T. H. Vanderspurt, S. C. Emerson, R. Willigan, T. Davis, A. Peles, Y. She, S. Arsenault, R. Hebert, J. MacLeod,

G. Marigliani, & S. Seiser

12 June 2008

United Technologies Research Center, East Hartford, CT

A Novel Slurry Based Biomass Reforming Process

(DE-FG36-05GO15042)

This document does not contain any proprietary, confidential, or otherwise restricted information.

Project ID #PD31

2

OverviewTimeline

Start – May 2005End – March 2009≈50% Complete

BudgetTotal Project Funding

DOE share - $2.9MContractor share - $737k

Funding Received in FY07$650k from DOE

Funding for FY08$800k (projected)

BarriersHydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year Research, Development and Demonstration Plan

S. Feedstock Cost and AvailabilityT. Capital Costs and Efficiency of Biomass Gasification/Pyrolysis Technology

PartnersUniversity of North Dakota Environment Energy Research Center

3

Objectives

(2007) Illustrate, through an initial feasibility analysis on a 2000 ton/day (dry) biomass plant design, that there is a viable technico-economical path towards the DOE's 2012 efficiency target (43% LHV) and assess the requirements for meeting the DOE's cost target ($1.60/kg H2).(2008) Demonstrate, through preliminary results, that an acid tolerant, model sugar solution reforming catalyst with acceptable kinetics has been synthesized and that a viable technical path for scale up (mass production) of this catalyst in a cost-effective way exists.(2008) Identify hydrolysis conditions for a simulated biomass system and a viable technico-economical path towards the achievement of the hydrolysis of the real biomass system.(2008) Demonstrate, through extensive test results, an acid tolerant, long life, cost-effective biomass hydrolysis product reforming catalyst.

4

Approach: Biomass Slurry to Hydrogen Concept

Fuel flexible, using raw, ground biomass such as wood or switch grass Carbon neutral means of producing HydrogenH2 separation: Leverage experience with Advanced Pd membranes

Slurry of ≈10 %Ground Biomass(Wood) in Dilute Acid

44% cellulose19% hemicellulose13% “other”23% lignin<1% “ash”<1% protein 0.11 kg H2/kg Biomass (dry)

5

Characterization

Successfully Employed to Develop High Activity, Long Lived (>5X) Catalysts

Temp C, Initial Down Ramp 4.9% CO, 10.5%CO2, 33%H2O, 30.3%H2

220 230 240 250 260 270 280 290

(Mirc

oMol

es C

O/S

ec)/G

ram

Cat

alys

t

0

10

20

30

40

50

60

70

80

Pt /Mo0.1Ce0.7Zr0.2 173 m2/gPt/Mo0.1Ce0.7Zr0.2 191m2/g Pt/ Ce0.65Zr0.35 187 m2/g Run 2Pt/ Ce0.65Zr0.35 187 m2/g Run 1

Pt/Mo Doped CeZrOx

Pt/CeZrOx

Higher Activity Catalyst with Similar Pt & Surface AreaTemp C, Initial Down Ramp 4.9% CO, 10.5%CO2, 33%H2O, 30.3%H2

220 230 240 250 260 270 280 290

(Mirc

oMol

es C

O/S

ec)/G

ram

Cat

alys

t

0

10

20

30

40

50

60

70

80

Pt /Mo0.1Ce0.7Zr0.2 173 m2/gPt/Mo0.1Ce0.7Zr0.2 191m2/g Pt/ Ce0.65Zr0.35 187 m2/g Run 2Pt/ Ce0.65Zr0.35 187 m2/g Run 1

Pt/Mo Doped CeZrOxPt/Mo Doped CeZrOx

Pt/CeZrOx

Higher Activity Catalyst with Similar Pt & Surface Area

High active surface area Large pore Nanocrystalline structure

~100% NM dispersion

Conceptual Catalyst Design Quantum Mechanical Atomistic Modeling for advanced catalysts

design

Catalyst Synthesis

⇔ ⇔ ⇔

1000 2000 30004000Wavenumbers (cm-1)

