EPA Presentation on Biodiesel

7/30/2019 EPA Presentation on Biodiesel

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MixAlco:

Biofuels and Chemicals

from Biomass

MixAlco:

Biofuels and Chemicals

from Biomass

Mark Holtzapple

Department of Chemical EngineeringTexas A&M University

College Station, TX


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Biofuels address Biofuels address

Energy shortageEnergy shortage

Global warmingGlobal warming


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BiofuelsBiofuels

CO2


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Lets envision an

ideal biofuel process

Lets envision an

ideal biofuel process


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FeedstockFeedstock

CO2


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Multiple FeedstocksMultiple Feedstocks

treestrees

grassgrass agricultural residuesagricultural residues

energy cropsenergy crops

municipal solid wastemunicipal solid waste

sewage sludgesewage sludge

animal manureanimal manure


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7878

10.910.9

33

4.34.3

400400

330330

220220

U.S. Biodegradable Wastes

Municipal Solid WasteMunicipal Solid Waste

Sewage SludgeSewage Sludge

IndustrialIndustrial BiosludgeBiosludge

Recycled Paper FinesRecycled Paper Fines

Agricultural ResiduesAgricultural Residues

Forestry ResiduesForestry Residues

ManureManure

AmountAmount(million(million tonnetonne/year)/year) Alcohol PotentialAlcohol PotentialWasteWaste (billion gal/year)

1010

1.41.4

0.40.4

0.50.5

5252

4343

2828

TotalTotal 1,0461,046

135135

U.S. Gasoline Consumption = 130 billion gal/yearU.S. Gasoline Consumption = 130 billion gal/year

U.S. Diesel Consumption = 40 billion gal/yearU.S. Diesel Consumption = 40 billion gal/year


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High-Productivity FeedstocksHigh-Productivity Feedstocks

Corn grain Sweet sorghum Energy cane3.4

20

30

P

roductiv

ity

Dry

tons/(ac

reyr)


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Sweet SorghumSweet Sorghum

Grows in ~35 US states


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Energy Cane


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Energy Cane


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High Agricultural IncomeHigh Agricultural Income

Corn grain Sweet sorghum Energy cane

($2.40/bu) ($40/tonne) ($40/tonne)

340

730

1090

GrossInco

me

$/(acrey

r)


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Low Environmental ImpactLow Environmental Impact

WaterFertilizer

Pesticides

Herbicides

Soil erosion

Corn Sweet EnergyGrain Sorghum Cane

High Low LowHigh Low Low

High Low Low

High Low Low

High Low Low

Environmental

cost per

unit of biomass


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Aquatic Biomass Water HyacinthAquatic Biomass Water Hyacinth


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Aquatic Biomass Water HyacinthAquatic Biomass Water Hyacinth


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Aquatic vs Terrestrial FeedstocksAquatic vs Terrestrial Feedstocks

Corn grain Sweet sorghum Energy cane Hyacinth Hyacinth

CO2 Enrich

3.4

2030Pro

ductivity

Dryto

ns/(acreyr) 70

100


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ProcessProcess

CO2


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Ideal Process PropertiesIdeal Process Properties

No sterilityNo genetically modified organisms (GMOs)

Adaptable

No pure cultures

Low capital

No enzymesHigh product yields

No vitamin addition

Co-products not required


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FuelFuel

CO2


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Fuel PropertiesFuel Properties

Ethanol MTBE Mixed

Alcohols

Octane high high high

Volatility high low low

Pipeline shipping no yes yes

Energy content low high high

Heat of vaporization high low low

Ground water damage no yes no


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Is there an ideal biofuel

technology?

Is there an ideal biofuel

technology?

