Production of Drop-in fuels from cellulosic biomass

Jesse Q. Bond, Syracuse University

UC Riverside, UMASS Amherst, UW Madison, U Delaware

Pacific Rim Biotechnology Summit

December 9, 2013

Overview

• Conceptual illustration of the challenges of drop in fuel production

• Deconstruction/Reconstruction

• Key functional groups in biomass conversion • Oxygen Removal

• C-C bond formation

• Outline a xylan/cellulose based strategy for heavy fuel production

Lignin

Hemicellulose

40-50%

25-35%

15-20%

Cellulose

Lignin

Hemicellulose

40-50%

25-35%

15-20%

Cellulose

Gasoline

Diesel Fuel

Jet Fuel

Lignin

Hemicellulose

25-35%

15-20%

40-50%

Cellulose

Gasoline

Diesel Fuel

Jet Fuel

Lignin

Hemicellulose

25-35%

15-20%

40-50%

Cellulose

Challenges

• Solid, polymeric feedstock

• High Oxygen content

• Relatively small monomers

• Complex!

Gasoline

Diesel Fuel

Jet Fuel

Cellulose

Gasoline

Diesel Fuel

Jet Fuel

Sugars

xylose

glucose

Primary Intermediates

furfural

5-HMF

levulinic acid

Secondary Intermediates

40-50%

25-35%

15-20%

Depolymerize (Hydrolysis)

Partial Oxygen removal C-C bond formation De-functionalization

Primary functional groups

Hydroxyls Carbonyls Alkenes

Heterocycles

Primary functional groups

Hydroxyls

Sugars

Polyols

Alcohols

Carbonyls Alkenes

Heterocycles

Primary functional groups

Hydroxyls

Sugars

Polyols

Alcohols

Carbonyls

Aldehydes

Ketones

Carboxylic acids

Alkenes

Heterocycles

Primary functional groups

Hydroxyls

Sugars

Polyols

Alcohols

Carbonyls

Aldehydes

Ketones

Carboxylic acids

Alkenes

Heterocycles

2-Butene ethylene

Primary functional groups

Hydroxyls

Sugars

Polyols

Alcohols

Carbonyls

Aldehydes

Ketones

Carboxylic acids

Alkenes

Heterocycles

2-Butene ethylene

MTHF DMTHF

Oxygen Removal (C-O bond cleavage) Dehydration

H+

T > 150 ○C + H2O

Oxygen Removal (C-O bond cleavage) Dehydration

H+

H+

H+

T > 150 ○C

T > 100 ○C

T > 100 ○C

+ H2O

+ H2O

+ H2O

Oxygen Removal (C-O bond cleavage)

• Acid catalyzed reactions

• Any number of materials • Aluminosilicates (SiO2-Al2O3)

• Sulfonated resins (A70)

• Mineral acids (H2SO4)

Dehydration

H+

H+

H+

T > 150 ○C

T > 100 ○C

T > 100 ○C

+ H2O

+ H2O

+ H2O

Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2

Ni, Pt, Ru

Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2

Ni, Pt, Ru

+H2

Ni, Pt, Ru

+2H2, -H2O

Ni, Pt, Ru

Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2

Ni, Pt, Ru

+H2

Ni, Pt, Ru

+2H2, -H2O

Ni, Pt, Ru

-H2O

-H2O

-H2O

H+

H+

H+

Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2

Ni, Pt, Ru

+H2

Ni, Pt, Ru

+2H2, -H2O

Ni, Pt, Ru

-H2O

-H2O

-H2O

H+

H+

H+

+H2

Ni, Pt, Ru

+H2

Ni, Pt, Ru

+H2

Ni, Pt, Ru

Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2, -H2O

Pt,Ru,Ni

+H2, -H2O

Pt, Ru, Ni

+3H2, -2H2O

RuCu, CuCrO4

Oxygen Removal (C-O bond cleavage)

• Hydrodeoxygenation • Hydrogenation (Metals)

• Saturation of C=C bonds • Convert C=O to C-OH • Cleave C-OH bonds via hydrogenolysis

• Dehydration (Acids) • Cleaves C-OH bonds • Forms C=C bonds

• Bifunctional Catalyts • Pt/SiO2-Al2O3

Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation

+H2, -H2O

Pt,Ru,Ni

+H2, -H2O

Pt, Ru, Ni

+3H2, -2H2O

RuCu, CuCrO4

Oxygen Removal (C-C bond cleavage) Decarboxylation and Decarbonylation

+ CO2 Decarboxylation

H+ or metal catalyzed

Oxygen Removal (C-C bond cleavage) Decarboxylation and Decarbonylation

+ CO + H2O

+ CO2 Decarboxylation

H+ or metal catalyzed

Decarbonylation H+ or metal catalyzed

Oxygen Removal (C-C bond cleavage)

