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Products Opportunities from Sugars in the Context of the Biorefinery
Products Opportunities from Sugars in Products Opportunities from Sugars in the Context of the the Context of the BiorefineryBiorefinery
Presented by John HolladayPacific Northwest National Laboratory
May 31, 2006
Liquid Fuels
Power
Products
CO2CO2
Biorefinery
Ash
Lignin
2
AcknowledgementsAcknowledgementsAcknowledgements
Jim WhitePacific Northwest National Laboratory (PNNL)
David JohnsonNational Renewable Energy Laboratory (NREL)
Joe BozellNREL (currently at University of Tennessee, Knoxville)
3
U.S. imports 11.8 million barrels of oil/dayand consumes more than 20 million barrels/day
U.S. imports 11.8 million barrels of oil/dayand consumes more than 20 million barrels/day
US consumption: 400 mil gal and 145 mil gal of diesel /day
4
Energy policy can be distilledinto four broad goals
Energy policy can be distilledEnergy policy can be distilledinto four broad goals into four broad goals
Diversify our energy mix and reduce dependence on foreign petroleum, thereby reducing vulnerability to disruption and increasing the flexibility of the marketto meet U.S. needsReduce greenhouse gas emissionsand other environmental impacts(water use, land use, criteria pollutants) from our energy production and useCreate a more flexible, more reliableand higher capacity U.S. energy infrastructure, thereby improving energy services throughout the economy, enabling use of diverse sources, and improving robustness against disruptionImprove the energy productivity(or energy efficiency) of the U.S. economy
US energy use is 382 Quads (quadrillion Btu)
5
Resource availability—biomassResource availabilityResource availability——biomassbiomass
DOE study identified 1.3 billion tons of dry biomass available in U.S. annually
Potentially could produce 130 billion gallons of liquid transportation fuels (ethanol, mixed alcohols, green gasoline biodiesel and green diesel)
Significant new technology developments needed to maximize production
Same resource could supply virtually all raw materials for the chemical industry
Oil-based crops could produce enough biodiesel to supply 2-5% of our current diesel consumption, but alternative crops and agricultural practices are required.
ORNL/TM/-2005/66
6
DOE’s Vision of BiorefineryDOEDOE’’ss Vision of Vision of BiorefineryBiorefinery
Biorefinery Concept60 billion gallons FuelPower (i.e. Lignin)60 billion lbs products
Cost targetsLiquid fuels $1.06/gal to be competitive with ethanol from starch
Liquid Fuels
Power
Products
CO2CO2
Biorefinery
Ash
Science 2006, 311, 484
Liquid transportation fuels will drive economy of scale 2,000-10,000 tons per day of biomass is reasonable
Chemical and materials products will help drive the economics of the biorefinery
7
Example Products from a Petroleum Refinery
C1: CH4, CO/H2
C2: Ethylene (50)
C3: Propylene (36)
C4: Butane (55)
C6: Aromatics (65)
HOOH
OO
OR
O
H
O
HOOH
On
HO OH
OH
OH3C
OH Syn gasproducts
O OO O O OHHO
OnO
( ) = approx bill lbs/y US consumption
8
Biorefinery Products can be organized similarly
C1: CO/H2
C3: Glycerol
C3: 3-HP
C4: 1,4-diacids
C5: (no petro)
O
OR
O
HOOH
OH
OH3C
OH
Polymers
O OOHHO
HOOH
O Cl
HO OH
RN O
Star
ch,
hem
icel
lulo
se,
Cel
lulo
seSyn gasproducts
C6: (no petro) OOH
OO
OH
HO
O
OHO
OHO
O
OHOH
OHOHOH
OH
9
Sugars Sugars ““Top 1OTop 1O””1,4-Diacids 2,5-Furan-
dicarboxylic acid3-Hydroxy-
propionic acidAspartic acid
Glucaric acid Glutamic acid Itaconic acid Levulinic acid
3-Hydroxy-butyrolactone
Glycerol Sorbitol Xylitol/Arabitol
OHOH
O
O
OOH
OO
OH OH OH
OOH
OHO
ONH2
OH
O
OH
OH
O
OHOH
OHOH
O
NH2
OH
OOH
OHO
OOH
O
O
O O
OH
OH OHOH
OHOH
OHOHOH
OHOH
OH
OHOHOH
http://www.nrel.gov/docs/fy04osti/35523.pdf
Key: Identification of technology needs!
10
Lignin Lignin ““Top 1OTop 1O”” ????
