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WP 2A Pyrolysis Biorefinery
Doug ElliottSeptember 28, 2005
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Presentation OrganizationPresentation OrganizationPresentation Organization
Biorefinery basics
U.S. Department of Energy program
Earlier PyNe efforts
Other Biorefinery concepts
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Important to Note:Important to Note:Important to Note:
In both PRESENT and FUTURE biorefineries:
Fuels production provides for large economies of scale
Bio-based products, while smaller in volume, provide greater rates of return and drive profit
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The Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of Pyrolysis
Part of a sugars-based biorefinery
Part of a Petroleum Refinery
Stand-alone facilities
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An Example of a Current BiorefineryAn Example of a Current BiorefineryAn Example of a Current Biorefinery
Corn Wet Mill
starch corn oilcorn glutenmeal
corn gluten feed
food & industrial starches
hydrolysis
glucose
fuelethanol
High fructosecorn syrup
sorbitol
• foodstuffs• pharma.
polyols isosorbide
hydrogenation
Othersweeteners
citric acid lysine
xanthan gumsitaconic acid
& other fermentation
products
industrial oils
lactic acid
PLApolymers
•resins & plasticsapplications
•polyesters•surfactants•pharmaceuticals
deicerssolventscoatings
glycerolfood oilsfeed oils
Corn Wet Mill
starch corn oilcorn glutenmeal
corn gluten feed
food & industrial starches
hydrolysis
glucose
fuelethanol
fermentation
sorbitol
• foodstuffs• pharma.
polyols isosorbide
hydrogenation
citric acid lysine
xanthan gumsitaconic acid
& other fermentation
products
industrial oils
lactic acid
PLApolymers
•resins & plasticsapplications
•polyesters•surfactants•pharmaceuticals
deicerssolventscoatings
glycerolfood oilsfeed oils
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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Current Ethanol ProcessCurrent Ethanol ProcessCurrent Ethanol Process
Corn Dry Grind Liquefaction Scarification
Fermentation PrimaryDistillation
DistillationRectifier
MolecularSieves
Centrifuge
Triple EffectEvaporator
DDGDryer
DDGAnimal Feed Ethanol
Solids
50%EtOH
95%EtOH
100%EtOH
Liquids
Water Recycle
Solids
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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Current Status of Ethanol Dry MillsCurrent Status of Ethanol Dry MillsCurrent Status of Ethanol Dry Mills
Economics are difficult� Current ethanol facilities are limited to only two products,
ethanol and DDG� Economics are highly dependent of value of the co-
product DDG� Significant energy costs are associated with the drying of
DDG� Markets for DDG are not always favorable and will
deteriorate as additional ethanol facilities come on line
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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Strategies for Creating Additional ValueStrategies for Creating Additional ValueStrategies for Creating Additional Value
Modify dry mills to include a quick steeping process that allows germ recoveryAdd an intermediate filtration process to recovery non-starch derived sugars (hemicellulose)Develop new fermentations for utilization of five carbon sugars (itaconic acid, succinic acid, etc)Develop new chemistry to produce value added products from hemi-cellulose (sugar alcohols, polyols)Include an energy component-pyrolyze “DDG or modified DDG” to produce bio-oil
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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The Holistic Ethanol FacilityThe Holistic Ethanol FacilityThe Holistic Ethanol Facility
Corn Quick Steep Scarification
Filtration Fermentation EthanolRecovery
MolecularSieves
“Fiber” Hydrolysis New DDGAnimal Feed
Ethanol
StarchEtOH 95%
EtOH100%EtOH
GermSeparation
Fermentation
CatalyticConversions
Pyrolysis
Fuel/PowerEG, PG
Glycerol, Etc
ItaconicSuccinic, Etc
Oil
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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% Lignin
% Oil
% Sugars
05
101520253035404550
Ove
rall
Pla
nt R
OI
0
7 3
6
11 3
9
15 3
10
22 3
11
29 3
12
37 3
13
44 3
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Percent Feedstock Utilized
EtOH BDO Oil Lignin
Integrated Biorefinery“Back of the Envelope Economics”
EtOH, BDO, Oil, Lignin
Integrated BiorefineryIntegrated Biorefinery“Back of the Envelope Economics”“Back of the Envelope Economics”
EtOHEtOH, BDO, Oil, Lignin, BDO, Oil, Lignin
2122 Tons/Day2122 Tons/Day$30/Dry Ton$30/Dry TonBDO @ $0.60/lbBDO @ $0.60/lb
T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005
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The Present View of the BiorefineryThe Present View of the BiorefineryThe Present View of the Biorefinery
LignocellulosicBiomass
Hydrolysis Fermentation
Ethanol Fuel
Distillation
Products
lignin
sugars
?
D.J. Stevens, PyNe, 2005
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The Present View of the BiorefineryThe Present View of the BiorefineryThe Present View of the Biorefinery
LignocellulosicBiomass
Hydrolysis Fermentation
Mixed Alcohol Synthesis
Gasification
Ethanol Fuel
Distillation
Products
Products(higher alcohols)
lignin
sugars
syngasAdditionalBiomass
Heat, electricity
D.J. Stevens, PyNe, 2005
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Possible Future BiorefineryPossible Future BiorefineryPossible Future Biorefinery
LignocellulosicBiomass
Hydrolysis Fermentation
UpgradingPyrolysis
Ethanol FuelDistillation
Products
Products
lignin
sugars
bio-oilAdditionalBiomass
Motor Fuel
Heat, electricity
D.J. Stevens, PyNe, 2005
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Hydrogenation Pathways with Ruthenium Catalyst
Hydrogenation Pathways with Hydrogenation Pathways with Ruthenium CatalystRuthenium Catalyst
OH
OCH3
CH2
OH
propyl guaiacol
propylmethoxycyclohexanoleugenol (propenylguaiacol)
methoxycyclohexanol
cyclohexanol
guaiacol
methyl-guaiacol
methylmethoxycyclohexanolmethylcyclohexanol
cyclohexanediol
methylcyclohexanediol
propylcyclohexanol
propylcyclohexanediol
D.C. Elliott, STCBC, September 2004
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Cyclohexanol MarketCyclohexanol MarketCyclohexanol Market
price $0.81-0.83/lb from benzenecost ~$0.35/lb w/25% ROIvolume 852 million lb (1972 est. U.S.)
