Hydrogen Generation from Biomass-Derived Carbohydrates via ... · Carbohydrates via the Aqueous-Phase Reforming (APR) ... UW NiSn Ovonics NiSn Virent NiSn A ... 2007 2nd Q 2007 3rd

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2005 DOE Hydrogen Program ReviewArlington, Virginia

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

Reforming (APR) Process

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

Reforming (APR) Process

Randy D. Cortright, Ph.D.Virent Energy Systems, Inc.

3571 Anderson StreetMadison, WI 53704

www.virent.com

May 23, 2005

This Presentation does not contain any proprietary or confidential information

Project ID# PD7

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OverviewOverviewBarriersProject Timeline

• Barriers addressedCost Reduction of Distributed Hydrogen Generation from Renewable LiquidsBy 2015, reduce cost to $2.50/gge

• Start Date - September 2005

• End Date - August 2008

Budget• Virent Energy Systems

Project Lead – Catalyst/Reactor• Archer Daniel Midland

Feedstock/Demonstration Unit Location

• UOP LLCSystems Engineering

• University of WisconsinFundamental Studies

Partners• Total project funding $2.62 M

DOE share $1.94 MContractor share $0.68 M

• Funding for FY05 None to Date

First Year ObjectivesFirst Year Objectives• Identify candidate sugar streams (Glucose), document plant integration

requirements and associated economic factors.

• Develop catalyst and reactor based on the Aqueous Phase Reforming (APR) process suitable for converting candidate sugar streams tohydrogen.

• Design a baseline hydrogen generation system utilizing the APR process.

• Calculate the thermal efficiency and economics of the baseline APR system.

• Assess the baseline APR system with respect to US Hydrogen program goals and make a go/no go decision to proceed with further development of a demonstration system.

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Second and Third Year ObjectivesSecond and Third Year Objectives

• Develop the detail design of the demonstration APR hydrogen generator system (50 kg/day).

• Fabrication of the integrated hydrogen generator system.

• Install and operate the APR hydrogen generator system at a sugar facility owned by ADM.

• Assess APR hydrogen generator system performance with respect to US Hydrogen program goals.

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ApproachAqueous Phase Reforming (APR)

ApproachAqueous Phase Reforming (APR)

Ethylene Glycol (AntiFreeze)

Glycerol from Biodiesel

Sorbitol from Glucose or Sucrose sugar

Glucose from Corn

Sugars and Sugar Alcohols from hemi-cellulose

Alkanes

H2/Alkane Mix

Pure H2

Virent

APR

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Reforming ThermodynamicsReforming Thermodynamics

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

-20

-15

-10

-5

0

5

10

15

20

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

CH4 : C

6H

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CH3(OH) : C

6H

8(OH)

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WGS

ln(P)

Reforming of Hydrocarbons

Water-Gas ShiftReforming of Oxygenated Compounds

CnH2n+2 + nH2O ↔ nCO + (2n+1)H2

CO + H2O ↔ CO2 + H2

CnH2yOn ↔ nCO + yH2

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Aqueous-phase Reforming of 1 wt% Methanol, Ethylene Glycol, Glycerol, Sorbitol & GlucoseAqueous-phase Reforming of 1 wt% Methanol, Ethylene Glycol, Glycerol, Sorbitol & Glucose

0

20

40

60

80

100

Methanol Ethylene Glycol Glycerol Sorbitol Glucose

H2 Selectivities

Alkane Selectivities

538 K

538 K

498 K

498 K

[Cortright, Davda, and Dumesic, Nature, Volume 418, page 964 (2002)]

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Reaction PathwaysReaction Pathways

C CO OH H

H H ][n

C COH x

Hx O

* *

H2

H2

H2O

C COH x

Hx O

* * * *

C CHH

* *

C-Ccleavage

alkanes

H2 CO,H2

H2O

H2OWGS

CO2,H2

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APR Processing of SorbitolAPR Processing of Sorbitol

Utilizes a Single ReactorGeneration of High Pressure HydrogenLow CO Concentrations

Low Temperature Reforming and Water-Gas Shift215 oC over Platinum-Based Catalyst

Liquid-Phase System Total Pressure 310 psia

Aqueous Stream

193 psi H2115 psi CO2

1.4 psi Hydrocarbons0.2 psi H2O

Less than 100 ppm CO

CO + H2O ↔ CO2 + H2

CnH2yOn ↔ nCO + yH2 PhaseSeparator

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Hydrogen from Biomass-Derived CompoundsHydrogen from Biomass-Derived Compounds

CornCorn StoverSugar Cane

Bagasse

Sugars

Sugar Alcohols

Hydrogen

HydrogenationAPR

Near Term

Hydrolysis

APRLong Term

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Catalyst Lifetime StudyCatalyst Lifetime Study

0.00

0.50

1.00

1.50

2.00

2.50

0 500 1000 1500

Hours on Stream

Wat

ts H

2 per

gra

m o

f cat

alys

t

Results from NSF STTR Phase I Project

Platinum-Based Catalyst10% Glycerol Feed

Two Month Run from September 2003 to November

2003

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Catalyst Activity StudiesCatalyst Activity Studies

0

2

4

6

8

10

12

14

16

18

20

Aug-03 Oct-03 Nov-03 Jan-04 Mar-04 Apr-04 Jun-04 Aug-04

Wat

ts H

2 per

gra

m o

f Cat

alys

t

Reported Results of ATP Project

ATP Goal

ATP Funded Project

Increased Activity due to Catalyst Composition, Reactor Design, and

Reaction Conditions

Ethylene Glycol Feed

70 vol% H2 in reactor Effluent

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Precious Metals CatalystPrecious Metals Catalyst

