National Renewable Energy Laboratory

Bioethanol: A Renewable Transportation Fuel from Biomass

Cynthia Riley Biotechnology Division for Fuels and Chemicals National Bioenergy Center
AIChE Spring Conference March 12, 2002
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel

Outline
Energy for Transportation Life Cycle Assessment Biomass Resources Ethanol Production Process
Biomass Hydrolysis Chemical Enzymatic Fermentation

Future The Biorefinery

U.S. Primary Energy Consumption - 1999

45 40 35

Nuclear

Quads/Yr

30 25 20 15 10 5 0 Residential Com m ercial Industrial Transportation

Renew ables

Petroleum -- Imported

Petroleum -- Domestic

Nat. Gas -- Imported

Nat. Gas -- Domestic

Coal

Sector of the Economy

Just under 7% of all energy consumed in U.S. is for non-fuel purposes.

U.S. Oil Imports and Prices

What is bioethanol?
Fuel ethanol made from non food biomass sources Requires new technology:
To break down (hydrolyze) cellulose and hemicellulose to sugar To ferment unusual sugars in biomass

Potential Midterm U.S. Biomass Supply

Millions Dry Tons per Year

600 500 400 300 200 100 0

Forest Residues Urban Wastes Ag Residues Mill Residues Energy Crops

$20

$30

$40

$50

Delivered Price ($/dry ton)

42 million acres (10% of total cropland) switches to bioenergy crops, includes 13 million acres of CRP land 181 million dry tons of switchgrass per year at $50 per ton or less.

Impact of Bioethanol on U.S. Gasoline

140 120 Billions of Gallons per Year (Gasoline Equivalents) 100 80 60 40 20 0
34.3
125

75

U.S. Gasoline Ethanol Market @ 20.5 Midterm MPG Technology

Ethanol Improved Technology

Life Cycle Assessmenta framework for making choices that support a sustainable society
Cradle to grave Accounts for all flows to and from the environment
Air, water and solid waste emissions Energy resources Other primary resources extracted from the environment

Basis for technology and policy decisions by business and government

Sustainability: the life cycle of fuels

Energy Crop, Waste, Residue Biomass Transport Hydrolysis and Fermentation

Ethanol

Feedstock Production

Feedstock Transport

Feedstock Conversion

Fuel Distribution

One Mile Traveled

Crude Oil Production

Crude Transport by barge, pipeline

Oil Refining to Gasoline

Gasoline

Avoiding fossil fuel use: bioethanol from corn stover

Biomass Resources and Issues

Quantity Wastes Ag. Crops and Residues Energy Crops Quality Composition Ease of Conversion Biomass Cost Production Collection and Transportation Sustainability Land, Air and Water Resources

MSW Ag. Crops and Residues

Grasses Trees

Biomass Composition Comparison

100% 80% 60% 40% 20% 0% poplar sawdust corn stover (fresh) bagasse (fresh)
protein
chlorophyll
soil
acetyl
Uronic acids
ash
extractives
lignin
galactan
arabinan
mannan
xylan
glucan

Major Steps in Enzymatic Process

Delivered feedstock Pre-processing

Many different technology options exist for each step

Pretreatment (hemicellulose extraction) Enzymatic cellulose saccharification Biomass sugar fermentation Beer product to distillation

Conditioning (if necessary)

Goals of Biomass Pretreatment

Acid-Catalyzed Process
Solubilized Hemicellulose
Hemicellulose Cellulose Lignin Cellulose Oligomers Monomers

Degradation Products

Solubilized Cellulose
Oligomers Glucose

All xylose, mannose, arabinose, galactose and portion of glucose released Remaining cellulose is highly digestible Minimal sugar degradation products

Lignin

Enzymes

Lignin

Biomass Pretreatment
Chemical partial hydrolysis prior to enzyme hydrolysis Reactor design is complex!
Continuous processing High solids, erosive, corrosive High temperature, pressure Heterogeneous catalysis of complex substrate Many simultaneous reactions

Tools for improving pretreatment

Multiple reactor sizes and configurations Impeccable analytical process chemistry Kinetic and molecular modeling Computational fluid dynamics

Conversion of Biomass

100 g raw solids (dry) feedstock

60 g pretreated solids (dry) process intermediate

27 g residue solids (dry) lignin coproduct

Pretreatment Equipment
4 L Batch Steam Digester 2 ton/day Sunds Prehydrolyzer

200 kg/day Sunds Two-stage Countercurrent Reactor System

Mass Transfer Resistances The Boundary Layer Theory

The hydrophobic surface of crystalline cellulose imparts a structuring to adjacent water molecules. 205 C
Bulk density or below 25% above bulk density 50% above bulk density 75% above bulk density

Enzymatic Hydrolysis
Enzymes offer greater opportunities for cost reduction in the long term compared to acid hydrolysis technology
Enzyme Biochemistry and specific activity Cellulase:Cellulose Interaction Cost of Enzyme Production
+2 +1 -1 -2