AromaticUS
demand (109 lb)
Lignin required
-theoretical-(109 lb)
Lignin required -current technology-
(109 lb)
BTX 45.3 90.7 907
Terephthalicacid 11.1 12.7 127
Phenol 5.09 9.75 78
Total 61.5 113 1,112
*current technology, assuming a 20% yield products1,2
113
339
lignin sugars
339 billion lbsugars
As much as25 billion gallons
of EtOH
113 billion lb lignin
11
“You can make anything you want from lignin……Except money”
12
Power and process heat to drive chemical recovery~1/3 fuel value of heating oil (~13,000 Btu/lb vs 39,000 Btu/lb)
Used as-is or with minor chemical or mechanical modification
Surfactants, DispersantsCarriers, Fillers & DiluentsRheology control BindersRetarders & Conditioners
Degraded into specific other compounds Activated carbonMonomers-PolymersChemicals (vanillin)Fuel
Current & Past Uses of Lignin
13
Lignosulfonate Current Use
Application World Consumption (2001) %
Concrete Admixture 45
Animal Feed Pellets 13
Road Binders, Dust Control 11
Animal Feed Molasses Additive 3
Pesticide Dispersant 5
Oil Well Drilling Muds 4
Other 19
(Source: Chemical Economics Handbook)
14
2001 2006Ave Yearly
Growth Rate
USA 291 284 -0.5
Canada 58 64 2.0
Japan 90 87 -0.7
W. Europe 318 338 1.2
Rest of World
297-315 262-287 -2.5
Total 1,053-1,074 1,035-1,060 -0.3
Lignosulfonate Consumption
Unit: 1,000 MT
(Source: Chemical Economics Handbook)
15
Evaluation ProcessEvaluation ProcessEvaluation ProcessDefined high-level product categories
High molecular weightLow molecular weight
Defined initial product slate within categoriesIdentify technology needsEvaluation / Scoring process
Degree of difficultyMarketMarket riskBuilding block utilityMixture vs pure chemical
16
How might lignin fit into the biorefinerytoday and tomorrow?
biomass pretreatment andseparation
oleochemicalplatform (underdevelopment)
sugarsplatform
lignin
thermochemicalplatform
CO/H2
EtOH,sugar products
conditioning, as needed
EtOH, higher alcoholsFT chemicals
high mwlignin products low mw
lignin products
near
mid
long
fatty acidsglycerol
combustion
lignin program activities
17
lignocellulosicfeedstock
insolubles
solubles
hemicellulose lignin
phase separation
aqueous organic
fiberize
wash
cellulosepulp
lignocellulosicfeedstock
insolubles
solubles
hemicellulose lignin
phase separation
aqueous organic
fiberize
wash
cellulosepulp
NREL Clean Fractionation Process
Organic SolventMixture
18
Near Term Opportunities with Lignin
Lignin CombustionProcess steam and power (1/3 Btu value of heating oils)Chemical recovery (kraft)
Mixed alcoholsFuel ethanol, propanol, butanol
Syn gasFischer-Tropsch chemicals
PyrolysisLignin fuels
Reformulated gasolines
19
Gasification Synthesis
Chemical Alcohols
Methanoln-Propanoln-Butanoln-Pentanol
SyngasForest
Residues
Thermochemical stand alone Gasification
Ethanol
Biochemical/ThermochemicalGasification Biorefinery
Ethanol via bioconversionCorn Stover
2,000 dMT/day
Ethanol198,400 gpd
Lignin-rich Residue 600 dMT/day
Steam &Power
Gas-FiredCHP Plant
SyngasProduction Synthesis
Chemical Alcohols 11,800 gpd n-Propanol
9,100 gpd n-Butanol11,800 gpd Amyl/Hex Alcohols
Biomass Residues/Pyrolysis Oils1,205 dMT/day
SyngasEthanol
98,000 gpd
Ethanol296,400 gpd
Ethanol via bioconversionCorn Stover
2,000 dMT/day
Ethanol198,400 gpd
Lignin-rich Residue 600 dMT/day
Steam &Power
Gas-FiredCHP Plant
SyngasProduction Synthesis
Chemical Alcohols 11,800 gpd n-Propanol
9,100 gpd n-Butanol11,800 gpd Amyl/Hex Alcohols
Biomass Residues/Pyrolysis Oils1,205 dMT/day
SyngasEthanol
98,000 gpd
Ethanol296,400 gpd
21
Biochemical/ThermochemicalGasification Biorefinery
Ethanol via bioconversion
Corn Stover
Lignin-rich Residue
Steam &Power
Coal-FiredCHP Plant
Gasification Synthesis
Chemical Alcohols Methanol
n-Propanoln-Butanoln-Pentanol
Syngas
Ethanol
Coal
22
Forest Residues
Water soluble pyrolysis oil
PyrolyticligninPyrolysis Hydrotreating/
hydrocracking
Pyrolysis to Gasoline integrated with mixed alcohol synthesis
“Green” Gasoline
“Green” Diesel
Reforming
AlcoholSynthesis
Syngas
Methanoln-Propanoln-Butanoln-PentanolEthanol
Fast Pyrolysis• Dry precursor• 0.5 s / 500 C / 1 atm• Inert atmosphere / solid
particle heat carrierProducts
• Pyrolysis oil (guaiacols, etc)• Aqueous phase (sugar
breakdown products)Commercial applications
• “Liquid smoke”• “resins” not commercial• “mixtures” not pure cpds
