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
Renew ables
30
Quads/Yr

Petroleum -- Imported
25 Petroleum -- Domestic
Nat. Gas -- Imported
20
Nat. Gas -- Domestic
15 Coal

10

0
Residential Com m ercial Industrial Transportation

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

600 Forest Residues

Millions Dry Tons per
Urban Wastes
500
Ag Residues
400 Mill Residues
Year

300 Energy Crops

200
100
0
$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

140 125
120
Billions of 100 75
Gallons per 80
Year
60 34.3
(Gasoline
Equivalents) 40
20
0
U.S. Gasoline Ethanol - Ethanol -
Market @ 20.5 Midterm Improved
MPG Technology Technology
 Life Cycle Assessment—a
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, Hydrolysis and
Residue Biomass Fermentation
Transport
Ethanol

Feedstock Feedstock Feedstock Fuel

Production Transport Conversion Distribution
One Mile
Traveled

Gasoline
Oil Refining
Crude
Crude Oil to Gasoline
Transport by
Production barge, pipeline
 Avoiding fossil fuel use:
bioethanol from corn stover
 Biomass Resources and Issues
• Quantity
– Wastes
– Ag. Crops and Residues
– Energy Crops
• Quality
MSW – Composition
– Ease of Conversion
Ag. Crops and
Residues • Biomass Cost
– Production
– Collection and Transportation
• Sustainability
Grasses – Land, Air and Water
Resources
Trees
 Biomass Composition Comparison

100% protein

chlorophyll

80% soil

acetyl

Uronic acids
60%
ash

extractives
40% lignin

galactan

arabinan
20%
mannan

xylan
0%
glucan
poplar corn stover bagasse
sawdust (fresh) (fresh)
Major Steps in Enzymatic Process
Delivered
feedstock
Many different
technology options
Pre-processing
exist for each step

Pretreatment
(hemicellulose
extraction)

Enzymatic Biomass Beer

Conditioning cellulose sugar product to
(if necessary) saccharification fermentation distillation
 Goals of Biomass Pretreatment
Acid-Catalyzed Process

Solubilized Hemicellulose

Hemicellulose Oligomers Monomers

× Degradation
Products
Cellulose
Lignin Solubilized Cellulose

Cellulose Oligomers Glucose

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

60 g pretreated 27 g residue
solids (dry) solids (dry)
100 g raw process lignin
solids (dry) intermediate coproduct
feedstock
 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 Entner-Doudoroff Pathway
D-Xylose L-Arabinose D-Glucose

L-arabinose isomerase
ATP
Xylose Isomerase L-Ribulose ADP
L-ribulokinase Glucose-6-P
ATP
D-Xylulose
ADP Gluconolactone-6-P
Xylulokinase L-Ribulose-5-P
ATP L-ribulose-5-P 4-epimerase 6-P-Gluconate
ADP
D-Xylulose-5-P Ribulose-5-P Ribose-5-P 2-Keto-3-deoxy-6-P-Gluconate

Transketolase Glyceraldehyde-3-P

Sedoheptulose-7-P 1,3-P-Glycerate
Glyceraldehyde-3-P ADP
ATP
Transaldolase 3-P-Glycerate

2-P-Glycerate
Erythrose-4-P Fructose-6-P ADP ATP
Fructose-6-P Phosphoenolpyruvate Pyruvate

Transketolase Glyceraldehyde-3-P Acetaldehyde + CO2

Ethanol
 Critical Success Factors
for Pioneer Plants
¾ 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 Liquor Solids

Enzyme Lime

Steam

Saccharification Conditioning
&
Wastewater Distillation & Fermentation
Treatment Ethanol Purification
Burner/Boiler
Lignin Turbogenerator
Residue
 Corn Stover Case Normalized Cost by Area
Capital Recovery Charge Raw Materials Process Electricity
Grid Electricity Total Plant Electricity Fixed Costs

Corn Stover 34%

Feedstock
Handling 5%
Pretreatment
and Conditioning 19%
Saccharification
and Fermentation 9%

Cellulase 8% (after ~10x cost reduction!)

Distillation and
Solids Recovery
11%
Waste Water
2%
Treatment

7%
Boiler/Turbogenerator
Utilities 4%

Storage 1%

-20% -10% 0% 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
$1.07 target for first c ommerc ial enzyme
pioneer plant
biorefinery by 2010
1.00 bioethanol
tec hnology

Long term target as bulk fuel

0.50

0.00
1990 2000 2010 2020 2030 2040 2050 2060
 Biorefineries of the Future
Products
Fuels:
• Ethanol
• Renewable Diesel
• Methanol
• Hydrogen

Electricity

Heat

Chemicals:
Biomass Conversion • Plastics
• Solvents
Feedstocks Processes • Pharmaceuticals
• Chemical Intermediates
• Phenolic Compounds
•Trees •Enzymatic Fermentation • Adhesives
•Grasses •Gas/liquid Fermentation • Furfural
• Fatty acids
•Bio-product Crops •Acid Hydrolysis/Fermentation • Acetic Acid
•Agricultural Crops •Gasification • Carbon black
•Agricultural Residues •Product Synthesis from Syn-gas • Paints
•Animal Wastes •Combustion • Dyes, Pigments, and Ink
•Municipal Solid Waste •Co-firing • 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