Production of Drop-In Hydrocarbon Fuels from Cellulosic

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

Smith, J.C., DOE. SciDAC review.

<http://www.scidacreview.org/0905/html/biofuel.html>

Biorefineries Could Produce Multiple Products from Lignocellulosics

Figure adapted from C. E. Wyman. ACS Conference. Washington, DC. (1990)

7

Biorefineries Could Produce Multiple Products from Lignocellulosics

Figure adapted from C. E. Wyman. ACS Conference. Washington, DC. (1990)

8

Production of Fuel Precursors from Cellulosic Biomass

9

86

119

131

130

RON BP

80C

93C

63C

78C

9

Degradation products are expected from highly reactive intermediates

Adapted from Weingarten, R. et. al Green Chem., 2010, 12, 1423–1429

10

OOH

OH

OHOH

n

OOH

OH

OH

OHOH

O

O H OH

OH+ H+ H+

Xylan Xylose Furfural Formic acid

Glucan Glucose 5-HMF Levulinic acid + Formic acid

O

O

OHOH

O

OH OH

O

O

OHOH

OH

OH

OH

O

OH

*OH

OH

O

O

OHOH

O *

OH

n H+ H+

H+

+

Highly reactive species

11 Current and Past Processes for

Furfural Production 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

CM Cai, T Zhang, R Kumar, CE Wyman. 2013. Journal of Chemical Technology

and Biotechnology. 89 (1) 2-10

Quaker Oats Batch Process

1. Mixer, 2. Reactor, 3. Screw Press, 4. Secondary Steam Generator, 5. Azetropic Distillation Column, 6. Decanter, 7. Condensers, 8. Recovery Column for low Boilers, 9. Furfural Dehydration Column.

HPS=High pressure Steam, LPS=Low Pressure Steam

12

Continuous Furfural Production from Bagasse in Belle Glade, Florida - 1997

Belle Glade Reactor Tubes - 1998

Issues with Current Technology

• Competition from low-priced Chinese furfural

• Equipment and particularly feeder lifetime

• High energy cost

– 25-30 t-steam/t-furfural for reaction and furfural recovery

• Limited furfural yields (<60% molar yields)

• Low value use of cellulose: mostly burned

15

• Maple wood chips and corn stover (1mm particle size, air dried)

• Sulfuric acid catalyst

• Organic solvents used:

– Methyl Isobutyl Ketone (MIBK)

– Tetrahydrofuran (THF)

• Reactor: 1 L Hastalloy Parr reactor

• Analysis by HPLC with Aminex HPX-87H/P column

Materials and Methods 16

Furfural Yields in Typical Aqueous Reaction with Sulfuric Acid

30 35 40 45 50 55 60

0

10

20

30

40

50

60

70

5-HMFLevulinic

Xylose

yie

ld (

%)

Reaction time (min)

Glucose

Xylose

Levulinic

5-HMF

Furfural

FurfuralFurfural

5-HMF

Xylose

Levulinic

acid

17

Major C6 Product is Glucose

30 35 40 45 50 55 60

0

10

20

30

5-HMF

Levulinic

Glucose

yie

ld (

%)

Reaction time (min)

Glucose

Levulinic

5-HMF

Glucose

5-HMF

Levulinic acid

18

19

• Hemicellulose is more readily hydrolyzed than cellulose

• LA is more stable product from glucose than 5-HMF

• Preservation of the least stable FP is crucial to maximize overall yields

• Two-stage reaction may be beneficial

– First: Furfural and 5-HMF production

– Second: LA production

From J.P. Lange et. al, ChemSUSChem. (2012). 5:150-166

Kinetics Limit Co-Production of Fuel Precursors from 5 and 6 Carbon Sugars

1. Increase Yields with 2 Phase Reaction and Simultaneous Organic Solvent Extraction

• Immiscible organic solvent, e.g., methyl isobutyl ketone (MIBK) was used

• Furfural partitions to organic phase – Furfural degradation limited in organic phase

– Furfural solubility in each phase governs degradation

• Mineral acid remains primarily in aqueous phase for recycle

– Hydrolysis, dehydration, and decarboxylation reactions require H+

– Hydrolysis and dehydration occur in aqueous phase

20

5 wt% maple wood loading based

on aqueous phase

MIBK

Aqueous

20

20 30 40 50 60 70 80

0

10

20

30

40

50

60

70

80

90

Total furfural in both phases

Furfural in aqueous phase

Furf

ura

l yie

ld (

%)

Reaction time (min)


Furfural in organic phase

Total furfural in both phases


Simultaneous Solvent Extraction by MIBK Improves Furfural Yields

Total furfural in both phases Total furfural in both phases



84% yield

21

Reaction condition: 0.1M H2SO4 at 170oC

T. Zhang, R. Kumar, C.E. Wyman, RSC Adv., 2013, 3, 9809-9819

20 30 40 50 60 70 80

0

10

20

30

40

50

60

70

80

90

Glucose

Xylose

Levulinic

5-HMF

Yie

ld (

%)

Reaction time (min)

Glucose

Xylose

Levulinic

5-HMF

Furfural

Furfural

Simultaneous Solvent Extraction by MIBK Improves 5-HMF Yields

22



Effect of Solvent on Composition of Residual Solids

30 40 50 600

10

20

30

40

50

60

70

80

90

100

soli

d f

ro

m 1

00

g

ma

ple

wo

od

reaction time (min)

other

xylan

glucan

lignin/humins

40 50 60 70 80

soli

d f

ro

m 1

00

g

ma

ple

wo

od

reaction time (min)

other

xylan

glucan

lignin

0

20

40

60

80

100

Raw


No Solvent With Solvent


Biphasic FF

production

20g raw

maple wood,

380g 0.1 N

H2SO4

Organic solvent

Organic phase: Organic

phase: 81.8% furfural,

30.6% 5-HMF, 6.0% LA

24

Solid residue with

aqueous phase:

32.5% yield (53%

glucan & 46% lignin)

Material Balance: Furfural, HMF, and LA • Biphasic furfural production: Parr reactor, 170oC, 50 min, 0.1M H2SO4, 5% solid loading

• Biphasic furfural production: Parr reactor, 170oC, 60 min, 0.1M H2SO4, 5% solid loading

Overall furfural yield = 84.3 %

Overall 5-HMF yield = 51.3 %

Overall levulinic acid yield = 19.0 %

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


• 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%


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


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


Substantial Lignin Removal by Co-Solvent System

30


Conditions: 170C 1% H2SO4, 1:1 THF:Water

Material Balance: High Overall Recovery of FPs with THF Co-Solvent Reaction

31


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

33

Past and Present Aqueous Phase Biomass

Processing Team

Bin Yang

Xia Li Michael Brennan

Chaogang Liu

Matthew Gray Suzanne

Stuhler Todd Lloyd Sigrid

Jacobsen

Rajeev Kumar

Deidre Willies

John Hannon

John Bardsley

Jonathan Mielenz

Jian Shi

Qing Qing

Mirvat Ebrik

Heather McKenzie

Jiacheng Shen

Taiying Zhang

Jaclyn DeMartini

Deepti Tanjore

Yi Jin

Michael Studer

Simone Brethauer

Charles Cai

Yueh-Du Tsai

Nikhil Nagane

Xiadi Gao

Hongjia Li

Samarthya Bhagia

Vanessa Lutzke

Jerry Tam

May-Ling Lu

Rachna Dhir

Questions?

Documents

Production of Drop-In Hydrocarbon Fuels from Cellulosic