CO2 Capture Technology Project Review Meeting
August 13 - 17, 2018, Pittsburgh, PA
Nano-engineered catalyst for the utilization of CO2 in dry reforming to produce syngas
DOE Contract No. DE-FE0029760
Shiguang Li, Gas Technology Institute (GTI)Xinhua Liang, Missouri University of Science and Technology (Missouri S&T)
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Project overview
Performance period: July 1, 2017 – June 30, 2020
Funding: $799,807 DOE ($200,000 co-funding)
Objectives: Develop nano-engineered catalyst supported on high-surface-area ceramic hollow fibers for the utilization of CO2 in dry reforming of methane (CO2 + CH4 → 2 H2 + 2 CO) to produce syngas
Team:Member Roles
• Project management and planning• Quality control, reactor design and testing• Techno-economic analysis (TEA ) and life cycle analysis (LCA)
Catalyst development and testing
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Introduction to GTI and Missouri S&T
Not-for-profit research company, providing energy and natural gas solutions to government and industry since 1941
Co-educational research university located in Rolla, Missouri
Prof. Liang Group: expertise in atomic layer deposition thin film coatings, catalyst synthesis and testing
IdeaMarket Analysis
Technology Analysis
Product Development
Lab and Field Testing
Demonstration
Commercialization
OFFICE SUBSIDIARY
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Background
CH4 + CO2 → 2H2 + 2CO with H2/CO ratio <1 due to the reverse water-gas shift reaction (CO2 + H2 ⇌ CO + H2O)
Different from methane steam reforming (CH4 + H2O → CO + 3 H2) where H2/CO ratio >3 due to water-gas shift reaction (CO + H2O ⇌ CO2 + H2)
Syngas: feedstock for fuels and chemicals production
H2/CO ratio determines the resulting products
Dry reforming syngas (H2/CO ratio = 0.7 - 1) can be used for producing high yield C5+ hydrocarbons
Higher H2/CO ratio can be achieved by blending with products from steam reforming
Typical catalysts: Precious metals (Pt, Rh, Ru): expensive Low-cost Ni: issue of sintering of the Ni particles
Background of dry reforming of methane using captured CO2
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Nano-engineered Ni catalyst prepared by atomic layer deposition (ALD) may resolve sintering issue
Higher activity Better stability
ALD is a commercial process in semiconductor industry
Advantages over traditional catalysts prepared by incipient wetness (IW)
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60
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0 100 200 300
Met
hane
con
vers
ion,
%
Time, hr
ALDIW
850
850
800
750
800
700 Ni/γ-Al2O3-
particle CO2 and CH4
cylinder gases used in testing
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Integration of the technology with coal-fired power plants
95%-99% purity CO2
CO2capture
unit
Pipeline CH4
Product:Syngas (H2 + CO)
T (oC) P (psig)800-850 1-10
Conditioning as needed
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Two conceptual process designs: 1) packed bed reactor, and 2) tube-shell transport reactor
Packed bed reactor: the reactor is filled with nano-engineered catalyst supported on 1-2 cm long hollow fibers
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Ceramic hollow fibers
OFiber internal surface, pores, and external surface coated with catalysts for reactions:
Feed:CO2 + CH4 to bore (tube) side
Product: syngas (H2 + CO)Collected from the shell side
Dead end
Tube-shell transport reactor:
CO2 + CH4 → 2 H2 + 2 CO
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Nickelocene Ni(C5H5)2Al2O3 surface
OH OHNi Ni
O O
CxHy C5H5
A Al2O3 surface
Nickelocene:
Nano-engineered Ni catalyst prepared by ALD
HydrogenH2B Al2O3 surface Al2O3 surface
Ni Ni
O O
CxHy C5H5
CxHy C5H6
NiNiOH OH
C Catalysts are calcined in air at 550 °C
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X-ray photoelectron spectroscopy analysis of α-Al2O3 nanoparticles supported Ni catalysts
In addition to Ni and NiO, NiAl2O4 formed during Ni ALD, which increases Ni-support interaction
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TEM image of α-Al2O3 nanoparticle-supported Ni catalysts
Particle size: 2-6 nm, average 3.1 nm Particles prepared by traditional methods are ~10-20 nm
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1 2 3 4 5
Freq
uenc
y, %
Particle diameter (nm)
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Novel α-Al2O3 hollow fiber with high packing density is being used as catalyst substrate in current project
Catalyst Geometry SA/V (m2/m3)
1-hole 1,1511-hole-6-grooves 1,7334-hole 1,70310-hole 2,013Monolith 1,3004-channel ceramic hollow fibers 3,000
Commercial substrates
Novel α-Al2O3 hollow fibers Four channels, 35 cm long OD of 3.2 mm and a channel inner
diameter of 1.1 mm Geometric surface area to volume
as high as 3,000 m2/m3
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Dry reforming performance of the α-Al2O3 hollow fiber supported Ni catalysts (Ni/α-Al2O3-HF )
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0 50 100 150 200 250
Met
hane
refo
rm ra
te, L
h-1 g
Ni-1
Time on stream, hr