23
Ethanol via bioconversion
Corn Stover
Lignin-rich Residue
Steam &Power
Gas-FiredCHP Plant
Pyrolysis Hydrotreating/ hydrocracking
Green GasolinePyrolytic
lignin
Coal
Biochemical/ThermochemicalPyrolysis Biorefinery
(Diesel is recycled to produce a lignin slurry feed)
Ethanol
24
Economics not demonstrated at scale
US 5,959,167, 6,172,272, US Patent Application SN 10/080,082
Hydrodeoxygenation (HDO)
Selective Ring Hydrogenation
(SRH)
Selective Hydrogenolysis (HT)
Etherification
Base Catalyzed Depolymerization
(BCD)
NaphthenicFuel Additive
Oxygenate Fuel Additive
Lignin
Hydrodeoxygenation (HDO)
Hydrocracking (HCR)
Aromatic Fuel Additive
.
Phenolic Intermediates
Hydrodeoxygenation (HDO)
Selective Ring Hydrogenation
(SRH)
Selective Hydrogenolysis (HT)
Etherification
Base Catalyzed Depolymerization
(BCD)
NaphthenicFuel Additive
Oxygenate Fuel Additive
Lignin
Hydrodeoxygenation (HDO)
Hydrocracking (HCR)
Aromatic Fuel Additive
.
Phenolic Intermediates
Lignin-based Fuels (NREL and U. of Utah)
25
Mid Term Opportunities with LigninHigh Molecular Weight Products
Carbon fiberEconomical purificationModifications to improve melt-spin ratesHigh carbon yields
Polymer FillersModifications to improve compatibility with polymersControlled alteration of molecular weight
PolyectrolytesControl of charge densityConsistent lignin propertiesControl of molecular weight
Thermoset resinsViscosity controlFunctional group enhancementOxidative and thermal stabilityColor
26
Carbon fiber is currently produced by pyrolysis of polymer grade polyacrylonitrile (PAN)Both the process and the raw materials are prohibitively expensive for automotive applicationsTo reduce costs
new precursors—kraft ligninnovel fiber production
DOE FreedomCarLightwieghting Materials Program
DOE DOE FreedomCarFreedomCarLightwieghtingLightwieghting Materials ProgramMaterials Program
27
DOE FreedomCarLightwieghting Materials Program
DOE DOE FreedomCarFreedomCarLightwieghtingLightwieghting Materials ProgramMaterials Program
Diverting 10% of U.S. lignin could replace half of the steel in all domestic passenger vehiclesKraft lignin, as a melt spun carbon fiber feedstock
improves availabilitydecreases sensitivity to petroleum cost, and decreases environmental impacts
28
DOE FreedomCarLightwieghting Materials Program
DOE DOE FreedomCarFreedomCarLightwieghtingLightwieghting Materials ProgramMaterials Program
Impurities cause bubble formation weakening of the fiber during melt spinning
short lengths of polysaccharidessalts (residual from kraft pulping)molecular weight polydispersityparticulate contaminantswater and other volatiles in dried lignin
Diatom Sand grain
29
DOE FreedomCarLightwieghting Materials Program
DOE DOE FreedomCarFreedomCarLightwieghtingLightwieghting Materials ProgramMaterials Program
Require low cost kraft lignin purification techniquesderivatization of the precipitated lignin
Scanning electron micrograph of carbonized lignin blend fibers produced during multi-filament spinning
Improved fracture patterns resulting from better mixing of melt prior to spinning
30
Carbon fiber for automobile applications
Lignin has potential for lower manufacturing costs than PAN
Reduced Processing costs Melt spun versus solution spunShorter residence time required in the oxidation/stabilization step
0
2
4
6
8
10
Base Textile Lignin
Variable costs Labor Other fixed costs Depreciation
$/lb
of
CF
$/lb
of
CF
Low-volume case High-volume case
0
2
4
6
8
10
Base Textile Lignin
Variable costs Labor Other fixed costs Depreciation
8.12
6.00
4.98
7.00
4.933.89
Manufacturing Cost Comparison
(Kline & Company March 29, 2004)
31
Carbon fiber for automobile applications
Lignin has potential for lower capital costs than PANReduced Processing costs
Melt spun versus solution spunShorter residence time required in the oxidation/stabilization step
0
2
4
6
8
0
2
4
6
8
3.89 3.763.513.64
Base investment
90% Baseinvestment
80% Baseinvestment
70% Baseinvestment
$/lb
of
CF4.92 4.81 4.594.70
Base investment
90% Baseinvestment
80% Baseinvestment
70% Baseinvestment
$/lb
of
CF
Manufacturing Cost Comparison
Commodity Textile PAN Precursor Lignin Precursor
(Kline & Company March 29, 2004)
32
Long Term Opportunities with Lignin
