biofuels: an opportunity for the gcri
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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. National Renewable Energy Laboratory. - PowerPoint PPT PresentationTRANSCRIPT
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Biofuels: An Opportunity for the GCRIDr. Michael A. Pacheco
Director of The National Bioenergy Center
November 3, 2006Future of Gulf Coast Refining Industry Symposium
Houston, Texas
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)
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.
Biomass 47%
Wind 2%
Hydroelectric 45%
Geothermal 5%Solar <1%
Renewable 6%
Natural Gas 23% Nuclear 8%
Petroleum 40% Coal 23%
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
ProductsProductsFuels
EthanolBiodiesel“Green” Gasoline & Diesel
PowerElectricityHeat
ChemicalsPlasticsSolventsChemical IntermediatesPhenolicsAdhesivesFurfuralFatty AcidsAcetic AcidCarbon BlackPaintsDyes, Pigments, and InkDetergentsEtc.
Food and Feed
Enzymatic Fermentation Gas/liquid Fermentation Acid Hydrolysis/
Fermentation Gasification Combustion Co-firing Trans-esterification
Conversion ProcessesConversion Processes
Range of Possible Biorefinery Concepts
Trees Grasses Agricultural Crops Residues Animal Wastes Municipal Solid Waste Algae Food Oils
Biomass FeedstockBiomass Feedstock
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
Edible Constituents of Biomass
O
NH O
OO
O
NH
OHON
H
O
NH
NH2
ONH
SH
O
O
ONH
NHN
O
NH
SON
H
OH
7
7
7O
O
O
O
O
O
CH 3
CH 3
CH 3
OHOH O
OOH
OH
OHO
O
OH
OHOH O
OOH
OH
OHO
O
OH
OH OH O
OOH
OH
OHO
O
OH
OHOH O
OOH
Non-Edible Constituents of Biomass
Lignin: 15%–25% Complex aromatic structure Very high energy content Resists biochemical conversion
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 feedstockO
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
O H
O H
O H
H O
HO
O HO
O
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
O H
O H
O H
H O
H O
O HO
O
O
O
O H
O H
O H
H O
HO
O HO
O
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
OH
O H
O H
HO
HO
O HO
O
O
O
O H
O H
O H
HO
HO
O HO
O H
O
HO
H 3C O
O H
O C H3
O CH 3
O
O
O
O H
O C H 3
O C H 3
H 3C O
OO
H O
H3C O
H O
O CH 3
O CH 3
OH
O
H O
H 3C O
O H
O C H 3
O C H 3
O
O
O H
O C H 3
O C H3
O C H3
O
O
O
O H
H O
O
O
O
O
O H
HO
O H
O H
O
O
O
O H
H O
OH
O H
O
O
O
O H
HO
O H
O H
O
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
O H
O H
O H
H O
H O
O HO
O
O
O
O H
O H
O H
H O
H O
O HO
O
O
O
O H
O H
O H
HO
HO
O HO
O
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
O H
O H
O H
H O
HO
O HO
O
O
O
O H
O H
O H
HO
H O
O HO
O
O
O
O H
O H
O H
HO
H O
O HO
U.S. Biomass Resource Potentials
Corn (largest volume grain and source of EtOH in U.S.) Potential to displace 10-20% of our gasoline
Soybeans, fats & greases (largest sources of biodiesel) Potential to displace 5-10% of our diesel
Over 1 billion tons/year of lignocellulosic biomass (trees, grasses, etc.) could be available in the U.S. Potential to displace 50-70% of our gasoline
Short-term: improve cost and efficiency of corn ethanol & biodieselMid to Long-term: focus on lignocellulose (trees, grasses, & residues)
FoodFood SuppliesSupplies
Not a FoodNot a FoodSupplySupply
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
Significance of the “Billion Ton” ScenarioBillion Barrel of Oil Equivalents
Ethanol is the 1st of Many Possible Biofuels
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 low-sulfur 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
Hydrocarbon Fuels – from hydrogenation of biomass constituents
LongTerm
Near Term
Ethanol Production
0
1
2
3
4
5
6
7
8
9
Cellulosic Ethanol2005 EPACT RFS - MinimumU.S. Ethanol Production
• Renewable Fuels Standard mandates 7.5 billion gallons by 2012• Total US gasoline market ~140 billion annual gallons
Actual and Projected U.S. Ethanol Production 1999-2012Billion Gallons of Production
Source: December 2005 Ethanol Today Magazine
Integrated Cellulosic Ethanol Biorefinery
0
0.5
1
1.5
2
2.5
3
Cellulosic EthanolCorn EthanolGasoline
From Biomass
From Coal and Natural Gas
From Petroleum
Btu
s R
equi
red
per
Btu
of F
uel
57% Efficiency
81% Efficiency
Fuel-to-Petroleum Ratio = 0.9
Energy Required to Produce EthanolTotal Btu spent for 1 Btu available at fuel pump
Based on “Well to Wheels Analysis of Advanced Fuel/Vehicle Systems” by Wang, et.al (2005).
