Biofuels: An Opportunity for the GCRI
Dr. Michael A. Pacheco
Director of The National Bioenergy Center
November 3, 2006
Future of Gulf Coast Refining Industry Symposium
Houston, Texas
1
National Renewable Energy Laboratory
• Only national laboratory dedicated to renewable energy and energy
efficiency R&D
– Fundamental science to technology solutions
– Collaboration with industry and university partners
– Research programs linked to market opportunities
• Originally the Solar Energy Research Institute, July 1977
• Designated a U.S. Department of Energy National Lab, Sept. 1991
• Current staff of 1100 and budget of $200 million/yr
U.S. Energy Supply (2004 data)
Solar <1%
Geothermal 5%
Nuclear 8%
Natural Gas 23%
Biomass 47%
Renewable
6%
Petroleum 40%
Coal 23%
Source: Renewable Energy Trends 2004; Energy Information Administration, August 2005.
Note: Total U.S. Energy Supply is 100.278 QBtu; Energy Information Administration, August 2005.
Wind 2%
Hydroelectric 45%
The “Good News”
the planet’s sustainable
carbon cycle dwarfs our
non-sustainable
use of fossil sources
Biomass Strengths
Biomass is:
 Abundant
 Renewable
 Carbon-neutral
 The only sustainable source
of hydrocarbons.
Biomass can:
 Fill the gap between demand
and availability of petroleum in
the near/mid term.
 Serve as a renewable source
of hydrogen in the long term.
How can Biofuels be an Opportunity for
the Gulf Coast Refining Industry ?
• Develop biofuel options that can utilize existing infrastructure:
including: refineries, petrochemical facilities, channels to market
• Look for technologies that create synergy with existing operations
• Focus on ensuring sufficient biomass resources, avoid competition
with food sources, and improve conversion efficiency to liquid fuels
• Develop alternative crude oils from biomass, versus alternative
products
• Reduce the power foreign National Oil Co’s have over GCRI
• Develop liquid biofuels that are more compatible with petroleum
products, with a higher in energy density than ethanol or biodiesel
• Identify and develop “game changing” technology to better position
the GCRI for the long term transition to C-neutral renewable fuels
Range of Possible Biorefinery Concepts
Biomass
Feedstock
 Trees
 Grasses
 Agricultural Crops
 Residues
 Animal Wastes
 Municipal Solid Waste
 Algae
 Food Oils
Conversion
Processes
 Enzymatic Fermentation
 Gas/liquid Fermentation
 Acid Hydrolysis/
Fermentation
 Gasification
 Combustion
 Co-firing
 Trans-esterification
Products
Fuels
 Ethanol
 Biodiesel
 “Green” Gasoline & Diesel
Power
 Electricity
 Heat
Chemicals
 Plastics
 Solvents
 Chemical Intermediates
 Phenolics
 Adhesives
 Furfural
 Fatty Acids
 Acetic Acid
 Carbon Black
 Paints
 Dyes, Pigments, and Ink
 Detergents
 Etc.
Food and Feed
Edible Constituents of Biomass
Starch: 70%–75% (corn)
 Readily available and hydrolysable
 Basis for existing U.S.
“biorefineries”
Oil: 4%–7% (corn),
18%–20% (soybeans)
 Readily separable from biomass
feedstock
 Basis for oleochemicals and
biodiesel
Protein: 20%–25% (corn),
80% (soybean meal)
 Key component of food
 Chemical product applications
Non-Edible Constituents of Biomass
Lignin: 15%–25%
H CO
3
HO
O CH
OC H OC H3
3
O
3
HO
3
3
O
OCH
3
O
HO
O
OH
O
O HO
OH
OH
O
O
O
OH
O
OH
HO
O HO
O
OH
OH
HO
O
O
OH
OH
OH
O
O
OH
HO
O
O
OH
O
OH
OH
O
OH
O
OH
HO
HO
O HO
O
OH
O HO
OH
OH
O
O
OH
OH
HO
O
O HO
OH
OH
O
OH
OH
O
O
HO
O HO
OH
O
OH
OH
OH
O
O
OH
O
O
OH
O
OH
O
O HO
O
OH
OH
O HO
OH
OH
O
HO
O HO
O
OH
O
HO
O HO
O
OH
HO
OH
OH
O
OH
OH
OH
O
O
OH
OH
O
O HO
O
O
O HO
OH
OH
O
HO
O HO
OH
OH
O
O
OH
OH
OH
O
OH
O
HO
O HO
OH
OH
OH
OH
O
HO
O
O
O
OH
OH
O
OH
O
HO
H CO
3
OCH
3
HO
O HO
OH
HO
OH
OH
HO
OH
OH
O
O
OH
OH
O
O
OH
O HO
O
HO
OCH OCH3
3
OH
HO
O
OH
OH
OH
H CO
3
OCH
3
OH
O
O
OH
O
OH
O
HO
OH
OCH
O
HO
O CH
OH
O
 Xylose is the second most
abundant sugar in the biosphere
 Polymer of 5- and 6-carbon
sugars, marginal biochemical feed
 Most abundant form of carbon
in biosphere
 Polymer of glucose, good
biochemical feedstock
OH
O CH
Hemicellulose: 23%–32%
Cellulose: 38%–50%
O
O
 Complex aromatic structure
 Very high energy content
 Resists biochemical conversion
H CO
3
O
3
OH
OH
U.S. Biomass Resource Potentials
Corn (largest volume grain and source of EtOH in U.S.)