Y82
cellodextrin

CBH1 from T. reesei

E1 from A. cellulotiticus

Biomass Sugar Fermentation

Ferment all Biomass Sugars Glucose, Xylose, Arabinose, Mannose, Galactose Resistant to toxic materials from pretreatment Furfural, HMF, Acetic, Uronic and other Acids, phenols, cations, sugar oligomers, Robust, able to out-compete contaminant microorganisms
Thermo-tolerant Ethanol tolerant pH tolerant High fermentation rates

Minimum metabolic byproducts

Pathways Required for Pentose Fermentation

Pentose Metabolism Pathways
D-Xylose
Xylose Isomerase

Entner-Doudoroff Pathway
D-Glucose
ATP ADP Glucose-6-P Gluconolactone-6-P 6-P-Gluconate 2-Keto-3-deoxy-6-P-Gluconate Glyceraldehyde-3-P

L-Arabinose
L-arabinose isomerase L-Ribulose L-ribulokinase ATP ADP L-Ribulose-5-P L-ribulose-5-P 4-epimerase Ribulose-5-P Transketolase Ribose-5-P

D-Xylulose Xylulokinase ATP ADP D-Xylulose-5-P

Sedoheptulose-7-P Transaldolase Erythrose-4-P

Glyceraldehyde-3-P

1,3-P-Glycerate ADP ATP 3-P-Glycerate 2-P-Glycerate ADP ATP Pyruvate Phosphoenolpyruvate Acetaldehyde + CO2

Fructose-6-P Fructose-6-P Transketolase Glyceraldehyde-3-P

Ethanol

Critical Success Factors for Pioneer Plants

Accurately estimate cost and performance!* Plant cost growth strongly correlated with:
Process understanding (integration issues) Project definition (estimate inclusiveness)

Plant performance strongly correlated with:

Number of new steps % of heat and mass balance equations based on plant data Waste handling difficulties Solid feedstock

* Understanding Cost Growth and Performance Shortfalls in Pioneer

Process Plants, a study by the Rand Corp. for DOE (1981)

Simple Bioethanol Process Flow Diagram

Feedstock Handling Pretreatment S/L Separation

Corn Stover

Steam & Acid Enzyme Lime

Liquor

Solids

Steam

Wastewater Treatment
Lignin Residue

Distillation & Ethanol Purification

Saccharification & Fermentation

Conditioning

Burner/Boiler Turbogenerator

Corn Stover Case Normalized Cost by Area

Capital Recovery Charge Grid Electricity Corn Stover Feedstock Handling Pretreatment and Conditioning Saccharification and Fermentation Cellulase Distillation and Solids Recovery Waste Water Treatment Raw Materials Total Plant Electricity Process Electricity Fixed Costs

34% 5% 19% 9% 8% 11% 2% 7%

(after ~10x cost reduction!)

Boiler/Turbogenerator Utilities Storage -20% -10% 0%

4% 1%
10% 20% 30% 40%

The costs of Cellulosic Conversion?

2.50
Enzyme tec hnology c ost trajec tory

2.00

1.50
Existing c orn ethanol and pioneer plant bioethanol tec hnology

1.00

$1.07 target for first c ommerc ial enzyme biorefinery by 2010

0.50

Long term target as bulk fuel

0.00 1990

2000

2010

2020

2030

2040

2050

2060

Biorefineries of the Future

Products
Fuels:
Ethanol Renewable Diesel Methanol Hydrogen

Electricity Heat

Biomass Feedstocks
Trees Grasses Bio-product Crops Agricultural Crops Agricultural Residues Animal Wastes Municipal Solid Waste

Conversion Processes
Enzymatic Fermentation Gas/liquid Fermentation Acid Hydrolysis/Fermentation Gasification Product Synthesis from Syn-gas Combustion Co-firing

Chemicals:
Plastics Solvents Pharmaceuticals Chemical Intermediates Phenolic Compounds Adhesives Furfural Fatty acids Acetic Acid Carbon black Paints Dyes, Pigments, and Ink Detergents Etc.

Summary
Environmentally acceptable scenarios exist in which bioethanol is a major energy carrier for a sustainable transportation sector. Significant progress has been made in developing the new technologies needed but they remain to be proven at the commercial scale.

But this entails big changes!

As do all transition paths to a sustainable world. If we reject potential paths because they involve large changes, we will probably have none left.

For More Information

Visit the 20 Bio Posters Upstairs!
Bioethanol Biobased Products Chemicals and Materials Enzyme Development Biomass Collection, Processing and Analysis Biomass Development Assessment Methods And also visit the Biofuels Web site at:

www.ott.doe.gov/biofuels

Acknowledgments
Funding Provided by U.S. Department of Energy, Office of Transportation Technologies, Office of Fuels Development

Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel