Hydrocarbon Drop-In Biofuels · PDF fileHydrocarbon Drop-In Biofuels. ... YEAST CELL...
Transcript of Hydrocarbon Drop-In Biofuels · PDF fileHydrocarbon Drop-In Biofuels. ... YEAST CELL...
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John HolladayPacific Northwest National Laboratory
PO Box 999, MSIN: P8-60, Richland, WA [email protected]
Hydrocarbon Drop-In BiofuelsEngine Research CenterUniversity of Wisconsin-MadisonJune 8, 2011
PNNL-SA-77610
• At low % of total market supply & demand, refiners can adapt
• As % blend increases, issues arise in refining and blending:
• Refinery “balance” (light / heavy, H2, octane, vapor pressure, …)
• Petrochemical feedstocks(naphtha, pen-hex, BTX, light paraffins & olefins, …)
• Ethanol competes with gasoline, batteries, H2, and mass-transit, while only liquid fuels compete in most diesel & jet markets
Energy Security and MarketSupply & Demand Balance
Source: Energy Information Administration, “Oil: Crude Oil and Petroleum Products Explained” and AEO2009, Updated February 2010, Reference Case.
Dr. Paul Bryan
DOE-EERE Advanced Biofuels ConsortiaNABC—Lignocellulosics, NAABB—Algae
Solix BiofuelsCoyote Gulch
Texas A&MPecos Site
National Alliance for Advanced Biofuels and Bioproducts
Slide 4
H3C CH3CH3CH3
UOP 5076-06
Natural Oils—Options like Ecofining: Product is a High Quality Pure Hydrocarbon
CH3HO
O H2
CO2
H2O +
+ H3C CH3
H3C CH3
HC
O
O
O
O
O
O
CH3
CH2+CH3
CH3H2O
CO2 H3C
H3C H3C CH3
CH3H3C
ReactorSystem
Water
CO2
Propane & Light Ends
Green Diesel
Product
Make-up Hydrogen
Separator
Feed
Acid Gas Removal
Green Naphtha
or Jet
2.2 – 3.5%
UOP Catalyst
Triglyceride
Free Fatty Acid
Straight Chain Paraffins
+H3C CH3
+
CH3CH3
CH3H3C
CH3 H3CCH3
Green Diesel
& Green Naphtha
Propane
National Advanced Biofuels Consortium
The National Advanced Biofuels Consortium (NABC) is a collaboration among U.S. Department of Energy national laboratories, universities, and private industry that is developing technologies to produce infrastructure-compatible, biomass-based hydrocarbon fuels.
NABC : For Open Distribution
Picture courtesy of http://www.bantrel.com/markets/downstream.aspx
Crude Oil Refinery: Infrastructure Conversion
NABC Strategies and Technologies
Converting biomass into infrastructure- compatible materials
Fermentation of Lignocellulosic Sugars
Team led by Amyris
RENEWABLE CHEMICALS AND FUELSANY FEEDSTOCK
INDUSTRIAL SYNTHETIC BIOLOGY PLATFORM
NABC: For Open Distribution
FLS Process Strategy Overview
NABC: For Open Distribution
Mevalonate Pathway
YEAST CELL
hydrolysate
Diesel & Chemical Precursor
FarneseneSynthase
Farnesene
[1] [2] [3] [4]
[1] Cane juice[2] Fermentation broth[3] Separations[4] Purification
Results: Dilute Acid/Enzyme Hydrolysis of Pine
NABC: For Open Distribution
Acid PretreatedLow severity: 190°C, 3 minutes, 0.63% sulfuric acid in liquid
Acid PretreatedHigh severity: 210°C, 3 minutes, 1.0% sulfuric acid in liquid
Catalysis of Lignocellulosic Sugars
Team led by Virent
NABC: For Open Distribution
Catalysis of Lignocellulosic Sugars
NABC: For Open Distribution
Process options to produce hydrocarbons from lignocellulosic sugars
Catalysis of Lignocellulosic Sugars
NABC: For Open Distribution
Sugar Hydrolysate
BioReformate
Heating biomass can give a bio-oil or synthesis gas
Fast Pyrolysis (reference)Ambient pressure T = 400-600 C Residence times 0.5 sOil yields around 70% (wt%)
Fast pyrolysis oil:High water content: 15-30%High O content: 35-40%High acidity; pH = 2.5, TAN > 100 mg KOH/g oilUnstable (phase separation, reactions)Low HHV: 16-19 MJ/kg
NABC: For Open Distribution
Bio-Oil
SynGas
Biomass
Heat
Vapor
Bio-Char
Fast pyrolysis oil is converted to fuels in a 2-step process (reference case)
The carbon recovery based on bio-oil was about 50%Holmgren, J. et al. NPRA national meeting, San Diego, March 2008.