 Potential to displace 10-20% of our gasoline
Food
Supplies
Soybeans, fats & greases (largest sources of biodiesel)
 Potential to displace 5-10% of our diesel
Over 1 billion tons/year of lignocellulosic biomass (trees,
Not a Food
grasses, etc.) could be available in the U.S.
 Potential to displace 50-70% of our gasoline
Supply
Short-term: improve cost and efficiency of corn ethanol & biodiesel
Mid to Long-term: focus on lignocellulose (trees, grasses, & residues)
Significance of the “Billion Ton” Scenario
Billion Barrel of Oil Equivalents
Based on ORNL & USDA Resource Assessment Study by Perlach et.al. (April 2005)
http://www.eere.energy.gov/biomass/pdfs/final_billionton_vision_report2.pdf
Ethanol is the 1st of Many Possible Biofuels
Near
Term
Ethanol – as a blending agent from either grain or cellulosic
material from Ag and/or Forestry industry
Biodiesel – Transesterified vegetable oils blended with diesel
Green Diesel – fats, waste oils, or virgin oils converted to lowsulfur diesel in petroleum refinery
Other Fermentation Products – examples include: butanol,
acetates, lactates, and other possibilities
Pyrolysis Liquids – alternative feedstock to petroleum refinery
or gasification facility
Synthesis Gas – for conversion to Fischer-Tropsch liquids,
methanol, dimethyl ether, or mixed alcohols
Algae-derived Fuels – alternative source of triglycerides for
biodiesel or green diesel, and a carbohydrate source
Long
Term
Hydrocarbon Fuels – from hydrogenation of biomass
constituents
Ethanol Production
Actual and Projected U.S. Ethanol Production 1999-2012
Billion Gallons of Production
9
8
Source: December 2005 Ethanol Today Magazine
Cellulosic Ethanol
2005 EPACT RFS - Minimum
U.S. Ethanol Production
7
6
5
4
3
2
• Renewable Fuels Standard mandates 7.5 billion gallons by 2012
• Total US gasoline market ~140 billion annual gallons
12
20
11
20
10
20
09
20
08
20
07
20
06
20
05
20
04
20
03
20
02
20
01
20
00
20
19
99
1
0
Integrated Cellulosic Ethanol Biorefinery
Energy Required to Produce Ethanol
Total Btu spent for 1 Btu available at fuel pump
3
Btus Required per Btu of Fuel
From Biomass
From Coal and Natural Gas
2.5
Fuel-to-Petroleum Ratio = 10
From Petroleum
45% Efficiency
2
57% Efficiency
Fuel-to-Petroleum Ratio = 0.9
1.5
81% Efficiency
Energy
in the
Fuel
1
0.5
0
Gasoline
Corn Ethanol
Based on “Well to Wheels Analysis of Advanced Fuel/Vehicle Systems” by Wang, et.al (2005).
