Ligno-cellulosic Feedstocks Conversion

State of the Technology

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

Second Gen. Biofuels

Sugar Platform Thermo-chemical Platform

Dale A. Monceaux Principal Cincinnati, Ohio, USA

Third Gen Biofuels

World Oil Consumption

Petroleum & First Generation Biofuels

World Oil Consumption

First Generation Biofuels - Production

Million Barrels per Day May, 2008 Statistics

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.

First Generation Biofuels - Feedstocks

General Comment

Oil prices increase 700% in ten years.

Corn prices increase 200% in 100 years. America can stop paying farmers not to farm. Americas migration from farms to cities will be reversed.

261 mm gpy ethanol 11.3 mm bpd gasoline

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

Second Generation Biofuels Technologies

Biomass Process Matrix
H2SO3 DILUTE ACID HCl H2SO4 ACID HYDROLYSIS H2SO4 2-STAGE PROCESS SUGAR

Second Generation Biofuel Technologies

Research & Development Areas
Sugar Platform

CONC. ACID

HCl GAS HCl LIQUID

Chemical Chemical / Biochemical

Thermochemical

LIGNOCELLULOSE FEEDSTOCKS

DILUTE H2SO4 ENZYME HYDROLYSIS

CONC. H2SO4 PRETREAT ENZYME HYDROLYSIS

SUGAR

CAUSTIC ENZ. HYDROLYSIS & FERMENTATION

Metallic Catalyst Biocatalyst

ORGANOSOLV THERMOMECHANICAL

PRODUCT

CATALYTIC REFORMING GASIFICATION SYNTHESIS FERMENTATION

PRODUCT

PRODUCT

Carbohydrate Chemistry

Simple Sugars
Monosaccharides (reducing sugars)

Second Generation - Sugar Platform Chemistry and Process Basics

Xylose, Glucose / Dextrose Fructose Sucrose, Maltose

Disaccharides

Complex Sugars
Polysaccharides

Starch, Cellulose, Hemi-cellulose, Beta-glucan, Arabinoxylan

General Carbohydrate Classes

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

Starch - Cellulose Comparison

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

H CO 3 HO O O OCH OC H3 3 OH O HO O HO OH OCH 3 H CO 3 OCH 3 OCH OCH3 3 OH O O HO OH H CO 3 OCH 3 O HO O OH OH OH O OH O HO O HO O OH OH O HO HO O O O HO O HO O OH OH O HO OH O OH OH O OH OH O HO OH O OH OH O OH O HO HO O HO O OH OO H OH O HO OO H OH O OH OH O OH O OH OH O HO O HO O OH O OH O OH O OH OH O HO O HO OH O OH O HO OH O OH O OH OH O OO H OH OH O HO O HO O OH OH OH O HO OH O OH OH O HO O HO OO H OH O HO OH O OH O OH OH O OCH 3 O OH O OH OH OCH 3 O OO H HO O HO O OH O HO HO O OH O OH O HO O HO O OH OO H OH OH O HO O HO O OH OH O OH OH O HO O HO OH O O HO OO H OO H OCH H CO 3 O OH HO O OH

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

Plant Cell Wall Model

Cellulose Crystalline Structure

Cellulose is a crystalline structure that resists water penetration

This makes disassembly very difficult since the enzymes and acid catalysts are in solution.

CHARMM 1 ns simulation SDSC DataStar John Brady, Cornell NREL subcontractor

Buckeridge et al., 2004

Detail of Water Boundary Layer

Water boundary layer is ~1.7x bulk water

Biomass Feedstocks
General Composition

Hard Hard Wood Wood

CHARMM 1 ns simulation SDSC DataStar

Soft Soft Wood Wood

Corn Corn Stover Stover

Wheat Wheat Straw Straw

Bagasse Bagasse

0 0

10 10

20 20

30 30

40 40

50 50

60 60

70 70

80 80

90 90

100 100

Wt. Wt. Percent Percent (dry (dry basis) basis)

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

Uronic Uronic Acid Acid

Ash Ash

Corn Stover Composition

Biomass Feedstocks
Improvements in Analysis
lignin protein structural inorganics soluble inorganics ash uronic acids acetyl minor sugars sucrose extractives xylan glucan

100 90 80 70 Percent Dry Weight

Corn Stover
Cellulose 33.9% Xylan 24.2%

Other Hemi. 5.2% Lignin 11.4% 9.7%

Acetyl 3.9%

Protein 1.2%

60 50 40 30 20

Extractives

(dry weight basis)