CO2


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ResearchersResearchersFaculty Mark Holtzapple

Richard Davison

Post Docs

Praveen Vadlani Vincent Chang

Xu Li

Masters

Murlidahar Nagwani Chang Ming Lee

Champion Lee

Seth Adleson

Robert Rapier

William Kaar

David Gaskin

Hiroshi Shirage

Wilbelto Adorno-Gomez

Shelly Williamson

Maria Almendarez

Ramasubramania Narayan Patricia O'Dowd

Hung-Wen Yeh

Manohar Vishwanathappa

Brian Lipscomb

John Miles Andrew Moody

Somsak Watanawanavet

PhD

Nan Sheng Chang Shushien Chang

Mitch Loescher

Kyle Ross

Susan Domke

Salvador Aldrett-Lee

Cateryna Aiello-Mazzarri

Wenning Chan

Piyarat Thanakoses

Xu Li

Cesar Granda

Guillermo Coward-Kelly Li Zhu

Se Hoon Kim

Frank Agbogbo

Zihong Fu

Jonathan O'Dwyer Maxine Jones

Rocio Sierra Ramirez

Jorge Lara


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Research StatisticsResearch Statistics

Year started = early 1991

Time spent = 14 years Labor = ~130 personyears

Total funding = $2.7 mill


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You cant have it all!You cant have it all!

Cheap

Good

Fast

UniversityIndustry


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PatentsPatents

5,986,133

6,478,965

5,969,189

6,262,3135,962,307

5,874,263

5,865,898

5,693,296

6,043,392

6,395,926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcohol

FuelsFuels

HydrogenateHydrogenate

MixedMixed

KetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium Carbonate

LimeLime


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MixAlco Process Version 1MixAlco Process Version 1

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln


FuelsFuels


MixedMixed

KetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat


LimeLime

Carboxylate

Salts


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PretreatmentPretreatment

FermentFerment DewaterDewaterPretreatThermalThermal

ConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln


FuelsFuels

MixedMixed

KetonesKetonesBiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium Carbonate

LimeLime

Carboxylate

Salts


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Lime TreatmentLime Treatment

TT= 100= 100ooCC

tt= 1 h= 1 hLime loading = 0.1 g Ca(OH)Lime loading = 0.1 g Ca(OH)22/g biomass/g biomass

Water loading = 5 to 15 g HWater loading = 5 to 15 g H22O/g biomassO/g biomass


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In situ DigestionIn situ Digestion

Weigh ~ 2 g of biomassWeigh ~ 2 g of biomass

Place biomass inPlace biomass in tea bagtea bag

PlacePlace tea bagstea bags in porous sackin porous sack

Place porous sacks in cattle rumenPlace porous sacks in cattle rumen IncubateIncubate

Remove porous sackRemove porous sack

WashWash tea bagstea bags

DryDry

Weigh residueWeigh residue


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In-SituDigestionIn-Situ Digestion

SugarSugar--

canecane

bagassebagasse

AfricanAfrican

milletmillet

strawstraw

SorghumSorghum

strawstrawTobaccoTobacco

stalksstalks

4848--hDigestion

hDige

stion

(gdigested/gfed)

(g

digested/gfed) 1.01.0

0.80.8

0.60.60.40.4

0.20.2

0.00.0

UntreatedUntreated

LimeLime--treatedtreated


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Pretreatment Vessels


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Advanced Lime TreatmentAdvanced Lime Treatment

Biomass + Lime

Gravel

Air


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Building the PileBuilding the Pile

~100 ft


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Crew directing the flow



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Lignin RemovalLignin Removal

0

5

10

15

20

25

30

0 50 100 150 200 250 300

Time (days)

Lignin

Contentin

Treated

Bagasse

li

nin/100

ofba

asse

0

5

10

15

20

25

30

0 50 100 150 200 250 300

Time(days

Lignin

Contentin

Treated

Bagasse

50 100 150 200 250 300

Time (days)

50 100 150 200 250 300

Time (days)

30

25

20

15

10

5

0

Lignin

Content(glignin

/100gbagasse) 30

25

20

15

10

5

0

Lignin

Content(glignin

/100gbagasse) 30

25

20

15

10

5

0

LigninContent(glignin/100gbagasse) 30

25

20

15

10

5

0

LigninContent(glignin/100gbagasse)

25oC

50oC57oC 25oC

50oC57oC

No Air Air


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Mixed-Acid Fermentation

0

10

20

30

40

50

60

0 0.2 0.4 0.6 0.8 1

Conversion

Totalacidconcentration

(g/L)

5

LRT

(days)

101520.5

2

4

8111418

VSLR

(g/(Ld))Air

No Air

Lime Treatment: 2 weeks, 25oC

Terrestrial Inoculum


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FermentationFermentation

Ferment DewaterDewaterPretreatPretreatThermalThermal


Lime KilnLime Kiln


FuelsFuels

MixedMixed



LimeLime

Carboxylate

Salts


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Environments where organic

acids naturally form

Environments where organic

acids naturally form

animal rumenanimal rumen

-- cattlecattle

-- sheepsheep

-- deerdeer-- elephantselephants

anaerobic sewageanaerobic sewage digestorsdigestors swampsswamps

termite gutstermite guts


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Why are organic acids favored?Why are organic acids favored?

