Process for methanol synthesis from CO2-rich syngas

Patent metadata

Field	Value
Publication number	US-12049438-B2
Application number	US-202118037312-A
Country	US
Kind code	B2
Filing date	Nov 12, 2021
Priority date	Nov 17, 2020
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

The disclosure describes a process for methanol synthesis remarkable in that it comprises the steps of (a) providing syngas (3), (b) providing at least one first catalytic composition (9) comprising at least one first methanol synthesis catalyst; (c) putting into contact said syngas (3) with said first catalytic composition (9) under first temperature conditions, to provide a first gaseous effluent (15); (d) providing at least one second catalytic composition (17) comprising at least one second methanol synthesis catalyst; (e) putting into contact at least a part of said first gaseous effluent (15) with said second catalytic composition (17), to provide a second gaseous effluent (23) and a second liquid effluent (21); (f) recovering methanol from first (15) and/or second (23) gaseous effluent. The use of a first catalytic composition (9) that comprises at least one first methanol synthesis catalyst in such a process for methanol synthesis is also described.

First claim

The invention claimed is:

1. A process for methanol synthesis characterized in that it comprises the following steps:
a) providing a syngas feedstreamcomprising hydrogen and carbon oxides, wherein the carbon oxides are selected from carbon dioxide or a mixture of carbon dioxide and carbon monoxide provided that the molar ratio of carbon dioxide over carbon monoxide in the mixture is equal to or greater than 1.0, and that said syngas feedstream comprises at least 12.0 mol % of CO 2 based on the total molar content of said syngas feedstream;
b) providing a first catalytic composition that comprises at least one first methanol synthesis catalyst;
c) putting into contact said syngas feedstream with said first catalytic composition under first reaction conditions comprising first temperature conditions, to provide a first gaseous effluent and optionally a first liquid effluent;
d) providing a second catalytic composition that comprises at least one second methanol synthesis catalyst wherein said at least one second methanol synthesis catalyst is the same or different from said one first methanol synthesis catalyst;
e) putting into contact at least a part of said first gaseous effluent with the second catalytic composition under second reaction conditions comprising second temperature conditions, to provide a second gaseous effluent and a second liquid effluent;
f) recovering methanol from one or more selected from the first gaseous effluent and the second gaseous effluent;

wherein the first temperature conditions are at least 275° C., wherein the second temperature conditions are lower than the first temperature conditions and second temperature conditions are ranging between 180° C. and 250° C.,
wherein said first gaseous effluent is subjected to a separation step before being put into contact with the second catalytic composition in step (e) to remove at least a part of methanol and water;
wherein at least a part of the second gaseous effluent is recycled to be put into contact with said first catalytic composition again.

2. The process according to claim 1 , characterized in that said syngas feedstream comprises more than at least 15.0 mol % to more than at least 20.0 mol % of CO 2 based on the total molar content of said syngas feedstream.

3. The process according to claim 1 , characterized in that the carbon oxides present in the syngas feedstream is a mixture of carbon dioxide and carbon monoxide, said mixture has a molar ratio of carbon dioxide over carbon monoxide equal to or greater than 2.0.

4. The process according to claim 1 , characterized in that the carbon oxides present in the syngas feedstream is a mixture of carbon dioxide and carbon monoxide, said mixture has a molar ratio of carbon dioxide over carbon monoxide equal to or greater than 3.0.

5. The process according to claim 1 , characterized in that the molar ratio of hydrogen to carbon dioxide in the syngas feedstream is at least 2.0.

6. The process according to claim 1 , characterized in that the first gaseous effluent comprises at least 1.0 mol % of methanol based on the total molar content of the first gaseous effluent.

7. The process according to claim 1 , characterized in that the first temperature conditions comprise a temperature ranging between 275° C. and 350° C.

8. The process according to claim 1 , characterized in that the first temperature conditions the first temperature conditions are at least 280° C.

9. The process according to claim 1 , characterized in that the first temperature conditions the first temperature conditions are at least 290° C.

10. The process according to claim 1 , characterized in that the first temperature conditions the first temperature conditions are at least 300° C.

