Shiguang Li, GTIXinhua Liang, Missouri University of Science and Technology (Missouri S&T)

Nano-engineered catalyst for the utilization of CO2in dry reforming to produce syngas

DOE Contract No. DE-FE0029760

2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review MeetingAugust 26 - 30, 2019, Pittsburgh, PA

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78 History of Turning Raw Technology into Practical Energy Solutions

SUPPLY CONVERSION DELIVERY UTILIZATIONFOR A BETTER ECONOMY AND A BETTER ENVIRONMENT

World-class piloting facilities headquartered

in Chicago area

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Project overview Performance period: July 1, 2017 – September 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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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

PM: Particulate matter; FGD: Flue-gas desulfurization

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Background of dry reforming of methane using captured CO2

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

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Nickelocene Ni(C5H5)2Al2O3 surface

OH OHNi Ni

O O

CxHy C5H5

A Al2O3 surface

Nickelocene:

HydrogenH2B Al2O3 surface Al2O3 surface

Ni Ni

O O

CxHy C5H5

CxHy C5H6

NiNiOH OH

C Catalysts are calcined in air at 550 °C

Nano-engineered Ni catalyst prepared by atomic layer deposition (ALD) may resolve sintering issue

ALD is a commercial process in semiconductor industry

NiCp2

Hydrogenate the organic ligands bound to Ni

NiCp2 reacts with the surface -OH groups and the Cp ring is removed

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X-ray photoelectron spectroscopy analysis of α-Al2O3nanoparticles supported Ni catalysts

In addition to Ni and NiO, NiAl2O4spinel 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 (e.g. incipient wetness) are ~10-20 nm

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Packed bed catalytic reactor for dry reforming testing

H2

ArCO2

CH4

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ALD Ni catalyst showed advantages over traditional catalysts prepared by incipient wetness (IW)

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ALD Ni on γ-Al2O3 particles CO2 and CH4 cylinder gases used in testing

Higher activity due to highly dispersed nanoparticles: ~3.1 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

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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 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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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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200-h continuous testing of 20-cm long hollow fiber supported Ni ALD catalyst indicated good stability

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Designed and constructed reactor system at GTI for performance, deactivation and long-term stability tests

Furnace (reactor inside)

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Future plans

Task 8.0 – Catalytic reactor performance testing

Task 6.0 – Further improvement of the hollow fiber supported catalyst

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 testsBP2(4/1/19-9/30/20)

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 We are developing ALD nano-engineered catalysts for utilization of CO2 in

dry reforming of methane to produce syngas

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)

Uniform nano-engineered Ni nanoparticles were successfully deposited on high packing-density α-Al2O3 hollow fiber by ALD

200-h continuous testing of 20-cm long hollow fiber supported Ni ALD catalyst indicated good stability

Designed and constructed reactor system at GTI for performance, deactivation and long-term stability tests

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Acknowledgements

Financial and technical support

DOE NETL Andrew O'Palko, Bruce Lani, José Figueroa, and Lynn Brickett

Professor Liang Group Dr. Xiaofeng Wang Dr. Shoujie Ren

DE-FE0029760

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DisclaimerThis presentation was prepared by 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.

�Nano-engineered catalyst for the utilization of CO2 in dry reforming to produce syngas ��DOE Contract No. DE-FE002976078 History of Turning Raw Technology into Practical Energy SolutionsSlide Number 3Integration of the technology with coal-fired power plantsBackground of dry reforming of methane using captured CO2Nano-engineered Ni catalyst prepared by atomic layer deposition (ALD) may resolve sintering issueSlide Number 7Slide Number 8Slide Number 9ALD Ni catalyst showed advantages over traditional catalysts prepared by incipient wetness (IW) Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Slide Number 16Slide Number 17SummaryAcknowledgementsDisclaimer