11

Green Energy Today for a Better

Tomorrow

Hydrogen Generation from Biomass-Derived Carbohydrates via Aqueous-Phase Reforming

October 23, 2006

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Aqueous Phase Reforming (APR)Aqueous Phase Reforming (APR)A Revolutionary Process PlatformA Revolutionary Process Platform

�� GlycerineGlycerine

�� SorbitolSorbitol

�� GlucoseGlucose

�� SucroseSucrose

�� StarchesStarches

�� AlcoholsAlcohols

�� Ethylene GlycolEthylene Glycol

�� LignocellulosicLignocellulosicBiomassBiomass

VirentVirent APRAPR

LPGLPG

SuperNatural GasSuperNatural Gas™™(H(H22/Alkane Mix)/Alkane Mix)

Pure HPure H22

High ValueHigh Value ChemicalsChemicalsTemperatures < 260oC

Pressures ~450 psi

LiquidLiquid FuelsFuels

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-20

-15

-10

-5

0

5

10

15

20

300 400 500 600 700 800 900 1000Temperature (K)

CH4 : C

6H

14

CH3(OH) : C

6H

8(OH)

6

WGS

ln(P)

Reforming ThermodynamicsReforming Thermodynamics

⇒ Equilibrium is favorable for reforming of oxygenated compounds at low temperatures.

Reforming of Hydrocarbons

Water-Gas Shift

Reforming of Oxygenated Compounds

CnH2n+2 + nH2O ↔ nCO + (2n+1)H2

CO + H2O ↔ CO2 + H2

CnH2yOn ↔ nCO + yH2

4444

Reaction PathwaysReaction Pathways

C C O O H H

H H ][ n

C COH x

Hx O

* *

H2

H2

H2O

C COH x

Hx O

* * * *

C CHH

* *

C-C cleavage

alkanes

H2 CO,H2

H2O

H2O WGS

CO2,H2

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Intellectual PropertyIntellectual Property

�� Virent is the only company in the world that canVirent is the only company in the world that can commercialize the APR technologycommercialize the APR technology

�� Four patents issued and licensed from the WARF:Four patents issued and licensed from the WARF:�� One continuation pendingOne continuation pending�� Covers all probable compositions and conditions needed forCovers all probable compositions and conditions needed for

liquid phase reformingliquid phase reforming

�� Virent:Virent: Sole Technology LicenseeSole Technology Licensee�� Exclusive worldwide licenseExclusive worldwide license�� Right to sublicenseRight to sublicense

�� Minimum of eight new patent applications to be filed thisMinimum of eight new patent applications to be filed this quarter by Virentquarter by Virent

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Effects of Feed ConcentrationEffects of Feed Concentration

�� System EfficiencySystem Efficiency�� Combustion of Hydrogen forCombustion of Hydrogen for

Process Energy RequiredProcess Energy Required�� Higher FeedstockHigher Feedstock

Concentrations Reduce HeatingConcentrations Reduce Heating RequirementsRequirements

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50 60 70

wt % Glucose

Effic

ienc

ey (%

)

PurifierPurified CO2 Purified H2

Waste H

2 H

2 0, CO

2 AlkanesA

ir

APR Reactor

Reactor Heater

H20 CO2 N2

Exchanger Gas

Liquid

Water Separator

H2, CO2, Alkanes, H2O

Mixer

Liquid Feed

Feed Pump

Glu

cose

In

Wat

er

Glucose/Water Water

7777

APR ImprovementsAPR Improvements

(71 % LHV)

WH

SV (k

g of

Oxy

gena

ted

Com

poun

d/kg

of c

atal

yst h

)

2

1.8

1.6

1.4

1.2

1 Ethylene Glycol

0.8

0.6

UW Results (10 % LHV)0.4 1% EG 1% Sorbitol

0.2 WHSV 0.008

0

(60% LHV)

(55 % LHV)

(Thermal Efficiency) Based on LHV

(55% LHV) Theoretical 85 % LHVSorbitol

(50% LHV)