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH

1212OO

66 2 C2 C

22HH

55OH + 2 COOH + 2 CO

22G =G = --48.56 kcal/mol48.56 kcal/mol

CC66HH1212OO66 3 C3 C22HH33OOHOOH G =G = --61.8 kcal/mol61.8 kcal/mol

5 C5 C66HH1212OO66 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 44 + 6 H+ 6 H22OO

(67 mol%) (22 mol%) (11 mol%)(67 mol%) (22 mol%) (11 mol%)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid


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Typical Product Spectrum

at Different Culture Temperatures

Typical Product Spectrum

at Different Culture Temperatures

40oC 55oCC2 Acetic 41 wt % 80 wt %

C3 Propionic 15 wt % 4 wt %C4 Butyric 21 wt % 15 wt %

C5 Valeric 8 wt %


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Marine InoculumMarine Inoculum

0

1020

30

40

50

60

70

80

90

0 0.2 0.4 0.6 0.8 1

Conversion

Totala

cidconcentrati

on(g/L)

5

LRT

(days)

10

15

4111418

20.5

VSLR (g/(Ld))2

8

Marine Inoculum

Air

Terrestrial Inoculum

No Air

Storage + PretreatmentStorage + Pretreatment


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Storage + Pretreatment

+ Fermentation

Storage + Pretreatment

+ Fermentation

Biomass + Lime + Calcium Carbonate

Gravel

Air

Tarp Cover


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DewateringDewatering

FermentFerment DewaterPretreatPretreatThermalThermal


Lime KilnLime Kiln


FuelsFuels

MixedMixed



LimeLime

Carboxylate

Salts


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Vapor-Compression DewateringVapor-Compression Dewatering

Salt

Solution

(Fermentor

Broth)

Distilled Water

Filter

Salt Crystals

Compressor

Work


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Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreatThermal

Conversion HydrogenateHydrogenate

Lime KilnLime Kiln


FuelsFuels

MixedMixed



LimeLime

Carboxylate

Salts

Th l C iThermal Con ersion


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Thermal Conversion

Stoichiometry

Thermal Conversion

Stoichiometry

HH33CCOCaOCCHCCOCaOCCH33 33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH

33CCHCCH

22CHCH

22COCaOCCHCOCaOCCH

22CHCH

22CHCH

33

33CCHCCH

22CHCH

22CCHCCH

22CHCH

22CHCH

33 + CaCO+ CaCO

33

Calcium ButyrateCalcium Butyrate DipropylDipropyl KetoneKetone

OO OO OO


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Thermal Conversion KineticsThermal Conversion Kinetics

0

5

10

15

20

25

30

35

40

45

380 400 420 440 460 480 500

T (C)

t

(min

99

95

90

Conversion (%)


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HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreatThermalThermal

ConversionConversionHydrogenate

Lime KilnLime Kiln


FuelsFuels

MixedMixed



LimeLime

Carboxylate

Salts

Ketone HydrogenationKetone Hydrogenation


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Ketone Hydrogenation

Stoichiometry

Ketone Hydrogenation

Stoichiometry

O OH

H3CCCH3 + H2 H3CCCH3H

Acetone Isopropanol

H3CCCH2CH3 + H2 H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol


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Ketone HydrogenationKetone Hydrogenation

HH22

LiquidLiquid KetonesKetones

Catalyst = 200 g/L Raney nickelCatalyst = 200 g/L Raney nickel

Temperature = 130Temperature = 130ooCC

Time = 35 min (@ P = 15Time = 35 min (@ P = 15 atmatm))


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HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixed

