IP Library Granted Patent US 12,246,965
Granted Patent B2
US 12,246,965 · App. 17/638,423 · Granted Mar 11, 2025

On demand synthesis gas from methanol

Inventors: Peter Mølgaard Mortensen (Roskilde, DK); Robert Klein (Roskilde, DK); Kasper Emil Larsen (Humlebæk, DK); Kim Aasberg-Petersen (Allerød, DK)
Assignee: HALDOR TOPSØE A/S
C01B3/26B01J19/0053B01J19/08C01B2203/0216C01B2203/0283C01B2203/1082C01B2203/1223
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Quick Facts
Patent No.
US 12,246,965
App. No.
17/638,423
Granted
Mar 11, 2025
Kind
B2
Abstract

A reactor system and a process for carrying out the methanol cracking and reverse water gas shift reaction of a feedstock comprising methanol to synthesis gas are provided, where the heat for the endothermic methanol cracking and reverse water gas shift reaction is provided by resistance heating.

Claims (30)

1. A reactor system for production of synthesis gas from a feedstock comprising methanol in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions, said reactor system comprising:

a supply of feedstock comprising methanol and water;

a structured catalyst arranged for catalyzing methanol cracking and reverse water gas shift reactions of said feedstock, said structured catalyst comprising a macroscopic structure of an electrically conductive material, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material;

a pressure shell housing said structured catalyst, said pressure shell comprising an inlet for letting in said feedstock and an outlet for letting out product gas, wherein said inlet is positioned so that said feedstock enters said structured catalyst in a first end of said structured catalyst and said product gas exits said structured catalyst from a second end of said structured catalyst;

a heat insulation layer between said structured catalyst and said pressure shell;

at least two conductors electrically connected to said structured catalyst and to an electrical power supply placed outside said pressure shell, wherein said electrical power supply is dimensioned to heat at least part of said structured catalyst to a temperature of at least 500° C. by passing an electrical current through said macroscopic structure, wherein said at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to said first end of said structured catalyst than to said second end of said structured catalyst, and wherein the structured catalyst is constructed to direct an electrical current to run from one conductor substantially to the second end of the structured catalyst and return to a second of said at least two conductors;

an outlet for a first product gas comprising synthesis gas.

2. The reactor system according to claim 1 , wherein said structured catalyst is arranged to catalyze the methanation and steam reforming reactions.

3. The reactor system according to claim 1 , wherein said electrical power supply is dimensioned to heat at least part of said structured catalyst to a temperature of at least 700° C.

4. The reactor system according to claim 1 , wherein the feedstock additionally comprises CO 2 .

5. The reactor system according to claim 1 , wherein the feedstock additionally comprises H 2 , N 2 , CH 4 and/or Ar.

6. The reactor system according to claim 1 , further comprising electrically insulating parts provided in the structured catalyst and positioned between the at least two conductors.

7. A process for carrying out the methanol cracking and reverse water gas shift reaction of a feedstock comprising methanol and water to synthesis gas in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions, in a reactor system comprising a pressure shell housing a structured catalyst arranged for catalyzing said methanol cracking and reverse water gas shift reactions of a feedstock, said structured catalyst comprising a macroscopic structure of electrically conductive material, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material; wherein said reactor system is provided with heat insulation between said structured catalyst and said pressure shell; said process comprising the steps of:

pressurizing said feedstock,

supplying said pressurized feedstock to said pressure shell through an inlet positioned so that said feedstock enters said structured catalyst in a first end of said structured catalyst; allowing the feedstock to undergo a methanol cracking and reverse water gas shift reaction over the structured catalyst and outletting a product gas from said pressure shell, wherein said product gas exits said structured catalyst from a second end of said structured catalyst;

supplying electrical power via electrical conductors connecting an electrical power supply placed outside said pressure shell to said structured catalyst, allowing an electrical current to run through said macroscopic structure, thereby heating at least part of the structured catalyst to a temperature of at least 500° C., wherein said at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to said first end of said structured catalyst than to said second end of said structured catalyst, and wherein the structured catalyst is constructed to direct an electrical current to run from one conductor substantially to the second end of the structured catalyst and return to a second of said at least two conductors, thereby heating at least part of the structured catalyst to a temperature sufficient for said feedstock to undergo the methanol cracking and reverse water gas shift reaction over the structured catalyst, thereby heating at least part of the structured catalyst to a temperature sufficient for said feedstock to undergo the methanol cracking and reverse water gas shift reaction over the structured catalyst,

outletting a first product gas comprising synthesis gas from the reactor system.