May-02 Dec-02 Jun-03 Jan-04 Aug-04 Feb-05 Sep-05

Time

8888

Energy Densities of Oxygenated FuelsEnergy Densities of Oxygenated Fuels

Fuel Energy Density

(Wh/liter) Ethylene Glycol

(1:1 H2O:C) 3700 Glycerol (1:1 H2O:C) 3736 Sorbitol

(1:1 H2O:C) 3809 Glucose

(1:1 H2O:C) 3585 Methanol (1:1 H2O:C) 3572

Li-Ion Battery 200 (Current)

Energy densities based on hydrogen produced via APR

process

Ethylene Glycol, Glycerol, Sorbitol, and Glucose are non­flammable, non-toxic, and have

higher energy densities than methanol

Viable fuels for combined APR process and fuel cell technologies for future replacement of batteries

9999

VirentVirent’’ss 11stst Generation PrototypeGeneration Prototype

Integrated 300 cc/min system.

99.999% pure H2 with palladium filter.

Hydrogen Generation for Lab Use.

Can be significantly reduced in size.

10101010

DOE HDOE H22 from Glucosefrom Glucose

�� StartStart –– Sept 2005Sept 2005�� FinishFinish –– Aug 2008 (Tentative)Aug 2008 (Tentative) �� 10 % complete10 % complete

�� Feedstock Cost ReductionFeedstock Cost Reduction�� 2005 Feedstock Cost Contribution $3.80/gge2005 Feedstock Cost Contribution $3.80/gge�� 2010 Feedstock Cost Contribution $1.80/gge2010 Feedstock Cost Contribution $1.80/gge

�� By 2010, reduce HBy 2010, reduce H22 costs to $3.60/ggecosts to $3.60/gge�� Overall Efficiency 66%Overall Efficiency 66%

�� By 2015, reduce HBy 2015, reduce H22 cost to $2.50/ggecost to $2.50/gge

�� Total project fundingTotal project funding�� DOE shareDOE share --1,942 K1,942 K�� Contractor shareContractor share -- 679 K679 K

�� Funding received in FY05Funding received in FY05�� 100 K100 K

�� Funding received for FY06Funding received for FY06�� 200 K200 K

�� Funding Reduction in FY06 resulted inFunding Reduction in FY06 resulted in limiting work to catalyst developmentlimiting work to catalyst development

Timeline

Budget

Barriers

�� ADMADM�� University of WisconsinUniversity of Wisconsin

Partners

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Hydrogen Generation from SugarsHydrogen Generation from Sugars

Corn Corn Stover Sugar Cane

Bagasse

Sugars

Sugar Alcohols

APR Under Development

HydrogenHydrolysis

Hydrogenation C6H12O6 + H2 -> C6H14O6

APR Demonstrated

Glucose (C6H12O6)

6 to 11 cents/lb

Sorbitol (C6H14O6) 10 to 15 cents/lb

12121212

Projected Cost of HydrogenProjected Cost of Hydrogen Generation using the APR ProcessGeneration using the APR Process

USDOE Model H2A

Capital Cost Includes

APR PSA

Compression Storage

Dispensing

Current Performance

Sorbitol 45% Yield

Projected Performance

70% Yield

0

1

2

3

4

5

6

7

8

$0.05/lb 70% Yield

$0.05/lb 45% Yield

$0.10/lb 70% Yield

$0.10/lb 45% Yield

$0.15/lb 70% Yield

$0.15/lb 45% Yield

Hydr

ogen

Cos

t $/k

g

O & M Capital Cost Feedstock

Cost Model 6/6/2006

RDC/Virent

10% ROI, 7 Year Depreciation,

Reformer Replacement after 11 years Costs do reflect $0.43/kg byproduct credit for 45%