AlcoholAlcohol

FuelsFuels


MixedMixed

AcidsAcidsAcidAcidSpringingSpringing

DewaterDewaterFermentFermentPretreatPretreat


LimeLime

Carboxylate

Salts


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Acid SpringingAcid Springing

Ca(Ac)2

CO2

CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc R3N

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3


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HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixed

AlcoholAlcohol

FuelsFuels


MixedMixed

AcidsAcidsAcidAcidSpringingSpringing

DewaterDewaterFermentFermentPretreatPretreat


LimeLime

Carboxylate

Salts


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Hydrogenation StoichiometryHydrogenation Stoichiometry

H3CCOCH2CH2CH2CH2CH3 + H2O

H3CCOCH2CH2CH2CH2CH3 + 2 H2

H3CCOH + HOCH2CH2CH2CH2CH3

O O

O

H3CCOH + HOCH2CH2CH2CH2CH3

H

H

H3CCOH + 2 H2O

H3CCOH + H2OH

H

Acetic Acid Ethanol

Heavy Alcohol Ester

Ester Heavy Alcohol


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HydrogenationHydrogenation

Mixed Alcohols

H2

Water

Heavy Alcohols

Carboxylic

Acids

Esters Alcohols


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Chemical FlowchartChemical Flowchart

BBII

OO

MM

AA

SSSS

CalciumCalcium

AcetateAcetateAceticAcetic

AcidAcid

EthanolEthanol

EthylEthyl

AcetateAcetate

CalciumCalcium

MagnesiumMagnesium

AcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropyl

TertiaryTertiary

ButylButyl

EtherEther

DiisopropylDiisopropyl

EtherEther

IsobutyleneIsobutylene

CalciumCalcium

PropionatePropionate

PropionicPropionic

AcidAcid

nn--PropanolPropanol

PropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

CalciumCalcium

ButyrateButyrate

ButyricButyric

AcidAcid

nn--ButanolButanol

ButylButyl

ButyrateButyrate

DipropylDipropyl

KetoneKetone

44--HeptanolHeptanol

HH22

HH22

HH22

HH22

Properties of Fuel OxygenatesProperties of Fuel Oxygenates


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Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending ReidBlending Reid BlendingBlendingVapor PressureVapor Pressure OctaneOctane

@38@38ooC (C (kPakPa)) (R + M)/2(R + M)/2

AlcoholsAlcohols214214 Methanol (Methanol (MeOHMeOH)) 108108

124 Ethanol (124 Ethanol (EtOHEtOH)) 115115

9797 IsopropanolIsopropanol (IPA)(IPA) 1061066262 terttert--ButanolButanol (TBA)(TBA) 100100

3434 IsobutanolIsobutanol (IBA)(IBA) 102102

EthersEthers5555 MethyMethy tertiary butyl ether (MTBE)tertiary butyl ether (MTBE) 110110

3434 DiDi--isopropyl ether (DIPE)isopropyl ether (DIPE) 105105

17 Isopropyl tertiary butyl ether (IPTBE)17 Isopropyl tertiary butyl ether (IPTBE) 113113KlassKlass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic P, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press (1998).ress (1998).


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Energy ContentEnergy Content

GasolineGasoline

Mixed AlcoholsMixed AlcoholsVersionVersion 11

Mixed AlcoholsMixed AlcoholsVersionVersion 22

EthanolEthanol

34.9 125,00029.0 104,000

26.5 95,000

23.4 84,300

Energy

(MJ/L) (Btu/gal)


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Plant CapacityPlant Capacity

((tonne/htonne/h) (mill gal/yr)) (mill gal/yr)

VersionVersion 11 VersionVersion 22

Plant CapacityPlant Capacity

CityCityPopulationPopulation

2 1.52 1.5 2.3 40,0002.3 40,000

1010 7.67.6 11.311.3 200,000200,000

40 30.3 45.1 800,00040 30.3 45.1 800,000

160 121 181 3,200,000160 121 181 3,200,000

800 606 903 16,000,000800 606 903 16,000,000

BaseBaseCaseCase

Effect of Scale onEffect of Scale on


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Effect of Scale on

Capital Cost Versions 1&2

Effect of Scale on

Capital Cost Versions 1&2

0

50

100

150

200

250

300

0 100 200 300 400 500 600 700 800 900

Capacity (tonne/h)