Cellulosic Ethanol
Reducing the Cost of Ethanol From Stover
Minimum Ethanol Selling Price ($/gal)
$6.00
State of Technology
Estimates
$5.00
Feed $53/ton
$4.00
Enzyme
Conversion
Feedstock
Prior DOE Cost Targets
President's Initiative
$3.00
Costs in 2002 Dollars
Integrated large-scale
BC/TC processing
$2.00
2005 Yield
65 gal/ton
$1.00
Feed $30/ton
Yield 90 gal/ton
$0.00
2000
2005
2010
5
Parameters that Drive the Cost of Cellulosic
Ethanol via Biochemical Path
2005
Minimum Ethanol Selling Price
Installed Capital per Annual Gallon
Yield (Gallon/dry ton)
Feedstock Cost ($/dry ton)
Pretreatment
Xylan to Xylose Yield
Xylan to Degradation Products
Conditioning
Xylose Sugar Loss
Glucose Sugar Loss
Hydrolysis & Fermentation
Enzyme Contribution ($/gal EtOH)
Hydrolysis & Fermentation Time (d)
Xylose to Ethanol
Minor Sugars to Ethanol
2007
2008
$2.26
$3.04
65
$53
2009
2010
2011
2012
$1.07
$1.85
90
$35
$45
63%
13%
68%
12%
72%
10%
77%
9%
81%
8%
86%
6%
90%
5%
13%
12%
11%
10%
9%
8%
7%
6%
4%
4%
2%
2%
0%
0%
0.32
7
76%
0%
0.32
7
76%
40%
0.32
7
76%
40%
0.32
6
80%
40%
0.32
5
80%
80%
0.32
3
80%
80%
0.32
3
85%
85%
Other Near-Term Biofuel Technologies
Near
Term
Ethanol – as a blending agent from either grain or cellulosic
material from Ag and/or Forestry industry
Biodiesel – Transesterified vegetable oils blended with diesel
Green Diesel – fats, waste oils, or virgin oils converted to lowsulfur diesel in petroleum refinery
Other Fermentation Products – examples include: butanol,
acetates, lactates, and other possibilities
Pyrolysis Liquids – alternative feedstock to petroleum refinery
or gasification facility
Synthesis Gas – for conversion to Fischer-Tropsch liquids,
methanol, dimethyl ether, or mixed alcohols
Algae-derived Fuels – alternative source of triglycerides for
biodiesel or green diesel, and a carbohydrate source
Long
Term
Hydrocarbon Fuels – from hydrogenation of biomass
constituents
Oils, Fats & Greases as Bio-renewable
Petroleum Refinery Feedstocks
ISBL Petroleum Refinery
Catalytic
Cracker
Green
Gasoline
& Olefins
Oils and
Greases
Distillate
Hydrotreater
Green
Diesel
• Co-processing of oils
and greases with
petroleum fractions
• Utilize existing process
capacity
• Potential for lower
conversion costs (than
FAME)
• Higher quality diesel
blending component
• G/D flexibility
Based on Presentations at 1st International Biorefinery Workshop, Washington DC, July 20-21, 2005
- Future Energy for Mobility, James Simnick, BP
- From Bioblending to Biorefining, Veronique Hervouet, Total
- Opportunities for Biorenewables in Petroleum Refineries, Jennifer Holmgren, UOP
Green Diesel
• Hydrotreating of
biorenewable oils in
existing refinery units
• Lower capital costs
than biodiesel
• Excellent fuel
properties
Source: U.O.P. Corp.
1st International Biorefinery Conference, August 2005
Published Economic Comparison
(from UOP-NREL-PNNL study)
Net Present Value
• Biodiesel is least
competitive option in
this UOP/PNNL/NREL
study
• All fuels from soy
bean oil require fuel
subsidy
• “Green” fuels or
olefins from greases
in petroleum refinery
may generate positive
NPV even without
subsidy
Source: Arena, B. et.al., “Opportunities for Biorenewables in Petroleum Refineries”,
presented at Rio Oil & Gas Conference, held Sept 11-14, 2006
Mid-Term Biofuel Technologies
Near
Term
Ethanol – as a blending agent from either grain or cellulosic
material from Ag and/or Forestry industry
Biodiesel – Transesterified vegetable oils blended with diesel
Green Diesel – fats, waste oils, or virgin oils converted to lowsulfur diesel in petroleum refinery
Other Fermentation Products – examples include: butanol,
acetates, lactates, and other possibilities
Pyrolysis Liquids – alternative feedstock to petroleum refinery
or gasification facility
Synthesis Gas – for conversion to Fischer-Tropsch liquids,
methanol, dimethyl ether, or mixed alcohols
Algae-derived Fuels – alternative source of triglycerides for
biodiesel or green diesel, and a carbohydrate source
Long
Term