8. The process according to claim 7 , wherein the first product gas comprising synthesis gas from the reactor system is provided to an adiabatic post converter comprising a fifth catalyst active for catalyzing steam methane reforming, methanation and reverse water gas shift reactions; and in said adiabatic post converter, letting at least a part of the product gas stream and a heated CO 2 rich gas stream undergo steam methane reforming, methanation and reverse water gas shift reactions to thereby provide a second product gas, said second product gas being a CO rich synthesis gas stream.

9. The process according to claim 7 , wherein the process further comprises the step of feeding the first product gas or the second product gas comprising synthesis gas to an upgrading unit and separating it into an upgraded synthesis gas stream and one or more off-gas stream.

10. The process according to claim 9 , wherein the process further comprises the step of recycling one or more of the off-gas streams to upstream units of said upgrading unit.

11. A method for rapidly switching a metal-catalysed methanol cracking and reverse water gas shift reaction of a feedstock comprising methanol in a reactor system according to claim 1 , from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice-versa; said method comprising the steps of:

in said first steady-state reaction condition (A):

supplying said feedstock to the reactor system in a first total flow, and

supplying a first electrical power via electrical conductors connecting an electrical power supply placed outside said pressure shell to said structured catalyst, thereby allowing a first electrical current to run through said electrically conductive material,

thereby heating at least part of the structured catalyst to a first temperature at which said feedstock is converted to a first product gas mixture over said structured catalyst under said first steady-state reaction conditions (A); and said first product gas is outlet from the reactor system;

and, in said second steady-state reaction condition (B):

supplying said feedstock to the reactor system in a second total flow,

supplying a second electrical power via electrical conductors connecting an electrical power supply placed outside said pressure shell to said structured catalyst, thereby allowing a second electrical current to run through said electrically conductive material,

thereby heating at least part of the structured catalyst to a second temperature; at which said feedstock is converted to a second product gas mixture over said structured catalyst under said second steady-state reaction conditions (B); and said second product gas is outlet from the reactor system;

wherein said second electrical power is higher than said first electrical power; and/or said second total flow is higher than said first total flow.

