2 Nrel Stefan Czernik

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Hydrogen from Post-Consumer Residues

S. Czernik, R. French, R. Evans, E. Chornet

National Bioenergy Center

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

Berkeley, CA May 19-23, 2003


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Goal of the Project

This work is one of three tasks in the

Biomass to Hydrogen project.

Goal: develop and demonstratetechnology for producing hydrogen frombiomass at $2.90/kg purified hydrogen

by 2010. By 2015, be competitive withgasoline.


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Objectives of the Task

Explore feasibility of producing hydrogen from low-cost, potentially high-hydrogen-yield renewablefeedstocks that could complement biomass, increaseflexibility and improve economics of Biomass toHydrogen process.

Can help overcome a barrier of high cost and

availability of feedstock.

Demonstrate efficiency of pyrolysis/reforming

technology in application to readily available post-consumer wastes: plastics, trap grease, mixedbiomass and synthetic polymers.

Addresses the challenge of technology improvement.


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Potential for Hydrogen

Plastics wastes: 15 Mt/year; potential forproducing 6 Mt/year of hydrogen (energy

equivalent 0.8x1018J/year) enough to fuel15-20 million fuel cell vehiclesRequires development of collection programs and separation

technologies.Target streams: manufacturing residues (textiles), MRF tailings.

Trap grease recovered: 6 kg/year/person - 1.5Mt/year; potential for 0.5 Mt/year hydrogen.Assuming that processing costs will be comparable to those forresidual oil ($0.7/kg H2), trap grease presents a near-term market

opportunity for the production of hydrogen.


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Approach

Technology being developed for producing

hydrogen from biomass:

Pyrolysis or partial oxidation of biomass, plastics, and

other solid organic residues.Catalytic steam reforming of the resulting pyrolysisgases and vapors.

Catalytic steam reforming of biomass-derived liquidstreams (trap grease).

Opportunities to co-process different feedstocks.


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Process Reactions

500500--800C800C

PolymersPolymers Monomers and otherMonomers and othervolatile compoundsvolatile compounds

800C, cat.800C, cat.

CCnnHHmmOOkk + (n+ (n--k) Hk) H22OO n CO + (m/2 +nn CO + (m/2 +n--k) Hk) H22

n CO + n H2On CO + n H2O n COn CO22 + n H+ n H22


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Project Timeline

Hydrogen from Post-Consumer Residues Timeline

FY02 03 04 05 06 07 08 09

Production of Hydrogen by Catalytic SteamReforming of Trap Grease

Reforming tests using commercial catalyst

Reforming tests using NREL fluidizable catalysts

Feedstock clean up strategy and long-term catalyst

performance demonstration

Co-process trap grease with other biomass-derived liquids

80% yield, 150 hours on stream,

catalyst attrition losses.

Production of Hydrogen by IntegratedPyrolysis/Reforming of Plastics

Proof of Concept at Micro-Reactor/MBMS scale

Bench-scale tests using integrated bubbling bed reactor system

Bench-scale tests using plastic mixtures (gas clean up)

Bench-scale co-processing of biomass and other feedstocks

Production of Hydrogen from DifferentFeedstocks in Support of the Scale up Effort

Construction of bench-scale circulating fluid bed reformer

Bubbling and circulating bed tests on flexible feedstocks

80% yield, low attrition of catalyst

80% yield, low catalyst

attrition, long-durationactivity

Completed

80% yield from variety

of feedstocks


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Milestones

1. Production of hydrogen from plastics by

fluidized bed pyrolysis/reforming process;

yield 80% of stoich. (34 g H2/100 g PP).

September 2003.

2. Demonstrate efficiency of fluidisable,attrition resistant catalyst developed at

NREL for trap grease reforming; 80% of thestoich. yield (28 g H2/100 g grease).

September 2003.

Fl idi d B d I t t d P l i


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Fluidized Bed Integrated PyrolysisReforming System


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Process Conditions

Pyrolysis zone at 600 - 700C(Operated in both pyrolysis and POX mode)Steam flow: 240 g/hFeed rate: 60 g/h polypropylene

Reforming zone at 850CCommercial nickel-based catalyst

Molar (Steam/Carbon): 4.6

GC1HSV: 1600 h-1


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Product Gas Composition

0

10

20

30

40

50

60

70

80

0.0 2.0 4.0 6.0 8.0 10.0

Time, h

%v

ol.

0

5000

10000

15000

ppm,vol.

H2

CO2

CO

C2H4

CH4

650C 600C

Pyrolysis/Reforming of Polypropylene


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Yield of Hydrogen

Pyrolysis/Reforming of Polypropylene(stoich. yield: 42.9 g H2/100 g PP)

0

20

40

60

80

100

0 2 4 6 8 10

Time, h

%

stoich. Actual

If followed by WGS

650C 600C


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Trap Grease

Collected from different sites in the U.S. byPacific Biodiesel for DOE Biodiesel Program.

Mixture of C16 and C18 free fatty acids and fats;Elemental analysis:

C: 76.2%; H: 11.8%; O: 11.9%;

N: 0.02%; S: 70 ppm; ash: 0.1%;Process conditions:

Temperature: 850C, NREL fluidisable catalystGrease feed rate: 42 g/h, steam flow: 240 g/h

S/C: 5, GC1HSV: 970 h-1


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Trap Grease Product Gas Composition

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

0 5 0 1 0 0 1 5 0 2 0 0

Time, h

%vo

l.

H 2

C O

C O2

0.0

1.0

2.0

3.0

4.0

5.0

0 20 40 60 80 100 120 140 160 180

Time , h

%v

ol.

CH4

C2H4

C6H6


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Yield of Hydrogen

Reforming Trap Grease(Stoich. yield of H2: 35 g/100 g grease)

0

20

40

60

80

100

0 20 40 60 80 100 120 140 160 180

Time, h

Reforming

Reforming + WGS


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Other Accomplishments

Publications:

Chornet, E. and Czernik, S., Renewable fuels: Harnessinghydrogen, Nature 2002, 418, 928-929.

Czernik, S., French, R., Feik, C., Chornet, E.; Hydrogen byCatalytic Steam Reforming of Liquid Byproducts fromBiomass Thermoconversion Processes, I&EC Research2002, 41, 4209-4215.

Record of Invention filed in U.S. DOE.

Collaboration:Interface Research Corp., National Diesel Board,

American Apparel Manufacturers Association.


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Future Work

Complete milestones for FY 2003.

Demonstrate pyrolysis/reforming process forcomplex feedstocks (textiles, mixed plastics)

using commercial and NREL developed catalysts.

Demonstrate production of hydrogen by co-processing renewable (solid and liquid biomassand wastes) and fossil (natural gas) feedstocks.

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