NABC: For Open Distribution
HC
light products
mediumproducts
heavyproducts
H2
HT
H2O aqueousbyproduct
Hydroprocessed Bio-oil (from Mixed Wood)
PetroleumGasoline
Min Max Typical
Paraffin, wt% 5.2 9.5 44.2
Iso-Paraffin, wt% 16.7 24.9
Olefin, wt% 0.6 0.9 4.1
Naphthene, wt% 39.6 55.0 6.9
Aromatic, wt% 9.9 34.6 37.7
Oxygenate, wt% 0.8
Hydroprocessed Bio-oil makes jet fuel range fuels
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10
20
30
40
50
60
70
80
90
0 50 100 150 200 250 300 350
perc
ent d
istil
led
temperature, degrees Celsius (corrected to 1 atm)
batch 1
batch 2
naphtha
jet
44.2% 42.4%
NABC: For Open Distribution
Catalytic Fast Pyrolysis
UOP leads the team
NABC: For Open Distribution
Replace sand (heat transfer medium) with catalysts
Catalytic Fast Pyrolysis
Standard Fast Pyrolysis
Catalytic Fast Pyrolysis
NABC: For Open Distribution
Hydropyrolysis
RTI—Team Lead
NABC: For Open Distribution
RTI’s Transport Reactor SystemAdd H2 (reactive gas) during pyrolysis
Hydropyrolysis
Reactive gas to cap intermediates in pyrolysis vaporCatalytically enhanced hydrogen transfer to reduce oxygen content Use of process modeling to explore commercial concepts
NABC: For Open Distribution
Hydropyrolysis -Preliminary Screening Results
Improved hydrocarbon yields through effective catalytic hydrogen-transfer
NABC: For Open Distribution
Gas / P (psi)
Catalyst Char Yield (wt%)
He / 400 none 10.5
H2 / 400 none 21.0
H2 /400 2wt% DCat-CS1 21.8
Hydrothermal Liquefaction
PNNL—Team Lead
HydrothermalLiquefaction
Liquid hydrocarbons
H2
Catalyticupgrading
solids
Wet biomass
~350ºC, 200 atm, biomass slurry in waterminutes
NABC: For Open Distribution
Slow pyrolysis in pH-moderated, pressurized water
Hydrothermal Liquefaction –
NABC: For Open Distribution
biomass slurry in water~350ºC, 200 atm, residence time of minutes
Hydrothermal Liquefaction – Preliminary Results
NABC: For Open Distribution
Wood Wet feed (9.4 wt%) feed operated for 8 h @ temp and pressure45 g/h separated oil; 30% mass oil yield, 53% on carbon basis
10.9% oxygen on dry basis, 30 TAN, 9.8% moisture0.2% nitrogen, 0.01% sulfur, 0.03% ash, 0.34% solids
12% carbon conversion to gasgas 82% CO2, 12% H2, 6% CH4 and higher hydrocarbon
35% carbon in aqueous, 4.6 pH effluent; 44,000 ppm COD
Corn Stover 11.1 wt% double wet grind feed operated for 8 h @ similar conditions51 g/h separated oil ~1 wt% nitrogen in oil
Feedstock Composition
Operating Conditions
Measured Conversion Yields
Process Model inAspen Plus
Flow rates
Process Economics usingDiscounted Cash Flow Analysis
with Capital and Operating Costs
Fuel Product Yield
Cost $gal
Minimum FuelSelling Price
Analysis Team
NABC: For Open Distribution
R&D TEA LCA
Critical Issues Addressed
Critical Success Factors
Example Biochemical Targets (end Stage II)
Example Thermochemical Targets (end Stage II)
Acceptable fuels &intermediates quality demonstrated
TAN<0.5, O content < 0.2Final products show potential to meet ASTM standards
Intermediates pass 60 day stability testPotential for commercialreadiness demonstrated
Process is ready to pilot based on MB closure, scale/reproducibilityof data and well-defined operations
Reduced carbon footprint compared to fossil based fuels
Process achieves >50% GHG reduction compared to gasoline, jet or diesel benchmark
Carbon & energyefficiency maximized
Carbon and energy efficiency demonstrated to be >50%
Capital and operatingcosts minimized
-Reduction in cellulase cost contribution>50%-Feed concentration to reactor>50%
Reactor RT <5 sec (CFP)Reactor P < 500psig (HYP)
Catalyst/organismrobustness
-95% conversion of carbohydrate portion -Inhibitory compounds identified/mitigated
Lifetime >1 yearLoading <5:1
Toxicity levels < EPA limits
Analytical methods developed to identify compounds27
General ConclusionShift of emphasis at DOE (EERE) toward the fuels that should be produced from biomass resources (emphasis on replacing the “whole barrel of oil”NABC and NAABB leading in technology development (NAABB has a feedstock focus on algal oils and biomass; NABC a conversion focus)NABC emphasis on integration with refinery—use of infrastructure in place to make and deliver those fuels into our vehicle fleet todaySix technologies are being examined, pilot ready technology will be delivered at the conclusion
NABC: For Open Distribution
General ConclusionShift of emphasis at DOE (EERE) toward the fuels that should be produced from biomass resources (emphasis on replacing the “whole barrel of oil”NABC and NAABB leading in technology development (NAABB has a feedstock focus on algal oils and biomass; NABC a conversion focus)NABC emphasis on integration with refinery—use of infrastructure in place to make and deliver those fuels into our vehicle fleet todaySix technologies are being examined, pilot ready technology will be delivered at the conclusion
NABC: For Open Distribution
Questions
Special Acknowledgement to National Advanced Biofuels Consortium (NABC)
Led by the National Renewable Energy Laboratory Tom Foust (PI)
National Alliance for Advanced Biofuels and BioproductsLed by Danforth Plant Sciences Center / Los Alamos National (NAABB)Jose Olivares (PI)
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http://nabcprojects.org/ http://www.naabb.org/