6,400 million lb world (incl cyclohexanone)1992sales 20 million lb (incl cyclohexanone)1992
(most is used internally for adipic acid)uses adipic acid for nylon, esters for
plasticizers, cyclohexanone for caprolactam, cyclohexylamine for emulsion stabilizer
D.C. Elliott, STCBC, September 2004
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The Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of Pyrolysis
Part of a Petroleum Refinery� Biomass first would be converted to bio-oil, possibly at
distributed locations at small scale� Bio-oil can be partially upgraded by catalytic
hydrotreatment at larger scale in proximity of a petroleum refinery
� Upgraded bio-oil then would be co-fed with petroleum feedstocks through a catalytic process to produce conventional refinery product slate
� The global petroleum industry is showing more interest� From the Department of Energy perspective, this is a
medium-term approach
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Pyrolysis/Petroleum BiorefineryPyrolysis/Petroleum BiorefineryPyrolysis/Petroleum Biorefinery
LignocellulosicBiomass
Upgrading and Refining with Petroleum
Fast Pyrolysis Products
bio-oil
Motor Fuel
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The Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of Pyrolysis
Stand-alone facilities� Small size makes economics of fuel production difficult� May be more appropriate for heat and power
applications� High-value specialty chemicals may provide the
economic driver� Unlikely to gain strong support from DOE in the U.S.
because of current focus on petroleum displacement
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Concept of a BiorefineryConcept of a BiorefineryConcept of a Biorefinery
D. Radlein, Fast Pyrolysis Handbook, 1999
Pyrolyzer
Fuel Gas
Char Converter
Bio-oil
Ash Activatedcarbon
Biomass AnhydrosugarsHydrolysis & Fermentation
Reaction
Reaction
Reaction
Separation
Separation
Catalytic Reforming
NH3
lime
alcohol
water
Ethanol
Slow Release Fertilizers(N, Ca, Zn, Fe ...)
Noxolene™(NOx reduction)
BioLime™(NOx/SOx reduction)
Fuel EnhancersFlavor ChemicalsChemicalsFlavors
Adhesives
Diesel/boiler FuelSpecialty
Synthesis GasHydrogen
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Other Chemicals Produced from Bio-oilOther Chemicals Produced from BioOther Chemicals Produced from Bio --oiloil
Wood Preservative (Ensyn patent)Road deicers (Waterloo patent)Resin formulations (many patents)Levoglucosan and Levoglucosenone
Czernik & Bridgwater, Fast Pyrolysis Handbook 3, 2005
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Integrated Pyrolysis Combined CycleIntegrated Pyrolysis Combined CycleIntegrated Pyrolysis Combined Cycle
Biomass
char
chemicals
Bio-oil
gasrecycle
gas and steam turbines
electricityR.C. Brown et al. Iowa State UniversityInternational Journal of Power & Energy Systems24 (3) 2004
Forschungszentrum Karlsruhein der Helmholtz-Gemeinschaft
ITC-CPV HEFW
FW
fast pyrolysis
biomass preparation
liquid fuel synthesissingle pass operation
rail transport from many pyrolysis plants
to large, central plant for syngas generation and us e
entrained flow gasification~ 1200 °C, ≥ ≥ ≥ ≥ 60 bar, ττττ 2 - 3 s
gas cleaningwith heat recovery
electricity generationCC turbine, engine, FC
BACKBONE OF A BIOMASS REFINERYDifferent biomass and carbon feedstock
bio-oil/char -slurry
lignocellulosic biomass:wood, straw, hay ....
fossilfuel:
other biomass:coal ... starch, oil ...
pulverised coalcoal/water slurry
organic waste:paper, plastics, dung ...
co-generation of a marketable product mix
synthesis products:synfuel, chemicals, H 2
electricitylow Theat
O2
CO2
specialchemicals
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The University of GeorgiaBiorefinery/Carbon Cycling Program
The University of GeorgiaThe University of GeorgiaBiorefinery/Carbon Cycling ProgramBiorefinery/Carbon Cycling Program
Biorefinery
Biomass
Bio-Oil
Industrial emitter of greenhouse gases
Stack emissions are convertedto carbon based fertilizer
carbon fertilizer back into fields
NH3 and CO2scrubbing media
vanillic acidacetic acidguaiacolphenol ...
Hydrogen and Fischer-Tropsch Diesel
E.D. Threadgill / P. Harrell, U. Georgia website
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SummarySummarySummary
Numerous opportunities involving:� incorporation into sugar biorefinery� incorporation into a petroleum refinery� stand-alone with chemical, fuel, and power production� incorporation into a gasification and synthesis plant
Pyrolysis demonstration will lead to biorefineryProduct separation and recovery is a major hurdleFinding the right niche is key
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