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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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