NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Producing Clean Biomass Syngas

For Fuel Synthesis: Reforming

Catalyst Development

World Renewable Energy Forum

Kim Magrini

May 14, 2012

2

Outline

Biomass Syngas

Cleaning Strategies

Reforming Catalyst Development

• Bench scale

• Pilot Scale

Catalyst Deployment

3

Project rationale: Syngas cleaning significant process cost component

Robust methane/tar reforming catalysts High temperature sulfur sorbents Integrated syngas cleaning process

Syngas Cleaning Targets Methane conversion: 80% Benzene conversion: 99% Tars/HC conversion: 99% Meet $1.57 gal

Alcohols Gasoline Green Diesel FT Liquids

Products Feedstock Interface

Gasification

Gas Cleanup

&

Conditioning

By- products

Fuel Synthesis

Biomass Derived Syngas Cleaning

4

Gasification

Fluid Bed Catalytic

Tar Reforming

Regeneration

MAS/Fuel Synthesis

Sulfur Sorbents,

Contaminant Removal

Gasification

Recirculating Regenerating Tar Reforming

Gasification (Catalytic)

Regeneration

Fluid Bed Catalytic

Tar Reforming [1] [2] [3]

Biomass Syngas Cleaning Strategies

Feed Processing & Handling

Process Intensification

5

Reforming catalyst patent granted. Licensed by Rentech.

• Identify and benchmark the state of the art in tar reforming catalysts and sulfur sorbents

• Identify and develop candidate catalysts and sorbents with potential for improved performance

• Provide performance information for technoeconomic modeling of thermochemical biomass to ethanol processes

• Validate catalyst and sorbent performance at the pilot scale to meet syngas cleaning targets

• Down select best syngas cleaning process for 2012 pilot scale EtOH demonstration

• Prepare 1000 kg of catalyst for the demonstration

• Evaluate catalyst performance during demonstration

Project Start

Develop hot gas sulfur sorbents

Computational modeling of reforming catalysts starts

Recirculating regenerating reforming evaluated

Multi reactor catalyst system completed for syngas slipstream testing

Testing catalyst/sorbent combinations with raw syngas – assess cleanliness, optimize regeneration

2006

2007

2010

2008

2009

Evaluate new industrial reforming catalysts

Develop attrition resistant reforming catalysts; optimize regeneration with model syngas

Retrofit microactivity rapid catalyst test system

Evaluate pilot scale tar reforming and regeneration

2012

2011

1000 kg of catalyst prepared for demonstration

Demonstrate tar reforming for 100’s h with biomass syngas

Reforming Catalyst Chronology

6

Developing Tar Reforming (Bench to Pilot Scale)

0

20

40

60

80

100

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

% E

thyle

ne

Co

nve

rsio

n

Time (h)