Hydrocarbon Fuels – from hydrogenation of biomass
constituents
Fast Pyrolysis and Bio-oil as Feed to
Power Plant or Petroleum Refinery
Bio-oil is is comprised of many oxygenated organic
chemicals, with water miscible and oil miscible fractions
Dark brown mobile liquid,
Combustible,
Not 100% miscible with hydrocarbons,
Modest heating value ~ 17 MJ/kg,
High density ~ 1.2 kg/l,
Acidic, pH ~ 2.5,
Pungent odour,
“Ages” - viscosity increases with time
Based on research at NREL (1990 - 2006)
Crude Pyrolysis Oil Cost Estimates
80
10
8
Base Case:
550 ton/d wood chips
59% oil yield
2 MBPD oil product
$ 44 million Capital
70
60
50
40
6
30
4
20
2
10
0
0
Base Case Incr size to Incr yield to
2000 tpd
70%
Source: V. Putsche, NREL report (2004)
$/BOE
$/Giga JouleJ
12
Decentralized Biomass Liquids Scenario
Alternate Feedstock for a Petroleum Refinery or Petrolchemical Plant
Mid-Term Biofuel Technologies
Near
Term
Ethanol – as a blending agent from either grain or cellulosic
material from Ag and/or Forestry industry
Biodiesel – Transesterified vegetable oils blended with diesel
Green Diesel – fats, waste oils, or virgin oils converted to lowsulfur diesel in petroleum refinery
Other Fermentation Products – examples include: butanol,
acetates, lactates, and other possibilities
Pyrolysis Liquids – alternative feedstock to petroleum refinery
or gasification facility
Synthesis Gas – for conversion to Fischer-Tropsch liquids,
methanol, dimethyl ether, or mixed alcohols
Algae-derived Fuels – alternative source of triglycerides for
biodiesel or green diesel, and a carbohydrate source
Long
Term
Hydrocarbon Fuels – from hydrogenation of biomass
constituents
Gasification Offers Many Feed & Product Options
Primary Energy
Source
Syngas Step
Conversion Technology
Products
Syngas to Liquids (GTL) Process
Natural
Gas
Fischer
Tropsch
(FT)
Upgrading
Diesel
Naphtha
Lubes
Coal
Syngas to Chemicals Technologies
Syngas
(CO + H2)
Biomass
Acetic Acid
M ethanol
Hydrogen
Extra
Heavy
Oil
M ixed Alcohols (e.g. ethanol, propanol)
Others (e.g. Triptane, DM E, etc)
Slide courtesy of BP Corporation
Biofuels via Biomass Gasification
• “SunDiesel” strongly
supported by Volkswagen
• Attractive LCA of high
quality diesel and HCCI
engine technology
• Excellent overall
conversion efficiency to
liquid fuels
• Several fuels options
from SynGas
Excerpted from Renewable Fuels for Advanced Powertrains RENEW, by Frank Seyfried, Volkswagen,
presented at 1st International Biorefinery Workshop, July 20-21, 2005, Washington D.C.
Well to Wheels Analysis (Volvo Study)
Excerpted from Automotive Fuels from Biomass, by Anders Roj, Volvo,
presented at 1st International Biorefinery Workshop, July 20-21, 2005, Washington D.C.
Thermochemical Route to Alcohols
Feed Handling and
Conditioning
Dried
Biomass
Gasification
Crude
Syngas
Tar Reforming
And Scrubbing
Scrubbed
Syngas
Syngas
Compression
High P
Syngas
Mixed Alcohol
Synthesis
Reforming:
CxHyOz + H2O(g)
H2 + xCO
CO2 + H2
Gasification:
COx + H2
C + H2O(g)
Product
Separation
C3 +
Alcohols
2012 Targets for Tar Reforming:
- Promoted metal/support catalyst
- CH4 < 3 vol%
- Benzene < 10 ppmv
- Heavy tars < 1 g/nM3
Preliminary
Separation
Mixed
Alcohols
Water gas shift: H2O + CO
Crude
Products
Overall gas conditioning reactions
Methanol
Biomass
Ethanol
Parameters that Drive the Cost of Cellulosic
Ethanol (Mixed Alcohols) via Thermochem Path
2002
Process Description
M ixed Alcohol M ESP ($/gal ethanol equivalent)
M inimum Ethanol Selling Price ($/gal ethanol)
Higher Alcohol Co-Product Value (% mkt value)
Installed capital cost ($/annual gal M A)
M ixed Alcohol Yield (gal/dry ton) - 75% EtOH
Feedstock cost ($/dry ton)
Cleanup and Conditioning
Exit methane conc. (mol% - dry basis)
C6 HC reforming - % conv
Tar reforming - %tar conv
Required sulfur level
Catalytic Fuel S ynthesis
Synthesis Reactor Pressure (psia)
Single pass CO conversion
CO selectivity to alcohols
2005
2008
2010
2012
Tar
Sequential
Increased
Improve
Consolidate
Removal & Tar & Light
