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
25-35% 40-50% Cellulose 15-20% Lignin Hemicellulose
25-35% 40-50% Cellulose 15-20% Lignin Gasoline Hemicellulose Jet Fuel Diesel Fuel
25-35% 40-50% Cellulose 15-20% Lignin Gasoline Hemicellulose Jet Fuel Diesel Fuel
25-35% 40-50% Cellulose 15-20% Lignin Challenges Solid, polymeric feedstock High Oxygen content Relatively small monomers Hemicellulose Complex! Gasoline Jet Fuel Diesel Fuel
25-35% 40-50% Cellulose 15-20% Depolymerize (Hydrolysis) Sugars xylose Partial Oxygen removal C-C bond formation De-functionalization Primary Intermediates Secondary Intermediates Gasoline furfural levulinic acid Jet Fuel glucose 5-HMF Diesel Fuel
Primary functional groups Hydroxyls Carbonyls Alkenes Heterocycles
Primary functional groups Hydroxyls Carbonyls Alkenes Sugars Polyols Heterocycles Alcohols
Primary functional groups Hydroxyls Carbonyls Alkenes Sugars Aldehydes Polyols Ketones Heterocycles Alcohols Carboxylic acids
Primary functional groups Hydroxyls Carbonyls Alkenes Sugars Aldehydes 2-Butene ethylene Polyols Ketones Heterocycles Alcohols Carboxylic acids
Primary functional groups Hydroxyls Carbonyls Alkenes Sugars Aldehydes 2-Butene ethylene Polyols Ketones Heterocycles Alcohols Carboxylic acids MTHF DMTHF
Oxygen Removal (C-O bond cleavage) Dehydration T > 150 C + H 2 O
Oxygen Removal (C-O bond cleavage) Dehydration T > 150 C + H 2 O T > 100 C + H 2 O T > 100 C + H 2 O
Oxygen Removal (C-O bond cleavage) Dehydration T > 150 C T > 100 C + H 2 O + H 2 O Acid catalyzed reactions Any number of materials Aluminosilicates (SiO 2 -Al 2 O 3 ) Sulfonated resins (A70) Mineral acids (H 2 SO 4 ) T > 100 C + H 2 O
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2 Ni, Pt, Ru
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2 Ni, Pt, Ru +H 2 Ni, Pt, Ru +2H 2, -H 2 O Ni, Pt, Ru
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2 Ni, Pt, Ru -H 2 O +H 2 Ni, Pt, Ru -H 2 O +2H 2, -H 2 O Ni, Pt, Ru -H 2 O
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2 Ni, Pt, Ru -H 2 O +H 2 Ni, Pt, Ru +H 2 Ni, Pt, Ru -H 2 O +H 2 Ni, Pt, Ru +2H 2, -H 2 O Ni, Pt, Ru -H 2 O +H 2 Ni, Pt, Ru
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2, -H 2 O Pt,Ru,Ni +H 2, -H 2 O Pt, Ru, Ni +3H 2, -2H 2 O RuCu, CuCrO 4
Oxygen Removal (C-O bond cleavage) Hydrogenation, Hydrogenolysis, and Hydrodeoxygenation +H 2, -H 2 O Pt,Ru,Ni +H 2, -H 2 O Pt, Ru, Ni +3H 2, -2H 2 O RuCu, CuCrO 4 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/SiO 2 -Al 2 O 3
Oxygen Removal (C-C bond cleavage) Decarboxylation and Decarbonylation Decarboxylation or metal catalyzed + CO 2
Oxygen Removal (C-C bond cleavage) Decarboxylation and Decarbonylation Decarboxylation or metal catalyzed + CO 2 Decarbonylation or metal catalyzed + CO + H 2 O
Oxygen Removal (C-C bond cleavage) Decarboxylation and Decarbonylation Decarboxylation or metal catalyzed + CO 2 Decarbonylation or metal catalyzed + CO + H 2 O +2H 2, -H 2 O Ni, Pt, Ru -H 2 O +H 2 Ni, Pt, Ru
Production of primary platforms xylans +H 2 O -3H 2 O xylose furfural cellulose +H 2 O glucose -3H 2 O +2H 2 O, -HCOOH 5-HMF levulinic acid
Production of primary platforms xylans +H 2 O -3H 2 O xylose furfural Options for FFA and LA? cellulose +H 2 O -3H 2 O +2H 2 O, -HCOOH glucose 5-HMF levulinic acid
Furfural Furfural Upgrading Aldol Condensation Base catalyst
Furfural Furfural Upgrading Aldol Condensation Base catalyst Aldol Condensation Base catalyst
Furfural Furfural Upgrading Aldol Condensation Base catalyst Metal H 2 Aldol Condensation Base catalyst Metal/Acid H 2 Linear Alkanes C 8 C 13 Metal H 2
Furfural Furfural Upgrading Aldol Condensation Base catalyst Metal H 2 Aldol Condensation Base catalyst Metal/Acid H 2 Linear Alkanes C 8 C 13 Metal H 2
Furfural Furfural Upgrading Aldol Condensation Base catalyst Metal H 2 Aldol Condensation Base catalyst Metal/Acid H 2 Linear Alkanes C 8 C 13 Metal H 2
Levulinic Acid Upgrading Levulinic Acid +H 2 Ru/C 4-HPA
Levulinic Acid Upgrading Levulinic Acid +H 2 Ru/C 4-HPA -H 2 O g-valerolactone
Levulinic Acid Upgrading Levulinic Acid +H 2 Ru/C 4-HPA -H 2 O g-valerolactone Pentenoic acid
Levulinic Acid Upgrading Levulinic Acid +H 2 Ru/C 4-HPA -H 2 O -CO 2 g-valerolactone Pentenoic acid
Levulinic Acid Upgrading Levulinic Acid Branched Alkanes C 12 C 20 +H 2 Ru/C H 2 Ni, Pt, Pd, Ru 4-HPA -H 2 O -CO 2 g-valerolactone Pentenoic acid
Levulinic Acid Upgrading Levulinic Acid Branched Alkanes C 12 C 20 +H 2 Ru/C H 2 Ni, Pt, Pd, Ru 4-HPA -H 2 O -CO 2 g-valerolactone Pentenoic acid
Levulinic Acid Upgrading Levulinic Acid Branched Alkanes C 12 C 20 +H 2 Ru/C H 2 Ni, Pt, Pd, Ru 4-HPA -H 2 O -CO 2 g-valerolactone Pentenoic acid
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.