IP Library › Granted Patent US 12,637,355
Granted Patent B2
US 12,637,355 · App. 17/759,933 · Granted May 26, 2026

Method for generating carbon monoxide, method for producing precursor, and material for chemical looping system

Inventors: Yasushi Hashimoto (Tokyo, JP); Yasushi Sato (Tokyo, JP); Yasushi Sekine (Tokyo, JP)
Assignees: ENEOS CORPORATION; WASEDA UNIVERSITY
C01B32/40
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Quick Facts
Patent No.
US 12,637,355
App. No.
17/759,933
Granted
May 26, 2026
Kind
B2
Abstract

A method for generating carbon monoxide includes: a generation step of generating carbon monoxide by supplying carbon dioxide to a first material containing a first element included in elements of group 11 and a second element included in elements of groups 8 to 10, 12, and 13; and a reduction step of reducing the second element oxidized in the generation step by supplying hydrogen to a second material containing the oxidized second element and the first element. The generation step and the reduction step are repeated a plurality of times.

Claims (11)

1 . A method for generating carbon monoxide, the method comprising:

a first reduction step of generating water and a first material containing copper and indium by supplying hydrogen to a precursor that is a composite oxide containing Cu 2 In 2 O 5 , thereby reducing the precursor;

a generation step of generating carbon monoxide by supplying carbon dioxide to the first material and generating a second material by oxidizing the indium; and

a second reduction step of generating the first material by reducing the indium oxidized by supplying hydrogen to the second material, wherein

the generation step and the second reduction step are repeated a plurality of times after the first reduction step.

2 . The method for generating carbon monoxide according to claim 1 , wherein the oxidized indium is In 2 O 3 .

3 . The method for generating carbon monoxide according to claim 1 , wherein the first material contains indium oxide, and the indium oxide has a particle size of 90 nm or less.

4 . The method for generating carbon monoxide according to claim 1 , further comprising a step of producing a precursor before the first time first reduction step, the step of producing a precursor comprising:

a first heat treatment step of heat-treating an aqueous solution containing a nitrate of the copper, a nitrate of the indium, and citric acid at a temperature of lower than 100° C.;

a second heat treatment step of heat-treating the aqueous solution at a temperature of 100° C. or higher and removing an organic substance to obtain an intermediate; and