Catalyst A

Catalyst B =Kinetic Expressions Derived

From Reaction Data

Superior Performance

⇔

Hydrogen from BiomassUTRC Catalyst Discovery Approach

Act

ivity

Unfavorable

6

Simplified Biomass Hydrolysis and Reforming ProcessesModeling Basis

Dilute acid hydrolysis(C6H10O5 )n + nH2O nC6H12O6

Liquid phase reformingC6H12O6 + 6H2O 12H2 + 6CO2

C6H12O6 3CO2 + 3CH4

H2 separationPd membrane is used for H2 separation

Lignin combustionC7.4H14O1.4 + 10.2O2 7.4CO2 + 7H2O

Sulfur recovery SO2 + 0.5O2 SO3

SO3 + H2O H2SO4

H3O+

feedbiomassofLHVconsumedEnergyrecoveredEnergyHproductofLHVEfficiencyEnergy LHV 2 −+

=

7

Key Features of Proposed Biomass Reforming Plant

consumedEnergyfeedbiomassofLHVRecoveredEnergyHproductofLHVEfficiencyEnergyProcess 2

++

=

ConsumedEnergyFeedBiomassofLHVHProductofLHVEfficiencyHPlant 2

2 +=

•Sulfur/acid tolerant Pt-alloy rafts/nano-engineered mixed metal oxide catalysts will be developed for liquid phase oxygenates (sugar) reforming

•Lignin, byproduct fuel gas and unrecovered H2 are burned to provide thermal energy thus increasing system efficiency.

•Recycling of the hot water used for hydrolysis increases system intensity.

•Sulfur recovery & recycle as H2SO4 lowers costs and minimizes emissions

•54.2% LHV energy efficiency (46.6% plant H2 efficiency) achieved through comprehensive thermal integration

feedbiomassofLHVconsumedEnergyrecoveredEnergyHproductofLHVEfficiencyEnergy LHV 2 −+

=

DOE H2A definitions

UTRC definition

8

Summary from 2007

• Biomass reforming plant design with a system HYSYS simulation LHV efficiency of 54% is proposed.

• The thermally integrated design yields high efficiency and minimizes sulfur emissions.

• Major drivers on the efficiency were identified in parametersensitivity studies.

• > 50% LHV efficiency operating regime identified through DOE studies.

• Hydrolysis and reforming catalyst/reactor performance targets identified.

• Hydrogen production cost of $1.60/kg H2 is achievable with this process.

9

Explore Oxide Doping to Impact Reactant–Pt Binding Energies

VASP DFT Calculations; Assumptions:• Reforming reaction requires at least some Pt Sites• Glycerol reacts on Pt• H2S as a surrogate for other poisons; competes for sites• Work is continuing• Other deactivation mechanisms not yet considered

Calculated binding energies, E, for H2O, glycerol, and H2S molecules on hydrated oxide surfaces and hydrated Pt monolayer on pure and doped oxides.

10

Upgraded Testing Reactor to Improve ReproducibilityMove to Stirred Zirconium Autoclave

Reproducibility of Pt/alumina reference motivated reactor switchPt-dissolution from vendor catalyst

Introduction of feed into batch reactor contributed to variabilityLow diffusivity of glycerolNo significant agitation for convective mixing (N2 sweep gas only)Small variability in catalyst pellet placement complicates diffusion resistance

Titanium Batch Reactor

Operating Conditions:Pressure (≤2000 psig)

Temperature (≤300 °C)

Stirred Zirconium Autoclave

Stirred autoclave operates at constant C/Co=1.0 fot t≥0

11

Glycerol to Hydrogen Rate for Various Catalysts 240 °C, 2.5 wt% (0.283 M) Glycerol (0.283 M)

0.5% Pt/Al2O3

2% Pt/ZrO2

2.09% (Nb)ZrO2

0.35% (Nb)ZrO2

2% CeZrO2

Rat

e x

10-8

, mol

/s-g

act

ive

Pt

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

12

Sugar / Sugar Alcohol Reaction ConditionsTemperature and concentrations ranges set based on charring studies