Yield case

13131313

Glycerol Supply / DemandGlycerol Supply / Demand

0

200

400

600

800

1000

1200

1400

20

01

20

03

20

05

20

07

20

09

20

11

kto

nn

es/

yr

Global Capacity

Global Demand

14141414

Global Hydrogen MarketGlobal Hydrogen Market

Ammonia

Refinery

Methanol

Other

Merchant Onsite

Merchant Bulk

40205 ktonnes of Hydrogen

Total Glycerol Projected to be available in 2012 is equivalent to 40 – 100 ktonnes of Hydrogen

15151515

Reactor PerformanceReactor Performance

Single Pass Conversion

50 wt% Glycerol Reactor Thermal

Efficiency

⎟⎠⎞

⎜⎝⎛ −×

GasProductofLHV EnergyProcess0.1100

80%

82%

84%

86%

88%

90%

92%

94%

96%

98%

100%

0 2 4 6 8

Days

Con

vers

ion/

Rea

ctor

The

rmal

Ef

ficie

ncy

Conversion

Reactor Thermal Efficiency

Process Thermal Efficiency 78.5 % of LHV of Feed

16161616

Basic System Flow SchematicBasic System Flow Schematic

Feed Pump Heatx APR

RXN

ICE Gen Set

Catalytic Burner

Condenser

Separator

CHP/Exhaust

500-600oC

<260oC

17171717

COCO22WaterWaterHeatHeat

APR: ICE IntegrationAPR: ICE IntegrationMadison Gas & Electric ProjectMadison Gas & Electric Project

�� Can operate inCan operate in ““unteatheredunteathered”” modemode�� Can be run in Combined Heat and Power modeCan be run in Combined Heat and Power mode�� Can meet cost & reliability targets with near zeroCan meet cost & reliability targets with near zero

emissionsemissions

HeatHeat

Ford 1.6 literFord 1.6 literHCNGICE GensetHCNGICE Genset

HH22AlkanesAlkanes

COCO22

APRAPR

GlycerolGlycerolWaterWater

SuperNatural Gas™ kWe

18181818

Green Energy Machine (GEM)Green Energy Machine (GEM)Alpha UnitAlpha Unit

APR Reactor System

Condenser System

Separator System

APR Gas Delivery

Feed System Liquid

Handling System

Control Electronics

19191919

LurgiLurgi’’ss BiodieselBiodiesel Production fromProduction from Seed OilsSeed Oils

20202020

Conversion of Crude GlycerolConversion of Crude Glycerol

0

1

2

3

4

5

6

Day 1 Day 3 Day 4

wat

ts/g

ram

0%

10%

20%

30%

40%

50%

60%

70%

80%

alkane w/g H2 w/g purity conversion

21212121

BiodieselBiodiesel Glycerol CompositionGlycerol Composition�� Observed Contamination EffectsObserved Contamination Effects�� Methanol Increases Hydrogen YieldMethanol Increases Hydrogen Yield�� Can Process Stream with Free Fatty Acid/Soap ContentCan Process Stream with Free Fatty Acid/Soap Content

up to 3 %up to 3 %�� Can Process Streams with Trace Amounts ofCan Process Streams with Trace Amounts of BiodieselBiodiesel�� High Concentrations of Salts (greater than 1 %) causeHigh Concentrations of Salts (greater than 1 %) cause

plugging problems in APR reactorplugging problems in APR reactor�� Chloride Salts cause corrosion problemsChloride Salts cause corrosion problems

�� Evaporation TreatmentEvaporation Treatment�� Reduces salt contentReduces salt content�� Low levels of sulfates (50Low levels of sulfates (50 –– 100100 ppmppm))

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Distillation

Adsorption

Water Glycerol MeOH FFA

Catalyst

Bio Diesel

MeOH

Burner

Water

Bio Diesel Process

MeOH

APR

Glycerol

APR Products H2

Supernatural Gas LPG

ls Liquid Fuels

Steam

Utilization of Glycerol

Evaporation

Evaporation

MeO

H S

tripper

Oil / Fats

Catalyst

Pharm-Grade

Polyo