Simple AromaticsHydroxylated aromaticsAromatic aldehydesAromatic acids / diacidsβ-ketoadipic acid, aliphatic acidsAromatic and aliphatic polyolsAlkanesQuinones
Technology barriers Selective catalysis
DehydroxylationsDemothoxylationsDealkylationsOxidationHydrogenolysisC-H activationAryl-OH bond activationEtc
Working with heterogeneous starting materialsUse of mixtures for productsSeparations
33
The β-Ketoadipate Pathway
OH
OH
-OOC OH
OH
COO-COO-
-OOC
O O-OOC
O O
COO-COSCoAO
COO-COO-O
COO-COO-
O O-OOC-OOC
-OOC
naphthalenephenanthrenetoluenebenzenecinnamatephenolanilinesalicylatebenzoate
shikimate4-hydroxybenzoate4-coumarateferulatevanillateconiferyl alcoholquinatecyclohexane carboxylate4-chlorobenzoate
catecholprotocatechuate
β-carboxymuconate
γ-carboxymuconolactone
β-ketoadipate enol lactone
muconate
muconolactone
β-ketoadipate
succinyl-CoA + acetyl CoA
β-ketoadipyl-CoA
34
phenols, cresols, substituted phenols
phenolic acids, catechol
acetic acid, phenol, substituted phenols, CO,
methane
acetylene, ethylenephenol, substituted
phenols
Vanillin, dimethylsulfide,
methyl mercaptan dimethyl sulfoxide
OH
O
O
OH
O
OCH 3
O
OH
L
OCH 3
H3CO OHOH
OCH3
OH
OH
H3CO
OL
L
hydrogenation
alkali fusion
microbial conversions
fast thermolysis
oxidative
hydrolysis
vanillic, ferulic, coumaric and other
acids
lignin with increased level of
polymerization
oxidized lignin for paints and coatings
pyrolysis
enzymatic oxidation
Summary of transformations in the literature
35
Possible new products and uses of lignin
Aromatic rich pyrolysis oils
Mixed organic acids / aromatic acids BTX type liquid
fuels Copolymers with HMF
(high strength & heat resistance)
Copolymers in polyesters
Low cost fillers
Mixed phenolics
Various quinones
Mixed benzylicaldehydes
OH
O
O
OH
O
OCH3
O
OH
L
OCH3
H3CO OHOH
OCH3
OH
OH
H3CO
OL
L
polyurethanes and heat resistant polyurethanes
thermoplastic elastomers
block co-polymers
Carbon fibers and carbon composites
Macromolecules
36
Economics of displacing lignin as source of power and heatValue add of productsMarket development
New macromoleculesMixed streams of small molecules
Health of today’s domestic pulp millsTechnology
Technology base is small as compared to sugarsWorking with structurally heterogeneous materialsWorking with oxidatively reactive materials
SeparationsLignin-cellulose (biomass)Product separations
Barriers to future uses of lignin
37
% Lignin
% Oil
% Sugars
05
101520253035404550
Ove
rall
Plan
t RO
I
0
7 3
6
11 3
9
15 3
10
22 3
11
29 3
12
37 3
13
44 3
14
Percent Feedstock (Sugars, Oil and Lignin) Utilized for Chemicals
EtOH BDO Oil Lignin2122 Tons/Day$30/Dry TonBDO @ $0.60/lb
Payoff of Integrated Biorefinery--EtOH, BDO, Oil, Lignin--
38
Enabling the bio-industrial revolutionEnabling the bioEnabling the bio--industrial revolutionindustrial revolution
Feedstock costs must continue to drop in real terms to become more competitive
Improvements in agronomic practicesBiomass conversion technologies
Processing technology must evolveGovernment investment in basic researchIndustry commitment to invest and develop process technology related to aqueous processing of dilute solutionsNovel catalysts, both biological and chemical, are required
Product business models are criticalNew toolsPlatform chemical conceptPartnerships between traditional chemical and agricultural firms need to emerge
39
Final considerationsFinal considerationsFinal considerations
Globally, there’s no shortage of hydrocarbons, only a shortage of high-quality hydrocarbonsSubstantial investment is needed to drive new technologies that will reduce the cost of conversion of low quality hydrocarbons into high quality liquid transportation fuels and chemicalsNew technologies to further improve efficiency must continue to be developedNew relationships between owners/producers of hydrocarbons and hydrocarbon converters must be formed for broad based development of domestic energy supplies that are economically viable
40
Challenges and risksChallenges and risksChallenges and risks
Technical challenge: Successfully deploy new and robust conversion and carbon-management processes given the scale and complexity of the energy infrastructure.Business challenge: Economic risk of volatile oil prices. Investment in this space may become stranded if the cost of oil once again drops in response to both additional supplies and reduced demand.