1% 2.5% 5% 10%

300ºC

250ºC

225ºC

Glucose (cyclic)

1% 2.5% 5% 10%

300ºC

250ºC

225ºC

Xylose (cyclic)

Glycerol (C3)

1% 2.5% 5% 10%

300ºC

250ºC

225ºC

Xylitol (C5)

1% 2.5% 5% 10%

300ºC

250ºC

225ºC

Sorbitol (C5)

char, severechar, moderate

no char

1% 2.5% 5% 10%

X300ºC

250ºC

225ºC

char, minor

UTC PROPRIETARY

13

0.5% Pt/Al2O3 Testing- KHSO4 Addition Terminates H2 Production

• 2.5 wt% Glycerol (0.283M); 0.1M KHSO4 addition at 400 min• Immediate termination of H2 production• Increased production of C2 and C3+ Species

Time, min

0 200 400 600 800 1000

GC

Are

a

0

1000

2000

3000

4000

Tem

pera

ture

, C

120

140

160

180

200

220

240

260

280

300

320CH4

C2s C3s C4/C5s Temperature

Time, min

0 200 400 600 800 1000

Con

cent

ratio

n, %

0.0

0.1

0.2

0.3

0.4

0.5

Tem

pera

ture

, C120

140

160

180

200

220

240

260

280

300

320H2CO2COCH4Temperature

14Time, min

0 200 400 600 800 1000 1200

Con

cent

ratio

n, %

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Tem

pera

ture

, C

100

150

200

250

300CO2COCH4

H2

Temperature

0.5% Pt/Al2O3 Testing- Temperature Ramp

Temperature ramped from 180 °C to 240 °C2.5 wt% (0.283 M) GlycerolNo H2 production below 210 °CInitial H2 production due to temperature overshoot

H2 TCD lost Carrier

15

2% Pt/Ce0.6Zr0.4O2 Testing — H2 Production at <190 °C

2.5 wt% (0.283 M) Glycerol93% selectivity towards H2 through the entire temperature rangeEact = 74.2 kJ/molVendor prepared UTRC mixed metal oxideKHSO4 Addition Tests underway

Time, min

0 200 400 600 800 1000 1200

Con

cent

ratio

n %

0.0

0.1

0.2

0.3

0.4

Tem

pera

ture

, C

100

120

140

160

180

200

220

240

260H2CO2COCH4Temperature

Time, min

0 200 400 600 800 1000 1200

GC

FID

Cou

nt

0

500

1000

1500

2000

2500

3000

Tem

pera

ture

, C

100

120

140

160

180

200

220

240

260CH4 C2s C3/4/5s Temperature

1/T, K0.0019 0.0020 0.0021 0.0022 0.0023

log k

-10.4

-10.2

-10.0

-9.8

-9.6

-9.4

-9.2

16

Work For 2008-2009(2008) Demonstrate, through preliminary results, that an acid tolerant, model sugar solution reforming catalyst with acceptable kinetics has been synthesized and that a viable technical path for scale up (mass production) of this catalyst in a cost-effective way exists.(2008) Identify hydrolysis conditions for a simulated biomass system and a viable techno-economical path towards the achievement of the hydrolysis of the real biomass system.(2008) Demonstrate, through extensive test results, an acid tolerant, long life, cost-effective biomass hydrolysis product reforming catalyst.Pending future funding, further hydrolysis optimization; additional catalyst development, including atomistic modeling; and a 1-kW scale demonstration and final techno-economic analysis at the end of the project.

Status: Experimental effort now carried out in 2 liter stirred autoclave, earlier catalyst results called into question.Pt/Al2O3 outperforms uniformly loaded Pt/ZrO2 family at 240 °C on a per site basis without KHSO4

Pt/CeZrOx catalyst active at 180 °C without KHSO4.KHSO4 addition shuts down H2 production while increasing ethane productionRetest of Pt/CeZrOx Water Gas Shift Catalyst with KHSO4 underway