45% Efficiency
Energy in the Fuel
Fuel-to-Petroleum Ratio = 10
$0.00
$1.00
$2.00
$3.00
$4.00
$5.00
$6.00
2000 2005 2010
Min
imu
m E
than
ol
Sel
lin
g P
rice
($/
gal
) State of Technology Estimates
Feed $53/ton
2005 Yield65 gal/ton
Feed $30/tonYield 90 gal/ton
Costs in 2002 Dollars
EnzymeConversionFeedstockPrior DOE Cost TargetsPresident's Initiative
Integrated large-scaleBC/TC processing
5
Reducing the Cost of Ethanol From Stover
2005 2007 2008 2009 2010 2011 2012
Minimum Ethanol Selling Price $2.26 $1.07Installed Capital per Annual Gallon $3.04 $1.85Yield (Gallon/dry ton) 65 90Feedstock Cost ($/dry ton) $53 $45 $35
Pretreatment Xylan to Xylose Yield 63% 68% 72% 77% 81% 86% 90% Xylan to Degradation Products 13% 12% 10% 9% 8% 6% 5%Conditioning Xylose Sugar Loss 13% 11% 9% 7% 4% 2% 0% Glucose Sugar Loss 12% 10% 8% 6% 4% 2% 0%Hydrolysis & Fermentation Enzyme Contribution ($/gal EtOH) 0.32 0.32 0.32 0.32 0.32 0.32 0.32 Hydrolysis & Fermentation Time (d) 7 7 7 6 5 3 3 Xylose to Ethanol 76% 76% 76% 80% 80% 80% 85% Minor Sugars to Ethanol 0% 40% 40% 40% 80% 80% 85%
Parameters that Drive the Cost of Cellulosic Ethanol via Biochemical Path
Other Near-Term Biofuel Technologies
LongTerm
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 low-sulfur 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
Hydrocarbon Fuels – from hydrogenation of biomass constituents
Oils, Fats & Greases as Bio-renewable Petroleum Refinery Feedstocks
• 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
CatalyticCracker
DistillateHydrotreater
Oils andGreases
Green Gasoline& Olefins
GreenDiesel
ISBL Petroleum Refinery
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)
• 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
Net Present Value
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
LongTerm
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 low-sulfur 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
Hydrocarbon Fuels – from hydrogenation of biomass constituents
Bio-oil is is comprised of many oxygenated organic chemicals, with water miscible and oil miscible fractions
Fast Pyrolysis and Bio-oil as Feed to Power Plant or Petroleum Refinery
Based on research at NREL (1990 - 2006)
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
0
2
4
6
8
10
12
Base Case Incr size to2000 tpd
Incr yield to70%
$/G
iga J
ou
leJ
0
10
20
30
40
50
60
70
80
$/B
OE
Crude Pyrolysis Oil Cost Estimates
Source: V. Putsche, NREL report (2004)
Base Case: 550 ton/d wood chips 59% oil yield 2 MBPD oil product $ 44 million Capital
Decentralized Biomass Liquids ScenarioDecentralized Biomass Liquids Scenario
Alternate Feedstock for a Petroleum Refinery or Petrolchemical Plant
Mid-Term Biofuel Technologies
LongTerm
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 low-sulfur 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
Hydrocarbon Fuels – from hydrogenation of biomass constituents
Gasification Offers Many Feed & Product OptionsPrimary Energy
SourceSyngas Step Conversion Technology Products
Syngas(CO + H2)
Fischer Tropsch
(FT)Upgrading
Lubes
Naphtha
DieselSyngas to Liquids (GTL) Process
Mixed Alcohols (e.g. ethanol, propanol)
Syngas to Chemicals Technologies
Methanol
Acetic Acid
Others (e.g. Triptane, DME, etc)
Coal
Natural Gas
Biomass
Hydrogen
Extra Heavy
Oil
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.
