producing clean biomass syngas for fuel synthesis ... · 3 project rationale: syngas cleaning...
TRANSCRIPT
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)