Sucrose 6.2%

Uronic Acid 4.0%

10

Ash 3.5%

0 Old methods New methods

Biomass Feedstocks
Specific Composition

Effect of Stover Compositional Variability

100

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)

Starch Hydrolysis Reaction Mechanisms

Energy + Enzyme (Alpha Amylase)

Biomass Hydrolysis Reaction Mechanisms

Substrate + H2O
Energy + Catalyst (Acid)

Product
(Xylose, Xylans, Cellulose, Lignin)

Substrate + H2O
(Starch)

Product
(Dextrins)

(Biomass = Cellulose, Hemicellulose, Lignin)

Substrate + H2O Substrate + H2O

(Dextrins)

Enzyme

Product
(Glucose)

Enzyme (Gluco Amylase) Yeast + Nutrients

Product
(Glucose)

(Cellulose)

(Cellulase Package)

Substrate Substrate
(Glucose)

Yeast + Nutrients (Cellulase Package)

Product
(Ethanol, CO2, Biomass)

Product
(Ethanol, CO2, Biomass)

(Glucose)

Substrate
(Glucose, Glucans, Xylose, Xylans)

GMO + Nutrients

Product
(Ethanol, CO2, Biomass)

PilotPilot-Scale Acid Pretreatment System

Tracking Composition and Mass

Pretreated Corn Stover Solids
60.3% 30.7% 1.9%

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%

3.6% Xylan 24.2%

Cellulose Hydrolysis

Cellulose Enzymatic Hydrolysis Reaction

Higher C6 cake solids are critical to reducing production costs.

BAGASSE

CORN STOVER

Sugar Platform Fermentations

Choices and Challenges

Second Generation Thermochemical Platform Chemistry and Process Basics

Thermochemical Pretreatment
Gasification
Process Partial combustion in controlled O2 atmosphere Types Air Oxygen Steam

Thermochemical Pretreatment
Gasification Stoichiometry

Air / Oxygen Blown Gasifier Stoichiometry

8 CH2O + O2 +(4 N2)
Biomass

6 CO + 2 CO2 + 8 H2 + (4 N2)

Steam Blown Gasifier Stoichiometry

5 CH2O + 2 H2O
Biomass

3 CO + 7 H2 + 2 CO2

Ethanol from Synthesis Gas

Catalytic Route

Ethanol from Synthesis Gas

Biological Route

Ethanol from Synthesis Gas

Biological Route

Ethanol from Synthesis Gas

Biological Route Basic Reactions

6 CO + 3 H2O 6 H2 + 2 CO2

CH3CH2OH + 4 CO2 CH3CH2OH + 3 H2O

Clostridium ljungdahlii

Tanner, et. al., 1993

Ethanol from Synthesis Gas

Biological Route - Stoichiometry
Air / Oxygen Blown Gasifier
8 CH2O + O2 + (4 N2)
Biomass

2.33 CH3CH2OH + 3.33 CO2 + H2O + (4 N2)

Theoretical Yield : 136 Gal / Dry Ton Biomass

Third Generation Biofuel Technologies

Steam Blown Gasifier

8 CH2O
Biomass

1.67 CH3CH2OH + 1.67 CO2

Theoretical Yield : 136 Gal / Dry Ton Biomass - Air Blown 155 Gal / Dry Ton Biomass - Steam Blown

Third Generation Technologies

LS9

Third Generation Technologies

DuPont / British Petroleum

Sugar GMO Fermentation Hydrocarbon properties

Virent

Sugar GMO Fermentation Hydrocarbon properties

Greenfuel Technology

Sugar Catalytic / Chemical Hydrocarbon properties

CO2 Algae Lipids and carbohydrates

Third Generation Technologies

Amyris
Lignocellulosic Sugar Platform Biodiesel Starch & Sugar Bioethanol

Sugar GMO Fermentation Hydrocarbons

Synthetic Genomics

CO2 , Carbohydrates GMO Fermentation Lipid and carbohydrates

Biodiesel Derivative Chemistries

THANK YOU

Bioethanol Derivative Chemistries

Lignocellulosic Thermochemical Platform

Anaerobic Digestion

Operations & Maintenance Management

Always remember.... .a bad day fishing is still better than a good day at work.

Thank You
CINCINNATI, OHIO, USA