration of other catalyst types
– Single phase co-solvent reaction to produce furfural and 5-HMF in a single stage