Assignments (2)
CHANGE OF NAME Recorded Aug 13, 2025
From: HALDOR TOPSØE A/S
To: TOPSOE A/S
Reel/Frame 072435/0396 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 12, 2022
From: MORTENSEN, PETER MØLGAARD; KLEIN, ROBERT; LARSEN, KASPER EMIL; AASBERG-PETERSEN, KIM
To: HALDOR TOPSØE A/S
Reel/Frame 059967/0086 →
Priority Claims (2)
DK PA 2019 01149 · Oct 1, 2019 · national
DK PA 2019 01432 · Dec 6, 2019 · national
Continuity (1)
Related Publication 20220298015A1 · Sep 22, 2022
References Cited (158)
US 3499947A · Johnson · 1970 [cited by applicant]
US 4157356A · Bulford et al. · 1979 [cited by applicant]
US 4520224A · Kamimura · 1985 [cited by applicant]
US 5631302A · Koenig et al. · 1997 [cited by applicant]
US 5827901A · Koenig et al. · 1998 [cited by applicant]
US 5976723A · Boffito et al. · 1999 [cited by applicant]
US 6322757B1 · Cohn et al. · 2001 [cited by applicant]
US 6433029B1 · Fitzpatrick · 2002 [cited by applicant]
US 6746650B1 · Lesieur · 2004 [cited by applicant]
US 7960441B2 · Wolf · 2011 [cited by applicant]
US 8568581B2 · Sivasankar et al. · 2013 [cited by applicant]
US 9067847B2 · Bashir et al. · 2015 [cited by applicant]
US 11214488B2 · Rueger · 2022 [cited by applicant]
US 20020051741A1 · Abe et al. · 2002 [cited by applicant]
US 20020081253A1 · Abe · 2002 [cited by applicant]
US 20020094312A1 · Hanus et al. · 2002 [cited by applicant]
US 20020119084A1 · Boneberg · 2002 [cited by applicant]
US 20040016650A1 · Klug · 2004 [cited by applicant]
US 20040081875A1 · Milliken et al. · 2004 [cited by applicant]
US 20040197246A1 · Stevens et al. · 2004 [cited by applicant]
US 20040265225A1 · Watson et al. · 2004 [cited by applicant]
US 20060116543A1 · Bellet et al. · 2006 [cited by applicant]
US 20060124445A1 · Labrecque et al. · 2006 [cited by applicant]
US 20060254141A1 · Krause et al. · 2006 [cited by applicant]
US 20070045125A1 · Hartvigsen et al. · 2007 [cited by applicant]
US 20080023338A1 · Stoots et al. · 2008 [cited by applicant]
US 20080169449A1 · Mundschau · 2008 [cited by applicant]
US 20090220390A1 · Grouset · 2009 [cited by applicant]
US 20090235587A1 · Hawkes et al. · 2009 [cited by applicant]
US 20090289227A1 · Rising · 2009 [cited by applicant]
US 20090307975A1 · Wolf · 2009 [cited by applicant]
US 20100111781A1 · Takahashi et al. · 2010 [cited by applicant]
US 20100296984A1 · Ando et al. · 2010 [cited by applicant]
US 20110020207A1 · Siegert · 2011 [cited by applicant]
US 20110136027A1 · Chen et al. · 2011 [cited by applicant]
US 20110253550A1 · Hoffmann · 2011 [cited by applicant]
US 20110253551A1 · Lane et al. · 2011 [cited by applicant]
US 20110293510A1 · Grannell et al. · 2011 [cited by applicant]
US 20120228150A1 · Kang et al. · 2012 [cited by applicant]
US 20120288776A1 · Nagaosa · 2012 [cited by applicant]
US 20120326090A1 · Han et al. · 2012 [cited by applicant]
US 20130345326A1 · Bashir et al. · 2013 [cited by applicant]
US 20140272734A1 · Braun et al. · 2014 [cited by applicant]
US 20140291162A1 · Sala et al. · 2014 [cited by applicant]
US 20150129805A1 · Karpenko et al. · 2015 [cited by applicant]
US 20150175509A1 · Almqvist et al. · 2015 [cited by applicant]
US 20150299871A1 · Chen et al. · 2015 [cited by applicant]
US 20160002036A1 · Kolaczkowski et al. · 2016 [cited by applicant]
US 20160355932A1 · Reytier et al. · 2016 [cited by applicant]
US 20170106360A1 · Meriam · 2017 [cited by applicant]
US 20180066371A1 · Hong et al. · 2018 [cited by applicant]
US 20180127668A1 · Masel · 2018 [cited by applicant]
US 20180194632A1 · Jakobsson et al. · 2018 [cited by applicant]
US 20190085250A1 · Anzelmo et al. · 2019 [cited by applicant]
US 20190112187A1 · Mortensen et al. · 2019 [cited by applicant]
US 20190144376A1 · Højlund et al. · 2019 [cited by applicant]
US 20200095124A1 · Rueger · 2020 [cited by applicant]
US 20200354216A1 · Mortensen · 2020 [cited by applicant]
US 20210113983A1 · Mortensen et al. · 2021 [cited by applicant]
US 20210171344A1 · Mortensen et al. · 2021 [cited by applicant]
US 20210238035A1 · Mortensen et al. · 2021 [cited by applicant]
US 20220081289A1 · De Sarkar et al. · 2022 [cited by applicant]