+2H2, -H2O

Ni, Pt, Ru

-H2O

H+

+H2

Ni, Pt, Ru

Decarboxylation and Decarbonylation

+ CO + H2O

+ CO2 Decarboxylation

H+ or metal catalyzed

Decarbonylation H+ or metal catalyzed

xylose

glucose

furfural

5-HMF levulinic acid

Production of primary platforms

xylans H+

+H2O

H+

-3H2O

H+

-3H2O

H+

+2H2O, -HCOOH

H+

+H2O

cellulose

xylose

glucose

furfural

5-HMF levulinic acid

Production of primary platforms

xylans H+

+H2O

H+

-3H2O

H+

-3H2O

H+

+2H2O, -HCOOH

H+

+H2O

cellulose

Options for FFA and LA?

Aldol Condensation Base catalyst

Furfural Furfural Upgrading

Aldol Condensation Base catalyst

Furfural

Aldol Condensation Base catalyst

Furfural Upgrading

Aldol Condensation Base catalyst

Furfural

Aldol Condensation Base catalyst

Linear Alkanes C8 – C13

Metal

H2

Metal

Metal/Acid

H2

H2

Furfural Upgrading

Aldol Condensation Base catalyst

Furfural

Aldol Condensation Base catalyst

Linear Alkanes C8 – C13

Metal

H2

Metal

Metal/Acid

H2

H2

Furfural Upgrading

Aldol Condensation Base catalyst

Furfural

Aldol Condensation Base catalyst

Linear Alkanes C8 – C13

Metal

H2

Metal

Metal/Acid

H2

H2

Furfural Upgrading

Levulinic Acid

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

g-valerolactone

Levulinic Acid

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

g-valerolactone Pentenoic acid

Levulinic Acid

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

H+

g-valerolactone Pentenoic acid

Levulinic Acid

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

H+ H+

-CO2

g-valerolactone Pentenoic acid

Levulinic Acid Branched Alkanes

C12 – C20

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

H+ H+

-CO2

H+

Ni, Pt, Pd, Ru H2

g-valerolactone Pentenoic acid

Levulinic Acid Branched Alkanes

C12 – C20

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

H+ H+

-CO2

H+

Ni, Pt, Pd, Ru H2

g-valerolactone Pentenoic acid

Levulinic Acid Branched Alkanes

C12 – C20

Levulinic Acid Upgrading

4-HPA

+H2 Ru/C

-H2O H+

H+ H+

-CO2

H+

Ni, Pt, Pd, Ru H2

Summary of xylan/glucan pathway

• Furfural fuel yields presently 80% of theoretical maximum • Limiting yield: xylan losses during pretreatment

• LA fuel yields presently 70% of theoretical maximum • Relatively low selectivity in LA production

• Preliminary economics are not competitive with petroleum • Also not astronomical (MSP ~ $5.00 /gallon)

• Warrants future consideration as a pathway to distillates

Acknowledgements

• Charles Wyman (UCR) • Taiying Zhang • Rajeev Kumar

• Jim Dumesic (UW) • David Martin Alonso

• George Huber (UW) • Ani Upadhye

• Raul Lobo (UD) • Andrew Foster

• Geoff Tompsett (WPI)

• DARPA, DOE

Acknowledgements This work was supported through funding from the Defense Advanced Research Projects Agency (Surf-cat: Catalysts for Production of JP-8 range molecules from Lignocellulosic Biomass). The views, opinions, and/or findings contained in this article/presentation are those of the author/presenter and should not be interpreted as representing the official views or policies, either expressed or implied, of the Defense Advanced Research Projects Agency or the Department of Defense. In addition, this work was supported in part by the U.S. Department of Energy Office of Basic Energy Sciences and the New York State Energy Research and Development Authority (NYSERDA). References Bond, J.Q., Martin Alonso, D., and Dumesic, J.A., “Catalytic strategies for the conversion of lignocellulosic carbohydrates to fuels and chemicals,” in Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals, Wyman CE, Ed, Wiley Blackwell, Oxford, UK, 2013 Martin Alonso, D., Bond, J.Q., and Dumesic, J.A., “Catalytic Conversion of Biomass to Biofuels,” Green Chemistry, 2010, 12, 1493–1513. Bond, J.Q., et. al., Production of renewable jet fuel range alkanes and commodity chemicals from integrated catalytic processing of biomass, Energy and Environmental Science, In review.