11. The process according to claim 1 , characterized in that the at least one first methanol synthesis catalyst and the at least one second methanol synthesis catalyst are the same.

12. The process according to claim 1 , characterized in that the at least one first methanol synthesis catalyst and/or the at least one second methanol synthesis catalyst is or comprises a copper zinc oxide catalyst; wherein, the copper zinc oxide catalyst is prepared by co-precipitation.

13. The process according to claim 1 , characterized in that the at least one first methanol synthesis catalyst and/or the at least one second methanol synthesis catalyst is or comprises an indium oxide catalyst; wherein, said indium oxide catalyst comprises a promoter comprising at least one metal.

14. The process according to claim 13 , characterized in that when an indium oxide catalyst comprises a promoter comprising at least one metal, said at least one metal is selected from ruthenium, rhodium, gold, iridium, palladium, silver, osmium, platinum, copper, nickel, cobalt and any combinations thereof.

15. The process according to claim 1 , characterized in that the at least one first methanol synthesis catalyst and/or the at least one second methanol synthesis catalyst is or comprises one or more selected from an indium oxide catalyst, Cu—ZnO, Cu—ZnO/Al 2 O 3 , Cu—ZnO—Ga 2 O 3 /SiO 2 , Cu—ZnO—Al 2 O 3 /ZrO 2 , ZnO, Au/ZnO, Au/Fe 2 O 3 , Au/TiO 2 , Au/ZrO 2 , Au/La 2 O 3 , Au/ZnFe 2 O 4 , Fe 2 O 3 , Au/Fe 2 O 3 , CeO 2 , TiO 2 , ZrO 2 , La 2 O 3 , Zn/Fe 2 O 3.

16. The process according to claim 1 , characterized in that at least a part of the second gaseous effluent is recycled to be put into contact with said first catalytic composition again.

17. A method of using at least one first catalytic composition that comprises at least one first methanol synthesis catalyst in the process for methanol synthesis according to claim 1 , wherein said method is characterized in that it is performed in an installation comprising at least two reactors in series wherein
a first reactor comprises said at least one first catalytic composition, and
at least one subsequent reactor placed downstream of said first reactor comprises at least one second catalytic composition comprising at least one second methanol synthesis catalyst wherein at least one second methanol synthesis catalyst is the same or different from one first methanol synthesis catalyst;
wherein the method comprises providing a syngas feedstream comprising hydrogen and carbon oxides to the first reactor to contact said syngas feedstream with said at least first catalytic composition, wherein the carbon oxides are selected from carbon dioxide or a mixture of carbon dioxide and carbon monoxide provided that the molar ratio of carbon dioxide over carbon monoxide in the mixture is equal to or greater than 1.0; wherein said syngas feedstream comprises at least 12.0 mol % of CO 2 based on the total molar content of said syngas feedstream;
wherein the temperature within said first reactor is at least 275° C. and further wherein the second temperature conditions are lower than the first temperature conditions and second temperature conditions are ranging between 180° ° C.and 250° C.; and wherein the installation further comprises a first gas/liquid separator disposed between the first reactor and at least one subsequent reactor.

18. The method of claim 17 , characterized in that the at least one subsequent reactor comprising said at least one second catalytic composition forms at least one subsequent catalytic bed, and at least one reverse water-gas shift catalyst is introduced at the end of said one or more subsequent catalytic beds; wherein said one or more reverse water-gas shift catalysts are selected from Fe 2 O 3 , ZnNiFe 2 O 4 , Ba-Fe 3 O 3 -Al 2 O 3 -NiO, Cu-Mn sp

Assignees

• Totalenergies Onetech

Inventors

• Grasso Giacomo
• Curulla-Ferre Daniel
• Stewart Joseph

Classifications

• C07C29/154

  containing copper, silver, gold, or compounds thereof · CPC title

• C07C29/152 Primary

  characterised by the reactor used · CPC title

• B01J37/038

  to form slurries or suspensions, e.g. a washcoat · CPC title

• B01J37/035

  Precipitation on carriers · CPC title

• B01J37/0201

  Impregnation · CPC title