CA 2427464A1 · 1999 [cited by applicant]
CN 1483133A · 2004 [cited by applicant]
CN 101177239A · 2008 [cited by applicant]
CN 105188903A · 2015 [cited by applicant]
DE 102005046746A1 · 2007 [cited by applicant]
DE 102013102969A1 · 2014 [cited by applicant]
DE 102013226126A1 · 2015 [cited by applicant]
EP 0025205A1 · 1981 [cited by applicant]
EP 2491998A1 · 2012 [cited by applicant]
EP 2955158A1 · 2015 [cited by applicant]
EP 3249027A1 · 2017 [cited by applicant]
EP 2874738B1 · 2018 [cited by applicant]
EP 3415661A1 · 2018 [cited by applicant]
EP 3472370A1 · 2019 [cited by applicant]
EP 3574991A1 · 2019 [cited by applicant]
GB 0722025A · 1955 [cited by applicant]
GB 0915444A · 1963 [cited by applicant]
GB 1269311A · 1972 [cited by applicant]
GB 1338352A · 1973 [cited by applicant]
GB 2358148A · 2001 [cited by applicant]
JP S5218485A · 1977 [cited by applicant]
JP H56120U · 1993 [cited by applicant]
JP 2002201002A · 2002 [cited by applicant]
JP 2003226657A · 2003 [cited by applicant]
JP 2003320254A · 2003 [cited by applicant]
JP 2008001584A · 2008 [cited by applicant]
JP 2010195642A · 2010 [cited by applicant]
JP 2014152219A · 2014 [cited by applicant]
KR 1020090068427A · 2009 [cited by applicant]
KR 1020180075285A · 2018 [cited by applicant]
WO 0076651A1 · 2000 [cited by applicant]
WO 2004091773A1 · 2004 [cited by applicant]
WO 2007048641A2 · 2007 [cited by applicant]
WO 2007088923A1 · 2007 [cited by applicant]
WO 2010004300A1 · 2010 [cited by applicant]
WO 2012084609A1 · 2012 [cited by applicant]
WO 2013131778A2 · 2013 [cited by applicant]
WO 2014099567A1 · 2014 [cited by applicant]
WO 2014154253A1 · 2014 [cited by applicant]
WO 2014180888A1 · 2014 [cited by applicant]
WO 2015014527A1 · 2015 [cited by applicant]
WO 2016091636A1 · 2016 [cited by applicant]
WO 2017014635A1 · 2017 [cited by applicant]
WO 2017036794A1 · 2017 [cited by applicant]
WO 2017186612A1 · 2017 [cited by applicant]
WO 2017186615A1 · 2017 [cited by applicant]
WO 2018206235A1 · 2018 [cited by applicant]
WO 2018228723A1 · 2018 [cited by applicant]
WO 2019104375A1 · 2019 [cited by applicant]
WO 2019110266A1 · 2019 [cited by applicant]
WO 2019110267A1 · 2019 [cited by applicant]
WO 2019110268A1 · 2019 [cited by applicant]
WO 2019228796A1 · 2019 [cited by applicant]
WO 2019228797A1 · 2019 [cited by applicant]
WO 2019228798A1 · 2019 [cited by applicant]
WO 2020008008A1 · 2020 [cited by applicant]
WO 2020035574A1 · 2020 [cited by applicant]
WO 2020208008A1 · 2020 [cited by applicant]
Aasberg-Petersen, K., et al., “Synthesis gas production for FT synthesis,” Studies in Surface Science and Catalysis, vol. 152, Chapter 4, 2004, p. 258-405, Elsevier B.V., The Netherlands. [cited by applicant]
Danish Search Report dated Mar. 27, 2020 issued by the Danish Patent and Trademark Office in Danish Patent Application No. PA 201901437. (9 pages). [cited by applicant]
Danish Search Report for Danish Application No. PA 2019 01145 dated Mar. 12, 2020 (7 pages). [cited by applicant]
Danish Search Report issued in corresponding Patent Application No. PA 2019 01434 dated May 27, 2020 (8 pages). [cited by applicant]
European Search Report dated Jul. 11, 2018, by the European Patent Office for European Application No. 18175366.6 (7 pages). [cited by applicant]
International Preliminary Report on Patentability received for PCT Patent Application No. PCT/EP2019/062423, mailed on Dec. 10, 2020, 8 pages. [cited by applicant]
International Preliminary Report on Patentability received for PCT Patent Application No. PCT/EP2019/062424, mailed on Dec. 10, 2020, 8 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2019/062423, mailed on Aug. 26, 2019, 10 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2019/062424, mailed on Jul. 26, 2019, 11 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2020/076695, mailed on Nov. 23, 2020, 11 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2020/076698, mailed on Nov. 26, 2020, 9 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2020/076700, mailed on Nov. 26, 2020, 11 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2020/076704, mailed on Nov. 26, 2020, 11 pages. [cited by applicant]