Feed Handling andConditioning
Gasification
PreliminarySeparation
DriedBiomass
C3 +
Alco
ho
ls
BiomassCrude
Syngas
Mixed AlcoholSynthesis
SyngasCompression
Tar ReformingAnd Scrubbing
Cru
de
Pro
du
ctsH
igh
PS
yng
as
ScrubbedSyngas
Ethanol
Mixed
Alco
ho
ls
Met
han
ol
ProductSeparation
2012 Targets for Tar Reforming:- Promoted metal/support catalyst - CH4 < 3 vol%- Benzene < 10 ppmv- Heavy tars < 1 g/nM3
Overall gas conditioning reactions
Reforming: CxHyOz + H2O(g) H2 + xCO
Water gas shift: H2O + CO CO2 + H2
Gasification: C + H2O(g) COx + H2
Thermochemical Route to Alcohols
2002 2005 2008 2010 2012
Process DescriptionTar
Removal & Disposal
Sequential Tar & Light Reforming
Increased HC
Conversion
Consolidate Reforming
Improve Synthesis Catalyst
Mixed Alcohol MESP ($/gal ethanol equivalent) $1.96 $1.80 $1.71 $1.42 $1.25Minimum Ethanol Selling Price ($/gal ethanol) $1.83 $1.61 $1.45 $1.07 $1.07Higher Alcohol Co-Product Value (% mkt value) 85% 69%Installed capital cost ($/annual gal MA) $3.01 $2.71 $2.69 $2.36 $2.00Mixed Alcohol Yield (gal/dry ton) - 75% EtOH 75 89Feedstock cost ($/dry ton) $53 $53 $45 $45 $30Cleanup and Conditioning Exit methane conc. (mol% - dry basis) N/A 8% 5% 2% 2% C6 HC reforming - % conv N/A 70% 90% 99% 99% Tar reforming - %tar conv N/A 95% 97% 99.9% 99.9%
Required sulfur level1 ppmv (SMR)
1 ppmv (SMR)
1 ppmv (SMR)
50 ppmv (MA)
50 ppmv (MA)
Catalytic Fuel Synthesis Synthesis Reactor Pressure (psia) 2,000 2,000 2,000 2,000 1,000 Single pass CO conversion 38 38 38 38 50 CO selectivity to alcohols 80 80 80 80 90
Parameters that Drive the Cost of Cellulosic Ethanol (Mixed Alcohols) via Thermochem Path
D. Dayton
Thermochemical Ethanol Cost Targets
$0.00
$0.50
$1.00
$1.50
$2.00
$2.50
2002 2005 2008 2011
Min
imu
m E
than
ol
Sel
lin
g P
rice
($
per
gal
lon
)
ConversionFeedstockPrevious DOE Cost TargetsPresident's Initiative
State of Technology Estimates
Forest &Agricultural Resources67 gal/ton
Costs in 2002 DollarsForestResources56 gal/ton
D. Dayton
2030 Target Scenario for a Large Cellulosic Biorefinery to Integrate BC & TC Ethanol Paths
Ethanol via Bioconversion
Ethanol1,035,000 gpd
Lignin-rich Residue 1,500 ton/day
Steam & Power Lignin
CHP Plant
GasificationAlcohol
Synthesis
Higher Alcohols29,700 gpd
Syngas Ethanol133,500 gpd
Ethanol1,168,000 gpd409 MM gal/yr
Lignin-rich Residue 1,400 ton/day Yield: 117 gal/ton
Lignocellulosic Feedstock
10,000 ton/day
S. Phillips and J. Jechura
Longer Term Biofuel Technologies
LongTerm
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 low-sulfur 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
Hydrocarbon Fuels – from hydrogenation of biomass constituents
• 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
Up to 50 times more productive than traditional oilseed crops
Very large resource potential for producing biodiesel or “green diesel”
Algae as a Source of Biofuels
Based on Aquatic Species Program at NREL, from 1978-1996
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