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Second and Third Generation Biofuels: A Review of the Chemistry, Feedstocks, Processes and Projects
AIChEAIChE-Chicago Symposium 2008 Recent Developments in Refining, Energy, and Biotechnology 22 - 23 September, 2008
Introduction
Transportation Fuels First Generation Biofuels Biofuels Technology Matrix
Feedstock
Basic Chemistry Feedstock Composition
OECD: Organization for Economic Cooperation and Development: Australia, Austria, Belgium, Canada, the Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Japan, Luxembourg, Mexico, the Netherlands, New Zealand, Norway, Poland, Portugal, Slovakia, South Korea, Spain, Sweden, Switzerland, Turkey, the United Kingdom, and the United States.
General Comment
Corn prices increase 200% in 100 years. America can stop paying farmers not to farm. Americas migration from farms to cities will be reversed.
GOOD
Exxon records $40 billion in profits - 2007. US spends $500 billion + and countless lives protecting Middle Eastern oil fields.
BAD
(1) United States Department of Agriculture, 2006-2007 Crop Year, (2) Food and Agricultural Organization of the United Nations, 2005 Crop Year
CONC. ACID
LIGNOCELLULOSE FEEDSTOCKS
SUGAR
ORGANOSOLV THERMOMECHANICAL
PRODUCT
PRODUCT
PRODUCT
Carbohydrate Chemistry
Simple Sugars
Monosaccharides (reducing sugars)
Disaccharides
Complex Sugars
Polysaccharides
Simple Sugars
5 4 1 3 2
Simple sugars
Building blocks Quick access energy
Starches
Energy storage
Cellulose, Hemicellulose
Structural
Xylose C-5
4 6
5 2 1
Glucose C-6
Starch Structure
Amylose Amylose
Amylopectin
Cellulose
Glucan Structure
Arabinoxylan Structure
Beta Glucan
Cellulose
Crystalline Cellulose
Lignin Structure
Constituents of Biomass
Lignin: 15%25%
Complex aromatic structure Very high energy content Resists biochemical conversion
OCH
O 3
OH
Hemicellulose: 23%32%
Xylose is the second most abundant sugar in the biosphere Polymer of 5- and 6-carbon sugars, marginal biochemical feed
Cellulose: 38%50%
Most abundant form of carbon in biosphere Polymer of glucose, good biochemical feedstock
OH OH
Biomass Feedstocks
General Composition
Bagasse Bagasse
0 0
10 10
20 20
30 30
40 40
50 50
60 60
70 70
80 80
90 90
100 100
Cellulose Cellulose
John Brady, Cornell
Computer Simulations of Water Structuring Adjacent to Microcrystalline Cellulose 1beta Surfaces, J.F. Matthews, C.E. Skopec, P.E. Mason, P. Zuccato, R.W. Torget, J. Sugiyama, M.E. Himmel, and J.W. Brady, Carb. Res. 341, 138-152, 2006.
Hemicellulose Hemicellulose
Lignin Lignin
Extractives Extractives
Ash Ash
Biomass Feedstocks
Improvements in Analysis
lignin protein structural inorganics soluble inorganics ash uronic acids acetyl minor sugars sucrose extractives xylan glucan
Corn Stover
Cellulose 33.9% Xylan 24.2%
Acetyl 3.9%
Protein 1.2%
60 50 40 30 20
Extractives
Sucrose 6.2%
10
Ash 3.5%
Biomass Feedstocks
Specific Composition
90
100
80
90 80 Percent Dry Weight 70 60 50 40 30 20 10 0 HARDWOOD SOFT WOOD CORN STOVER SUGAR CANE BAGASSE CORN FIBER
starch fat cutin protein ash extractives lignin uronic acids acetyl arabinan galactan mannan xylan glucan
70
Number of Occurances
60
50
40
30
20
10
0
$0 .9 6 $0 .9 8 $1 .0 0 $1 .0 2 $1 .0 4 $1 .0 6 $1 .0 8 $1 .1 0 $1 .1 2 $1 .1 4 $1 .1 6 $1 .1 8 $1 .2 0 $1 .2 2 $1 .2 4 $1 .2 6 $1 .2 8 $1 .3 0 $1 .3 2 $1 .3 4 $1 .3 6 $1 .3 8
MESP ($/gal)
Product
(Xylose, Xylans, Cellulose, Lignin)
Substrate + H2O
(Starch)
Product
(Dextrins)
Enzyme
Product
(Glucose)
Product
(Glucose)
(Cellulose)
(Cellulase Package)
Substrate Substrate
(Glucose)
Product
(Ethanol, CO2, Biomass)
Product
(Ethanol, CO2, Biomass)
(Glucose)
Substrate
(Glucose, Glucans, Xylose, Xylans)
GMO + Nutrients
Product
(Ethanol, CO2, Biomass)
Liquor
Furfural
?
2.4% Glucose Lignin 11.4% 9.7% Xylose Other Extractives Sucrose Other Hemi Uronic Acid Acetyl Ash Protein
Pretreatment
Cellulose 33.9%
6.6%
Cellulose Hydrolysis
BAGASSE
CORN STOVER
Thermochemical Pretreatment
Gasification
Process Partial combustion in controlled O2 atmosphere Types Air Oxygen Steam
Thermochemical Pretreatment
Gasification Stoichiometry
6 CO + 2 CO2 + 8 H2 + (4 N2)
3 CO + 7 H2 + 2 CO2
6 CO + 3 H2O 6 H2 + 2 CO2
Clostridium ljungdahlii
Theoretical Yield : 136 Gal / Dry Ton Biomass - Air Blown 155 Gal / Dry Ton Biomass - Steam Blown
THANK YOU
Anaerobic Digestion
Always remember.... .a bad day fishing is still better than a good day at work.
Thank You
CINCINNATI, OHIO, USA