0.00 2.00 4.00 6.00 8.00 10.00 12.00

Watts/g Catalyst

1.0 Pt

Modified Pt "A"

Modified Pt "B"

Virent "A"

Virent "B"

Cat

alys

t

Catalyst Testing Progress February to June 2004Standard Testing Conditions

Alkane 0.07 0.13 0.09 3.87 5.12

Hydrogen 0.42 1.17 1.16 3.00 6.61

1.0 Pt Modified Pt "A" Modified Pt "B" Virent "A" Virent "B"

6/11/2004

5/21/2004

4/14/2004

3/2/2004

2/24/2004

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Investigation of Nickel-Based CatalystInvestigation of Nickel-Based Catalyst

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00

Watts /g Catalys t

Ovonics Raney Ni

Alfa Raney Ni

UW NiSn

Ovonics NiSn

Virent NiSn A

Virent NiSn B

H Pow er/g cat

A lk Pow er/g cat

Alk Pow er/g cat 1.28 1.06 0.19 1.29 2.97 5.97

H Pow er/g cat 0.37 0.34 1.10 0.46 1.12 2.84

Ovonics Raney Ni A lfa Raney Ni UW NiSn Ovonics NiSn Virent NiSn A Virent NiSn B

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Hydrogen from SorbitolHydrogen from SorbitolPurifierPurified CO2

Purified H2

Waste H

2H

2 0, CO

2Alk an esA

ir

APR Reactor

Reactor Heater

H20CO2N2

Exchanger Gas

Liquid

Water Separator

H2, CO2, Alkanes, H2O

Mixer

LiquidFeed

Feed Pump

Sor

bito

lIn

Wat

er

Sorbitol Water

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APR Catalytic Reactor ImprovementsAPR Catalytic Reactor ImprovementsPerformance at 100 % Conversion

0

0.2

0.4

0.6

0.8

1

1.2

1.4

Feb-02 Sep-02 Mar-03 Oct-03 Apr-04 Nov-04 May-05

Time

WH

SV (k

g of

Oxy

gena

ted

Com

poun

d/kg

of c

atal

yst h

)

UW Results1% EG

1% SorbitolWHSV 0.008 /h

10 % EG

30 % EG

30 % Sorbitol

30 % Sorbitol

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Projected Cost of Hydrogen Generation using the APR ProcessProjected Cost of Hydrogen Generation using the APR Process

Filling StationApplication

500 kg H2/day

5000 kg Sorbitol/day

CatalystIncluded in Capital Cost

10% ROI15 Year Depreciation

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

Sorbitol @ 15cents/lb

Precious MetalCatalyst WHSV

0.8/h

10 cents/lb FeedPrecious MetalCatalyst WHSV

1.6/h

5 cents/lbFeedstock

Nickel BasedCatalyst WHSV

0.4/h

H2 C

ost (

$/kg

)

Capital CostO & MFeedstock

1 kg H2 is approximately 1 gge

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Future Work - First Year TimelineFuture Work - First Year TimelineSEPT OCT NOV DEC JAN FEB MAR APR MAY JUNE JULY AUG

Glucose Sampling

(ADM)

Catalyst and Reactor Testing(Virent)

Fundamental Studies and Catalyst Characterization(University of Wisconsin)

10 kg/day Reactor(Virent)

50 kg/day Unit Design(Virent/UOP)

Go/No GoFor Glucose

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Future Work - Overall Project TimelineFuture Work - Overall Project Timeline

3rd Q2005

4th Q2005

1st Q2006

2nd Q2006

3rd Q2006

4th Q2006

1st Q2007

2nd Q2007

3rd Q2007

4th Q2007

1st Q2008

2nd Q2008

Go/No GoFor Glucose

Catalyst and Reactor Testing with Glucose

(Virent/UW)

Design, Fabrication, and Deliveryof 50 kg/day Unit

(Virent/UOP)

Operation of 50 kg/day Unit(ADM/Virent/UOP)

Delivery of50 kg/day Unit

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FacilitiesFacilities• 6500 square feet facility in Madison,

Wisconsin• 14 Technical Personnel• 9 test stands available• Catalyst Preparation Equipment• 3 GC, 1 TOC, 1 GCMS, and analytical

backup from ADM• Fully-equipped machine shop

Experienced machinist for prototype production

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Virent Laboratory Hydrogen Safety SystemVirent Laboratory Hydrogen Safety System• Hydrogen Exhaust System

Two inch SS tube running North to South in lab.Blower is rated at 17000 L/min.

All Test Stand Vent into this system.• Lab Hydrogen Monitor• Master Permit Relay

Permits test stands to operate unless Hydrogen Exhaust System or Lab Hydrogen Monitor are in alarm state.

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Supplemental InformationSupplemental Information

• Next Slides Contain Requested Supplemental Information

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Publications and PresentationsPublications and Presentations

• None to Date

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Hydrogen SafetyHydrogen Safety

The most significant hydrogen hazard associated with this project would be would be accumulation of a significant amount of hydrogen in the laboratory, for example near the ceiling. The impact to personnel, and/or destruction or loss of equipment or facilities could be devastating if that accumulation reached or exceeded the lower explosion limit (LEL) of 4% and subsequently did explode.

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Hydrogen SafetyHydrogen Safety

• Our approach to deal with this hazard is:

Limited Hydrogen InventoryHydrogen Exhaust SystemLaboratory VentilationHydrogen MonitorSafety Interlocks