INTERCEPTED HYDROLYSIS STRATEGIES FOR BIOMASS REFINERIES

1
INTERCEPTED HYDROLYSIS STRATEGIES FOR BIOMASS
REFINERIES

• Dr. J. Michael Robinson
• Jessica Burrow, Robert Caudle, Luis Galvan
• The University of Texas of the Permian Basin
• Financial upport from
• The Robert A. Welch Foundation
• NREL - The National Renewable Energy Laboratory
• DOE - Basic Energy Sciences, Advanced Research
  Projects
• ATP - Texas Higher Education Coordinating Board

2
Reality What is the major US energy need? What
is the major US biomass resource?
Liquid fuels 2/3 of all U.S. energy
3
Biomass fractionation to glucosean unsuccessful
strategy. WHY?

• Complex nature of biomass resources
• Severe conditions required
• Concomitant degradation reactions
• Lack of reagent selectivity between biomass
  components
• Commercially impractical reactors
• The heart of the biomass hydrolysis problem
• the inherent reactivity of glucose
  required for fermentation
• stover C6H12O6 2 CH3CH2OH 2
  CO2
• ?53 yield, 34 carbon efficiency, NREL
  2002 design

4
Problem Solved Intercepted Hydrolysis Strategies
100
5
Intercepted Cellulose Acid Hydrolysis
1 H2SO4 170C
Intercepted cellulose
6
Reduction Rates for Pine (69 CH2O)
0.7 H3PO4
Temperature
Temperature
Theoretical Pressure
Actual Pressure
Cellulose Rate
Differential Pressure
Hemicellulose Rate
7
Biomass IDAHH Fractionation and
Polyols-to-Hydrocarbons Reductions
Fractionation
e-
HI/I2
HI/H2O
IDAHH
Polyols
Biomass
Reduction 117 ºC, 1 h
H3PO4 0.7 185 ºC, 3 h 50 atm H2
100
C12 - C18 Hydrocarbons
Halogen Removal NaOH
e-
Ru/C
Lignin
8
Biomass Refinery via IDAHH
Biomass
H hydrolysis
lt180C
lt140C
Solid Residue
C5 sugars
C6 sugars
Lignin
H2 /Cat
H2 /Cat
C5 Polyols
C6 Polyols
H2 /Cat
HI/e-
H2 /Cat
Phenols
Hydrogen
Alcohols
Hydrocarbons
(Robinson, 2005 in progress)
Dumesic, 2002
Abreau, 1995
Robinson, 1996
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Biomass Refinery via IDAH Ox/Red
Biomass
H hydrolysis
lt180C
lt140C
Solid Residue
C5 sugars
C6 sugars
Lignin
O2 /Cat
H2 /Cat
C5 Acids
C6 Polyols
H2 /Cat
HI/e-
HI/e-
Phenols
Lactones
Hydrocarbons
(in progress)
(patent pending, 2004)
Robinson, 1996
10
Hemicellulose to Lactones
Valerolactones

85
Xylonic acid
15
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FUEL PRODUCTS VALUES

• HYDROCARBONS
• Compound Formula bp C BON
  Cetane
• Hexane C6H14 69 (solvent)
• Dimers C12H22 200
  78(83)
• Trimers C18H32 290
  25(30)
• OXYGENATES
• Methanol CH4O 65 101
• Ethanol C2H6O 78 115
• C5-lactone C5H8O2 208 113
• C6-lactone C6H10O2 219
  108 38

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INTERCEPTED HYDROLYSIS STRATEGIES FOR BIOMASS
REFINERIES

• IDAH Benefits
• Hydrolysis Problem Solved
• 100 Carbon efficiency
• Reactions in water
• Catalyzed chemical rxns
• Reagents recycled
• Only H2 or O2 or e- consumed
• H2 from carbohydrates
• Economical

• Valuable Products
• Polyols
• Gluconates
• Solvents (hexane)
• Liquid fuels
• gasoline, diesel, jet
• Alcohols
• Lactones
• Alkanoic Acids
• Polymers
• Phenols

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Strategy Question?

• Since the estimated cost range is
  0.45- 0.90/gal over a dozen products,
• and the amount of liquid is 200,
• vs biomass-glucose-ethanol process,
• then what strategy is most appropriate?
• IDAH?