HC
Synthesis
Reforming
Disposal Reforming Conversion
Catalyst
$1.96
$1.80
$1.71
$1.42
$1.25
$1.83
$1.61
$1.45
$1.07
$1.07
85%
69%
$3.01
$2.71
$2.69
$2.36
$2.00
75
89
$53
$53
$45
$45
$30
N/A
N/A
N/A
1 ppmv
(SM R)
8%
70%
95%
1 ppmv
(SM R)
5%
90%
97%
1 ppmv
(SM R)
2%
99%
99.9%
50 ppmv
(M A)
2%
99%
99.9%
50 ppmv
(M A)
2,000
38
80
2,000
38
80
2,000
38
80
2,000
38
80
1,000
50
90
D. Dayton
Thermochemical Ethanol Cost Targets
$2.50
Conversion
Feedstock
Previous DOE Cost Targets
President's Initiative
Minimum Ethanol Selling Price ($ per gallon)
State of Technology
Estimates
Costs in 2002 Dollars
Forest
Resources
56 gal/ton
$2.00
$1.50
Forest &
Agricultural Resources
67 gal/ton
$1.00
$0.50
$0.00
2002
2005
2008
2011
D. Dayton
2030 Target Scenario for a Large Cellulosic
Biorefinery to Integrate BC & TC Ethanol Paths
Lignocellulosic
Feedstock
10,000 ton/day
Ethanol via
Bioconversion
Steam &
Power
Ethanol
1,035,000 gpd
Lignin
CHP Plant
Ethanol
1,168,000 gpd
409 MM gal/yr
Lignin-rich Residue
1,400 ton/day
Yield: 117 gal/ton
Lignin-rich Residue
1,500 ton/day
Gasification
Syngas
Alcohol
Synthesis
Ethanol
133,500 gpd
Higher Alcohols
29,700 gpd
S. Phillips and J. Jechura
Longer Term Biofuel Technologies
Near
Term
Ethanol – as a blending agent from either grain or cellulosic
material from Ag and/or Forestry industry
Biodiesel – Transesterified vegetable oils blended with diesel
Green Diesel – fats, waste oils, or virgin oils converted to lowsulfur diesel in petroleum refinery
Other Fermentation Products – examples include: butanol,
acetates, lactates, and other possibilities
Pyrolysis Liquids – alternative feedstock to petroleum refinery
or gasification facility
Synthesis Gas – for conversion to Fischer-Tropsch liquids,
methanol, dimethyl ether, or mixed alcohols
Algae-derived Fuels – alternative source of triglycerides for
biodiesel or green diesel, and a carbohydrate source
Long
Term
Hydrocarbon Fuels – from hydrogenation of biomass
constituents
Algae as a Source of Biofuels
• Source of additional lipids and/or
carbohydrates
• Complements terrestrial biomass
production
 Reduces pressure on land use
 Avoids food vs fuel debate
 Option to utilize large waste CO2
resource
• Potential for greater productivity
than their terrestrial biomass
Based on Aquatic
Species Program at
NREL, from 1978-1996
 Up to 50 times more productive than
traditional oilseed crops
 Very large resource potential for
producing biodiesel or “green diesel”
Challenge of Making Fuels From Algae:
- A “Biological” Challenge
The biochemistry of lipid
and carbohydrate synthesis
Two main forms of carbon
storage:
 Triacylglycerides (lipids)
 Chrysolaminarin (glucan)
Goal: Control “lipid triggers”
that turn on lipid synthesis
pathway
Diesel/Jet Fuel From Algae
Possible Approaches for the Gulf Coast
Industry to Partner with NREL on Biofuels
1.
Contract R&D: Develop biofuel concepts that are uniquely suited to one
company. Several already in-progress at NREL. Results are proprietary
and protected.
2.
Program direction funding from DOE: Rare. Example is UOP project on
“Biorenewables in Petroleum Refining.” Low funding level. Results
become public. Company’s IP can be protected.
3.
Vertically integrated team: Biomass resource, conversion technology,
fuel blending and marketing. Good strategy for competitive solicitations
and industry-DOE cost sharing.
4.
Industry sector consortium CRADA: Industry partners cost-share R&D
on biofuel concepts that benefit all partners in that sector. Investment
protected through a mix of patents and other barriers to entry.
Summary & Conclusions
 Biomass is the only renewable
option for liquid transportation fuels
 Resource base sufficient to supply
a large fraction of demand, with good
potential to increase the resource
base
 A sustainable solution to meet the
supply-demand “gap” to be caused
by peaking world oil production and
rising demand
 On-going R&D will create many
opportunities that beyond today’s
biopower, ethanol, and biodiesel