Cat 1

Cat 2

Cat 14

Cat 18

Cat 26

Cat 27

C 11 NK

Cat 30

2007 C2H4 Reforming Only

Bench Scale

2010 CH4 Reforming and Regeneration in Model Syngas with H2S

Catalyst wt% NiO wt% MgO wt% K2O Support Ni/Mg

Cat. 32a 6.1 2.4 3.9 Al2O31 2

Cat. 34a 3 Al2O3

Cat. 34b 6 Al2O3

Cat. 34c 9 Al2O3

Cat. 34d 3 5.5 0.08 Al2O3 0.5

Cat. 34e 6 1.8 0.17 Al2O3 3.3

Cat. 34f 6 3.6 0.17 Al2O3 1.7

Cat. 34g 3 1.8 0.08 Al2O3 1.7

Cat. 34h 3 3.6 0.08 Al2O3 0.8

Cat. 34i 3 5.5 0.08 Al2O3 0.5

Cat. 34j 6 1.8 0.16 Al2O3 3.3

Cat. 34k 6 3.6 0.16 Al2O3 1.7

Cat. 34l 6 5.5 0.16 Al2O3 1.1

Cat. 34m 9 1.8 0.24 Al2O3 5

Cat. 34n 9 3.6 0.24 Al2O3 2.5

Cat. 34o 9 5.5 0.24 Al2O3 1.6

Cat. 35a 3 3 0.09 Al2O32 1

Cat. 35b 3 3 0.08 Zr-Al2O33 1

Cat. 35c 1.5 1.5 0.04 Zr-Ceria3 1

Cat. 35d 3 3 0.08 Ce-Zr- Al2O33 1

7

100

80

60

40

20

0% C

6H

6 C

on

ve

rsio

n

100

80

60

40

20

0% C

H4 C

on

ve

rsio

n

6050403020100

Time, minutes

Benzene FY08 Target

Methane FY08 Target

2008 CH4 Reforming in Oak Syngas

Developing Tar Reforming (Bench to Pilot Scale)

0%

20%

40%

60%

80%

100%

0:00 1:00 2:00 3:00 4:00

Co

nve

rsio

n (

%)

time-on-stream (h)

methane

benzene

toluene

phenol

naphthalene

anthr./phenanth.2006 CH4 Reforming In Oak Syngas

Methane Conversion During Continuous Regeneration

0

20

40

60

80

100

% C

H4 C

on

vers

ion

Bottled Syngas (Rentech)

Biomass Derived Syngas (NREL)

Syngas only, 890c

160ppm H2S, 32,000 mg/Nm3 tar, 910c

Syngas only, 900c

After multiple cycles of catalyst regeneration, 900c

After multiple hrs of no catalyst regeneration, 950c

2010 CH4 Reforming in Oak Syngas

SMARTS reactor

Cat

alys

t C

ircu

lati

on

Regenerated Catalyst

Spent Catalyst

Dirty Syngas

Reformed Syngas

8

Continuous Regenerating Tar Reforming

NREL patented Ni alumina fluidizable reforming catalysts are regenerable after use in H2S containing syngas

Regenerability extent determined by contact time and process conditions (gas compositions, temperature) -shorter contact times require less regeneration

NREL’s recirculating regenerating reformer is in place and readied for cold flow tests

1200 kg of CoorsTek support is ready for catalyst preparation (1000 kg) and cold flow evaluation (200 kg)

Catalyst preparation (1000 kg) in March FY2012: 6 wt% Ni/2.4% MgO/0.4 % K2O on alumina – Cat 51 – best performing composition

Cat

alys

t C

ircu

lati

on

Regenerated Catalyst

Spent Catalyst

Steam Air

H2

Dirty Syngas

Reformed Syngas

9

Cat

alys

t C

ircu

lati

on

Regenerated Catalyst

Spent Catalyst

Steam Air

H2

Dirty Syngas

Reformed Syngas

1000 kg Ni/K/Mg/Al2O3 Reform tars, methane to syngas US Patent 7,915,196

0

10

20

30

40

50

60

70

80

90

100

0 20 40 60 80 100 120 140 160 180 200

Me

than

e C

on

vers

ion

(%

)Time (min)

JM Catalyst Reforming Evaluation (Methane)

Ni 1

Ni 3

Ni 5

R3

R44

H2S Addition H2S Addition

Regeneration

30 kg JM catalyst Reform methane in H2S

Catalyst cost, performance and lifetime will be assessed with oak syngas for use in TEA and publications

Developing Tar Reforming (2012 Reforming Options)

10

Biopower Applications

2 DOD waste to energy projects Use forward operating base (FOB) waste for feedstock

Paper, plastics, packaging, food

Gasify waste to syngas for genset operation

NREL catalyst to be used for tar reforming (methane can be combusted) • Evaluating particulate and solid catalysts (monoliths)

• Providing regeneration processes if needed

• Providing post use catalyst characterization (identify and understand contaminant issues)

11

Acknowledgements

Whitney Jablonski Matt Yung Singfoong Cheah Yves Parent Jessica Olstad Mark Davis Mark Nimlos Katherine Gaston Steve Landin (CoorsTek) Steve Deutch Liz Rowsell (Johnson Matthey) Rich Bolin