ALD-Ni/Al₂O₃-HF
IW-Ni/Al₂O₃-HF
850 ºC 800 ºC 750 ºC 700 ºC Higher activity due to highly dispersed nanoparticles: ~3.6 nm Ni particles compared to ~10-20 nm particles prepared by traditional method
Better stability due to strong bonding between nanoparticles and substrates since the particles are chemically bonded to the substrate during ALD
CO2 and CH4cylinder gases used in testing
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Al2O3 ALD film increases Ni-support interaction, and thus improves catalytic performance
AlCH3
CH3
CH3OH OH OH
AlCH3
CH3
CH3
A)
B)
OH
Al(CH3)3
OH OH
Trimethylaluminum(TMA)
CH4
AlCH3
AlCH3CH3
H2O
WaterAl
CH3
CH3
CH3OH OH OH
AlCH3
AlCH3CH3 Al
CH3
CH3
CH3
CH3
OH OH OHAl Al
CH3CH3
H2O
H2OOH
CH4
OHOH
Binary reaction: 2Al(CH3)3 + 3 H2O Al2O3 + 6 CH4A reaction: 2AlOH* + 2Al(CH3)3 → 2[Al-O-Al(CH3)2]* + 2CH4
B reaction: 2[Al-O-Al(CH3)2]* + 3H2O → Al2O3 + 2AlOH* + 4CH4
Ni nanoparticleAl2O3 support
Ni nanoparticleAl2O3 ALD film
Al2O3 ALD
Al2O3 ALD Chemistry
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Dry reforming performance of the Al2O3 promoted Ni/α-Al2O3-HF catalysts
Catalyst Conversion (%)
H2/CO ratio
Methane reforming rate (Lh-1gNi
-1)
Ni/α-Al2O3-HF 88 0.85 2,500
2Al2O3-Ni/α-Al2O3-HF 91 0.85 2,600
5Al2O3-Ni/α-Al2O3-HF 90 0.84 2,600
10Al2O3-Ni/α-Al2O3-HF 88 0.85 2,500
800 °C, 15 psia, CO2 and CH4 cylinder gases used in testing
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CeO2 promoted Ni/α-Al2O3-HF catalysts
• CeO2 can potentially increase Ni-support interaction, and provide highly mobile oxygen to inhibit coking of the catalyst
• We improved the catalyst performance by CeO2 coating prepared by impregnation method
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3500
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Met
hane
refo
rm ra
te, L
h-1 g
Ni-1
TOS, hr
Ni/HF0.25Ce-Ni/HF0.42Ce-Ni/HF0.75Ce-Ni/HF
850 °C 800 °C
1st cycle 2nd cycle
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3500
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Met
hane
refo
rm ra
te, L
h-1 g
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TOS, hr
Ni/HF0.25Ce-Ni/HF0.42Ce-Ni/HF0.75Ce-Ni/HF
850 °C 800 °C
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ALD reactor modified for depositing catalysts onto 20-cm-long hollow fibers
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Ni nanoparticles successfully deposited on 20-cm-long hollow fibers by ALD
Before Ni ALD After Ni ALD
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Dry reforming performance of the Ni ALD coated 20-cm-long hollow fibers
20-cm-long fibers were broken up into 1-cm-long fibers and tested in a packed bed reactor (CO2 and CH4 cylinder gases used in testing).
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Met
hane
refo
rm ra
te, L
h-1 g
Ni-1
TOS, hr
upper part
middle part
lower part
850 °CUpper part
Middle part
Lower part
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Tube-shell transport reactor designed, Ni coated 20-cm-long hollow fibers to be tested
ab
c d e
ag gf
Constant high temperature zone (800-850 °C)
Low temperature zone
Dead end (sealed)
Glazed part in low temperature zone
Catalytic active part in constant
temperature zone
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Future plans
BP1(18 months)
Task 8.0 – Catalytic reactor performance testing of the two configurations
Task 6.0 – Further improvement of the hollow fiber supported catalyst
Task 5.0 – Evaluation of 20-cm hollow fiber supported catalyst performance
Task 7.0 – Design and construction of reactor containing multiple hollow fibers
Task 11.0 – Life cycle analysis and technical and economic feasibility study
Task 10.0 – Catalyst deactivation and long-term stability tests
Task 9.0 – Supply of catalyst for deactivation and long-term stability tests
BP2(18 months)
In this project
After the current project Test the technology at a larger scale with captured CO2
We are here
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Summary
Novel α-Al2O3 hollow fiber increases surface area, and enables tube-shell transport reactor configuration.
ALD nano-engineered catalyst improves activity and stability for utilization of CO2 in dry reforming of methane to produce syngas (compared to catalysts prepared by conventional incipient wetness method).
Coating of Al2O3 or CeO2 on Ni/α-Al2O3-HF catalysts further improves dry reforming performance.
Uniform Ni was successfully coated on 20-cm-long hollow fibers using a modified ALD reactor.
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Acknowledgements Financial and technical support
DOE NETL: Bruce Lani and Lynn Brickett Professor Liang Group
Dr. Zeyu Shang Dr. Xiaofeng Wang Mr. Baitang Jin
DE-FE0029760
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Disclaimer
This presentation was prepared by Gas Technology Institute (GTI) as an account of work sponsored by an agency of the United States Government. Neither GTI, the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors herein do not necessarily state or reflect those of the United States Government or any agency thereof.