If we do not aggressively pursue domestic solutions now for bothexpanded conversion capacity and carbon management, we risk substantial and increasing economic and environmental damage.
If we do not aggressively pursue domestic solutions now for bothexpanded conversion capacity and carbon management, we risk substantial and increasing economic and environmental damage.
41
42
Property Lignosulfonates Kraft lignins Organosolvlignin
Molecular weight
20,000 - 50,000 2,000 - 3,000 < 1,000
Empirical formula*
C9H8.5O2.5(OCH3)0.8
5 (SO3H)0.4
C9H8.5O2.1S0.1(OCH3)0.8 (CO2H)0.2
C9H8.53O2.45(OCH
3)1.04
Ave. monomer MW
215 – 254 180 188
Polydispersity 6 – 8 2 - 4 2.4 - 6.4
Sulfonate 1.25 - 2.5 meq/g 0 0
Organic sulfur 4 – 8 % 1 - 1.5 % 0
Color Light to dark brown dark brown brown
SolubilitySol in H2O (all pH's) Insol in organics
Sol in alkali (pH >10.5), DMF, methyl cellosolve
Insol in waterSol in alkali and many organic
43
LIGNIN SOURCESLIGNIN SOURCESLIGNIN SOURCES
Precipitation from black liquor (pH adjustment--CO2 &/or acid)
Organo-solve processes
Remains of cellulose hydrolysis, ie lignocellulosicethanol plants
44
Lignin Oxidation ProcessesLignin Oxidation ProcessesLignin Oxidation ProcessesBleaching
Vanillin and DMSO synthesis
(about 3%)DMSOoxidize
Me2SS8, heat
(about 10%)base, 225o
metal oxidesligninsulfonates
CHO
OHOMe
HOH2C
OHO
OROMe
OMe OMeO
OMeOR
HOHOH2C
O
HOH2C
Cl
HO
OROMe
HOOMe
Cl
Cl
Cl
Cl
HOOCHOOC
Cl
Cl2
45
Proposed Mechanism for Co-salen oxidationsProposed Mechanism for CoProposed Mechanism for Co--salen oxidationssalen oxidationsOH
OHMeO OMe
(salen)Co O O
(salen)Co
OH
OMeO OMe
OH
OMeO OMe
O OCo(salen)
(salen)CoOH
OMeO OMe
O
OH
OHMeO OMe
H2O
(salen)Co
(salen)Co O OO2
46
Reaction Matrix
OOH
OHHOHO
OH
HOOCO
HOOC COOH
NH2
HOOC COOH
OHHOOC COOH
OHOHHO
COOH HOOC COOH
O
2, 2-ketoglutaric acid 3, glutamate
2-hydroxyglutaric acidglutaric acid
chemicalconversion
Renewable feedstocks(carbohydrate and lignin sources)
lignin
enzymaticconversion
1, β-ketoadipic acid
new polyesters,nylons
nylon-4polymers
1,2,5-pentanetriol
glucose from cellulose or starch
47
Current state of gasification processCurrent state of gasification processCurrent state of gasification process
Can any be eliminated or combined?Are radically different processes possible?What would it take to substantially improve various steps?What is the business case to support investment in total system production capacity?
Examine the entire process and understand all the boxes to drive economic competitiveness
48
R&D support must be technology driven – not productdrivenR&D support will be needed not only for lignin conversion but also for lignin conditioningCatalysis (chemical and biological) will be an important technology area to supportSupport of new separation technologies will be of particularvalue High molecular weight products must be accommodated in an R&D program as well as mixed low molecular weightmaterialsContinued development of rapid analysis technology will beneededSupport of technoeconomic analysis will be of particularvalue
Preliminary Recommendations