International Search Report and Written Opinion received for PCT Patent Application No. PCT/EP2020/076713, mailed on Nov. 26, 2020, 11 pages. [cited by applicant]
Search Report dated Apr. 24, 2020, issued in the Danish Patent Application No. PA201901433, 9 pages. [cited by applicant]
Search Report dated Apr. 24, 2020, issued in the Danish Patent Application No. PA201901435, 9 pages. [cited by applicant]
Search Report dated Jan. 28, 2019, issued in the Danish Patent Application No. PA201800249, 9 pages. [cited by applicant]
Wismann, Sebastian T., et al., “Electrified methane reforming: A compact approach to greener industrial hydrogen production,” Science, May 24, 2019, p. 756-759, vol. 364, American Association for the Advancement of Scie… [cited by applicant]
Xu et al., “Methane Steam Reforming, Methanation and Water-Gas Shift: I. Intrinsic Kinetics”, American Institution of Chemical Engineers Journal, vol. 35, No. 1, Jan. 1989, pp. 88-96. [cited by applicant]
Technology for Application of Industrial Control Computers, pp. 303-304, Beijing: Chemical Engineering Press, May 1982. [cited by applicant]
Introduction to Energy Chemistry, Dong Guanghua, etc., p. 124, Xuzhouo: China University of Mining and Technology Press, Sep. 2018. [cited by applicant]
U.S. Appl. No. 17/046,475 (Cited herein as US Patent Application Publication No. 2021/0171344 A1 of Jun. 10, 2021), Peter Mølgaard Mortensen, filed Oct. 9, 2020. [cited by applicant]
U.S. Appl. No. 17/054,572 (Cited herein as US Patent Application Publication No. 2021/0113983 A1 of Apr. 22, 2021), Peter Mølgaard Mortensen, filed Nov. 11, 2020. [cited by applicant]
U.S. Appl. No. 17/627,202, Peter Mølgaard Mortensen, filed Jan. 14, 2022. [cited by applicant]
U.S. Appl. No. 17/630,734, Peter Mølgaard Mortensen, filed Jan. 27, 2022. [cited by applicant]
U.S. Appl. No. 17/636,945, Peter Mølgaard Mortensen, filed Feb. 21, 2022. [cited by applicant]
U.S. Appl. No. 17/637,539, Peter Mølgaard Mortensen, filed Feb. 23, 2022. [cited by applicant]
U.S. Appl. No. 17/641,293, Peter Mølgaard Mortensen, filed Mar. 8, 2022. [cited by applicant]
Danish Search Report issued in corresponding Patent Application No. PA 2019 01324 dated May 27, 2020, 8 pages. [cited by applicant]
International Search Report (PCT/ISA/210) and Written Opinion (PCT/ISA/237) mailed on Feb. 23, 2021, by the European Patent Office as the International Searching Authority for International Application No. PCT/EP2020/08… [cited by applicant]
Keim, W., “Synthesis Gas Feedstock for Chemicals”, American Chemical Society, Jan. 1, 1987, vol. 25, No. 10, pp. 1-16. (16 pages). [cited by applicant]
Kongas, Rainer, “Review-Electrochemical CO2 Reduction for CO Production: Comparison of Low- and High-Temperature Electrolysis Technologies”, Journal of the Electrochemical Society, Feb. 14, 2020, 167:0044508. (12 pages). [cited by applicant]
Wang, Y., et al., “High temperature solid oxide H2O/Co2 co-electrolysis for syngas production”, Fuel Processing Technology, Nov. 14, 2016, vol. 161, pp. 248-258. (12 pages). [cited by applicant]
Danish Search Report for Danish Application No. PA 2019 01432 dated Mar. 27, 2020 (10 pages). [cited by applicant]
International Search Report (PCT/ISA/210) and Written Opinion (PCT/ISA/237) mailed on Nov. 27, 2020, by the European Patent Office as the International Searching Authority for International Application No. PCT/EP2020/07… [cited by applicant]
Boccuzzi, F, et al., “FTIR study of methanol decomposition on gold catalyst for fuel cells”, Journal of Power Sources, May 25, 2003, vol. 118, No. 1-2, pp. 304-310. [cited by applicant]
Zhou, L, et al., “Investigation of a novel porous anodic alumina plate for methane steam reforming: Hydrothermal stability, electrical heating possibility and reforming reactivity”, International Journal of Hydrogen Ene… [cited by applicant]
Bonis, L.J. and H.H. Hausner, Fundamental Phenomena in the Material Sciences, vol. 1: Sintering and Plastic Deformation, pp. v-101, 1964 (Year: 1964). [cited by applicant]