Hydrogen from BiomassCatalytic Reforming of Pyrolysis Vapors

R. Evans, L. Boyd, C. Elam, S. Czernik, R. French, C. Feik, S Phillips, E. Chornet

National Bioenergy Center inCollaboration with the Clark Atlanta University Team

U.S. DOE Hydrogen and Fuel Cells Merit Review Meeting

Berkeley, CA May 19-23, 2003

Project Goals

Demonstrate the production of hydrogen from biomass by pyrolysis –steam reforming for $2.90/kg by 2010Barriers: – Vapor Conditioning– Catalyst Development and Regeneration– Reactor Configuration– Heat Integration– Deployment: H2 + Co-products

Milestone:Verify advanced catalysts and reactor configuration for fluid bed reforming of biomass pyrolysis liquid at pilot scale (500 kg H2/day) with catalyst attrition rates < 0.01%/day. 4Q, 2009

Biomass Feedstocks

6 CO2 +6 H2O C6H12O6 +6 O2sunlight

Potential : 15% of the world’s energy by 2050.Fischer and Schrattenholzer, Biomass and Bioenergy 20 (2001) 151-159.

Crop residuesForest residuesEnergy cropsAnimal wasteMunicipal waste

Issues: Biomass Availability and Costs

Georgia Biomass Feedstock Supply

0

3

6

9

12

2000 2010 2020 2030 2040 2050

Mill

ion

Dry

tons

Ag Residue

Total~150 PJ of H2 energy5% of GA energy use

?

Pyrolysis Process Concept

Biomass PYROLYSIS Carbon Residue

Co-productsBio-oil

PhenolicIntermediatesSEPARATION

CATALYTIC STEAM REFORMING

H2O e.g., ResinsOctane additivesFine Chemicals

H2 (and CO2)

Biocarbon-Based Fertilizers

Inside Formations

Formation of Ammonium Bicarbonate

Inside the 15min Char Interior

CourtesyD. Day,Eprida/Scientific Carbons Inc.

Phase 2 SystemBiomass [100]

Pyrolysis bio-oil [30]H2O [30]Gas [5]

Preheater

Char[35]

FilterEductor

ReformerSteam[15]

SuperHeater

FlueGas

FilterH2 [7]

+ CO2 [60]+ CO [11]+ CH4 [2]

Reformer PreheaterHeat Recovery and IntegrationCompressionConditioningCoproduct OptimizationPyrolyzer Heat Optimization

Phase 3 Design Challenges

Catalyst Fines

Blakely Georgia Site

Pyrolysis Unit Performance

O2 Sensor after Char bed

O2 Sensor before Char bed

Exit Gas Temp

Char Bed Temp

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900

0 12 24 36 48 60 72 84

Time, hrs

Tem

pera

ture

(C)

0

0.2

0.4

0.6

0.8

1

1.2

Pres

ent <

-- O

2 -->

Abs

ent

Reformer Performance

Reformer Bed Temp

Orifice Plate Temp

Reformer DP

Orifice Plate DP

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2

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0 12 24 36 48 60 72 84

Time, hrs

Diff

eren

tial P

ress

ure

(in H

2O)

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Tem

pera

ture

, C

Gas Composition

H2

CO2

COCH4

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60

0 6 12 18 24 30 36 42 48 54 60 66 72 78 84

Time, hrs

Off-line

Phase 3 SystemBiomass [100]

Pyrolysis bio-oil[33] Preheater

Char[35]

H2O

FilterEductor

Reformer

FilterSteam

SuperHeater

FlueGas? Compressor

CondenserH2 + CO2 +

CO2 +

Dryer

PressureSwingAdsorption

CH4

Accumulator H2

Engine

ES&HES&HES&HES&H

Full time operation

Mass & Energy Balances

Mass Balance

Scopingeconomics

CommunicationSystems Demonstration

Systems integration

ComponentTechnologies

EarlyCommercial

Development to Reduce Costs

DebuggingProcess Understanding

III: PilotII: DesignI: Initial

DemonstrationR&D

: Circulating Fluid Bed

– Smaller Catalyst Particles Harder– Fluid Dynamics Higher Gas Flows– Direct Heating Partial Oxidation– Optimized Catalytic Coke Gasification

Reforming CxHyOz + H2O H2 + COx

Water gas shift: CO + H2O CO2 + H2

Coke Gasification: C + H2O CO + H2

Feed

SteamO2

Product

Project Time Line

0

100

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800J F M A M J J A S

O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S O N D J F M A M J J A S O N D

kg H

2/da

y

Ia

IIa

III

Bubbling Bed@ 10X

Best option (BB vs CFB) - Scale up at 3X

IIb

IbCirculating Bed Go/No Go:

CFB@ 10X

Milestone

2003 2004 2005 2007 2008 20092006Year

FY02 Review Comments

What are the Advantages of Pyrolysis/CSR vs Gasification/WGS?– Distributed Resource Centralized Reforming– Coproduct Better Economics– Smaller Scale Lower Capital + Feedstock Cost

Maintain a Communication Plan– RACI Analysis for Phase III

“Watch out for Safety”– Feature Safety in Phase 3– Change Site to University of Georgia Biomass

Research Facility to promote safety development and education and tech transfer to biomass industry

Safety ApproachU of GA Facility:• Train the Trainers• Process control forsafety AND efficiency(lower cost)

Must Develop:• A Facility to study system safety boundaries• A Statistical Basis for Safety Confidence

Safety Confidence

Cost

DataDrivenApproach

Safe UnSafe Margin of Error