C

apitalCost(mill$)

Mixed Ketone Selling PriceMixed Ketone Selling Price


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Mixed Ketone Selling Price

Version 1 (15% ROI)

Mixed Ketone Selling Price

Version 1 (15% ROI)

-40 -20 0 20 40

Biomass Cost ($/tonne)

1.00

0.80

0.60

0.40

0.20

0.00

Ketone

SellingPrice($/gal)

210

40160800

Capacity

(tonne/h)

Mixed Alcohol Selling PriceMixed Alcohol Selling Price


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Mixed Alcohol Selling Price

Version 1 (15% ROI)

Mixed Alcohol Selling Price

Version 1 (15% ROI)

-40 -20 0 20 40

Biomass Cost ($/tonne)

1.00

0.80

0.60

0.40

0.20

0.00

AlcoholSellingPrice($/gal)

2 10

40160800

Capacity

(tonne/h)


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Productivity in Puerto RicoProductivity in Puerto Rico


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Productivity in Puerto Rico

(dry ton/(acreyr))

Productivity in Puerto Rico

(dry ton/(acreyr))

Energy Cane

Source: Alex Alexander, The Energy Cane Alternative, Sugar Series 6, Elsevier

Sugar

Biomass

Fiber

Conventional

Sugarcane

5.8

8.8

14.6

9

21

30

40%

60%

70%

30%


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Energy Cane ProcessingEnergy Cane Processing

EnergyCane Extract

SugarMill

MixAlco

Process

Sugar

Alcohol

Fuel

Sugar

Biomass

Fiber

Residue

(Boiler Fuel)

Some Potential Commodity ProductsSome Potential Commodity Products


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Some Potential Commodity Products

from Sugar

Some Potential Commodity Products

from Sugar

FoodFood acidulantsacidulants Citric,Citric, gluconicgluconic,, succinicsuccinic acidsacids

Biodegradable polymersBiodegradable polymers

PolyhydroxyalcoanatesPolyhydroxyalcoanates

PolylacticPolylactic acidacid

Synthetic rubber precursorsSynthetic rubber precursors 2,32,3--butanediol, a precursor to butadienebutanediol, a precursor to butadiene

Fiber precursorsFiber precursors

1,31,3--propanediol, a component ofpropanediol, a component ofDuPont'sDuPont's SoronaSorona

C t li d P iC t li d P i


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Centralized ProcessingCentralized Processing

15.3 mi50% of area

planted


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Supply US Gasoline ConsumptionSupply US Gasoline Consumption

plants248alcgal10629

plantyrgasgal

alcgal2.1yr

gasgal10130Plants 6

9

=

=

2

2

mi900,90plantmi366plants248Area==

100% planted 302 mi


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Effect of Automotive EfficiencyEffect of Automotive Efficiency

302 mi1better(Current)

2better

3better

213 mi

174 mi


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Land required in BrazilLand required in Brazil

1 2 3


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Sweet SorghumSweet Sorghum

Grows in ~35 US states

William Rooney, Soil and Crop Sciences, Texas A&M University

Yield = 2025 dry ton/(acreyr)

100% planted 345 mi

1


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Land Area in United StatesLand Area in United States

1 2 3


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StarRotor Test StandStarRotor Test Stand


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engine = 49 55%

(75 100 miles/gallon)

Projected Engine EfficiencyProjected Engine Efficiency


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ConclusionsConclusions

The technology isThe technology is

-- greengreen--profitableprofitable

-- worldworld--widewide

-- simplesimple

Many potential productsMany potential products

-- ketonesketones-- alcoholsalcohols

-- organic acidsorganic acids

l i


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ConclusionsConclusions

NearNear--term applicationsterm applications-- wastewaste chemicalschemicals

MidMid--term applicationsterm applications-- wastewaste fuelsfuels

FarFar--term applicationsterm applications-- cropscrops fuelsfuels


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Thank you for yourtime and attention

EPA Presentation on Biodiesel

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Transcript of EPA Presentation on Biodiesel