a firing step of firing the intermediate to produce the precursor.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 2, 2022
From: HASHIMOTO, YASUSHI; SATO, YASUSHI; SEKINE, YASUSHI
To: ENEOS CORPORATION; WASEDA UNIVERSITY
Reel/Frame 060694/0365 →
Priority Claims (1)
JP 2020-018155 · Feb 5, 2020 · national
Continuity (1)
Related Publication 20230077049A1 · Mar 9, 2023
References Cited (55)
US 20140070144A1 · Chalabi et al. · 2014 [cited by applicant]
US 20140377158A1 · Andrus et al. · 2014 [cited by applicant]
US 20180207599A1 · Metcalfe · 2018 [cited by applicant]
US 20190085473A1 · Sugano et al. · 2019 [cited by applicant]
CN 1223474A · 1999 [cited by applicant]
CN 103230799A · 2013 [cited by applicant]
CN 103687665A · 2014 [cited by applicant]
CN 103861597A · 2014 [cited by applicant]
CN 105110332A · 2015 [cited by applicant]
CN 107754815A · 2018 [cited by applicant]
CN 110433813 · 2019 [cited by examiner]
JP H07136462A · 1995 [cited by applicant]
JP 2014528884A · 2014 [cited by applicant]
JP 2015016467A · 2015 [cited by applicant]
JP 2018529504A · 2018 [cited by applicant]
JP 2019051493A · 2019 [cited by applicant]
WO 2019099795A1 · 2019 [cited by applicant]
WO 2019163968A1 · 2019 [cited by applicant]
Larrazabal et al. “Enhanced Reduction of CO2 to CO . . . ”. ACS Catal. 6, 6265-6274 (2016). (Year: 2016). [cited by examiner]
Xiang et al. “Copper-Indium Binary Catalyst on a gas diffusion electrode . . . ”. ACS Appl. Mater. Interfaces, 12, 601-608 (2020). Received Sep. 2019. (Year: 2020). [cited by examiner]
Office Action (Communication pursuant to Rule 114(2) EPC/Third Party Observation) issued on May 15, 2025, in corresponding European Patent Application No. 21750719.3. (15 pages). [cited by applicant]
Tsoukalou et al., “Structural Evolution and Dynamics of an In2O3 Catalyst for CO2 Hydrogenation to Methanol: An Operando XAS-XRD and In Situ TEM Study”, Journal of the American Chemical Society, (2019), 141, pp. 13497-1… [cited by applicant]
Supporting Information for TM1, “The Structural Evolution of In2O3 Catalyst for Hydrogenation of CO2 to Methanol: an Operando XAS-XRD and in situ TEM Study”. (30 pages). [cited by applicant]
R.H. Piva et al., “Thermal stability and phase transformation in fully indium oxide (In01.5) stabilized zirconia”, Materials Characterization, (2017), 123, pp. 58-66. [cited by applicant]
H.C. Shin et al., “Mechanism of M Ferrites (M = Cu and Ni) in the CO2 Decomposition Reaction”, Chemistry of Materials, (2001), vol. 13, No. 4, pp. 1238-1242. [cited by applicant]
Series in Materials, Science and Engineering: Fundamental of Ceramics, edited by M.W. Barsoum, Taylor & Francis Group, LLC 2003, pp. 532-533. (3 pages). [cited by applicant]
M.A. Dar et al., “Effect of d-block element Co2+ substitution on structural, Mössbauer and dielectric properties of spinel copper ferrites”, Journal of Magnetism and Magnetic Materials, (2017), 436, pp. 101-112. [cited by applicant]
“Indium Oxide (In2O3) Nanopowder/Nanoparticles”. (4 pages). [cited by applicant]
Yu Qiu et al., “Copper and cobalt co-doped ferrites as effective agents for chemical looping CO2 splitting”, Chemical Engineering Journal 387, (2020), 124150. (7 pages). [cited by applicant]
CN Office Action issued in CN Application No. 202180012744.3; Mailed Mar. 15, 2023, 11 Pages (with Translation). [cited by applicant]
International Search Report (PCT/ISA/210) and Written Opinion (PCT/ISA/237), with English translations, dated Apr. 6, 2021, for International Application No. PCT/JP2021/001762. [cited by applicant]
Guo Weiwei et al., “Metal-Organic Framework-Derived Indium-Copper Bimetallic Oxide Catalysts for Selective Aqueous Electroreduction of CO2”, Green Chemistry, Feb. 4, 2019, vol. 21, No. 3, pp. 503-508, XP093120146. [cited by applicant]
Office Action (Communication pursuant to Rule 164(1) EPC) issued on Feb. 1, 2024, in corresponding European Patent Application No. 21750719.3. (15 pages). [cited by applicant]
Xiang Hang et al., “Copper-Lndium Binary Catalyst on a Gas Diffusion Electrode for High-Performance CO2 Electrochemical Reduction With Record CO Production Efficiency”, Applied Materials & Interfaces, vol. 12, No. 1, Ja… [cited by applicant]
“Steel oxide nanoparticles (In2O3 research grade)” and partial machine English translation. (4 pages). [cited by applicant]
“Inorganic Chemistry A Modern Approach” and partial machine English translation. (3 pages). [cited by applicant]
“Schreiber-Atkins Inorganic Chemistry” and partial machine English translation. (3 pages). [cited by applicant]
“Inorganic Materials Science for Engineering” and partial machine English translation. (6 pages). [cited by applicant]
“On the corrosion resistance of ceramics” and partial machine English translation. (11 pages). [cited by applicant]
Yu Qiu et al., “Efficient CO 2 to CO conversion at moderate temperatures enabled by the cobalt and copper co-doped ferrite oxygen carrier”, Journal of Energy Chemistry, 46, (2020), pp. 123-132. (10 pages). [cited by applicant]
“Particle size—Particle size distribution” and partial machine English translation. (17 pages). [cited by applicant]
Jianyang Wang et al., “Variation in the In2O3 Crystal Phase Alters Catalytic Performance toward the Reverse Water Gas Shift Reaction”, ACS Catal., (2020), 10, pp. 3264-3273. (10 pages). [cited by applicant]
Office Action (Notice of Reasons for Cancellation) issued on Mar. 26, 2025, in corresponding Japanese Patent Application No. 2024-701147 and machine English translation of the Office Action. (62 pages). [cited by applicant]
Office Action (Statement of Evidence) issued on Mar. 3, 2025, in corresponding Japanese Patent Application No. 2020-018155 and machine English translation of the Office Action. (7 pages). [cited by applicant]
Office Action (Statement of Objections) issued on Mar. 3, 2025, in corresponding Japanese Patent Application No. 2020-018155 and machine English translation of the Office Action. (99 pages). [cited by applicant]
Office Action (Notification of Reason(s) for Refusal) issued on Dec. 26, 2023, in corresponding Japanese Patent Application No. 2020-018155 and English machine translation of the Office Action. (3 pages). [cited by applicant]
Office Action (Communication pursuant to Article 94(3) EPC) issued on Sep. 29, 2025, in corresponding European Patent Application No. 21750719.3. (5 pages). [cited by applicant]
Office Action (Notice of Reason for Rejection of Amendment) issued on Nov. 13, 2025, in corresponding Japanese Patent Application No. 2020-018155 (Patent No. 7491505) and machine English translation of the Office Action… [cited by applicant]
Office Action (Notice of Grounds for Cancellation) issued on Feb. 27, 2026, in corresponding Japanese Patent Application No. 2024-701147 (Patent No. 7491505) and machine English translation of the Office Action. (125 pa… [cited by applicant]
Office Action (Notice of Delivery of a Copy of the Statement of Opinion) issued on Feb. 27, 2026, in corresponding Japanese Patent Application No. 2024-701147 (Patent No. 7491505) and machine English translation of the … [cited by applicant]
Office Action (Communication pursuant to Article 94(3) EPC) issued on Mar. 25, 2026, in corresponding European Patent Application No. 21750719.3. (5 pages). [cited by applicant]
Hirunsit et al., “Cu—Cr, Cu—Mn, and Cu—Fe Spinel-Oxide-Type Catalysts for Reforming of Oxygenated Hydrocarbons”, The Journal of Physical Chemistry C2013, (Aug. 8, 2025), No. 117, p. 23757-23765. [cited by applicant]
Qiu et al., “Enhanced Hydrogen Production Performance at Intermediate Temperatures Through the Synergistic Effects of Binary Oxygen Carriers”, Applied Energy 252 (2019) 113454, Aug. 8, 2025. (10 pages). [cited by applicant]
Fujifilm Wako Pure Chemical Corporation, “Safety Data Sheet”, (Aug. 21, 2025) and machine English translation. https://labchem-wako.fujifilm.com/sds/WOIW0105-0098JGHEJP.pdf. (19 pages). [cited by applicant]
Office Action (Examination report No. 1 for standard patent application) issued on Mar. 12, 2026, in corresponding Australian Patent Application No. 2021217843. (5 pages). [cited by applicant]