EP-4735168-A1 - CATALYSTS FOR REVERSE WATER-GAS SHIFT AND INTEGRATED FISCHER-TROPSCH PROCESSES

Abstract

The present disclosure relates generally to reverse water-gas shift processes, integrated Fischer-Tropsch processes, and a supported reverse water-gas shift catalyst for conducting these processes. The catalysts described herein include a support that is a cerium oxide support, a titanium oxide support, aluminum oxide support, a zirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; a promoter metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst; and optionally, at least one of platinum, palladium, or gold, present in an amount in the range of 0.05 to 10 wt%of the catalyst, based on the total weight of the catalyst.

Inventors

• GUO, Meiling
• Doskocil, Eric
• PATERSON, ALEXANDER JAMES

Assignees

• BP P.L.C.

Dates

Publication Date

20260506

Application Date

20230629

Claims (20)

1. A supported reverse water-gas shift catalyst comprising: a support that is a cerium oxide support, atitanium oxide support, an aluminum oxide support, azirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; a promoter metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst; and optionally, at least one of platinum, palladium, or gold present in an amount in the range of 0.05 to 10 wt%of the catalyst, based on the total weight of the catalyst.
2. The catalyst of claim 1, wherein the support makes up at least 70 wt%of the catalyst, on an oxide basis.
3. The catalyst of claim 1, wherein the support is a cerium oxide support.
4. The catalyst of claim 3, wherein the cerium oxide support comprises at least 90 wt%cerium oxide, on an oxide basis.
5. The catalyst of claim 1, wherein the support is a titanium oxide support.
6. The catalyst of claim 5, wherein the titanium oxide support comprises at least 90 wt%titanium oxide on an oxide basis.
7. The catalyst of claim 1, wherein the support is an aluminum oxide support or a zirconium oxide support.
8. The catalyst of claim 1, wherein the promoter metal is gallium.
9. The catalyst of claim 8, wherein gallium is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
10. The catalyst of claim 1, wherein the promoter is indium.
11. The catalyst of claim 10, wherein indium is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
12. The catalyst of claim 1, wherein the promoter metal is lanthanum.
13. The catalyst of claim 12, wherein lanthanum is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
14. The catalyst of claim 1, wherein the promoter metal is titanium.
15. The catalyst of claim 14, wherein titanium is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
16. The catalyst of claim 1, wherein the promoter metal is niobium.
17. The catalyst of claim 16, wherein niobium is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
18. The catalyst of claim 1, wherein the promoter metal is vanadium.
19. The catalyst of claim 18, wherein vanadium is present in the catalyst in an amount in the range of 2 to 20 wt%, based on the total weight of the catalyst.
20. The catalyst of claim 1, wherein the promoter metal is zirconium.

Description

CATALYSTS FOR REVERSE WATER-GAS SHIFT AND INTEGRATED FISCHER-TROPSCH PROCESSES BACKGROUND OF THE DISCLOSURE 1. Field The present disclosure relates generally to reverse water-gas shift catalysts, processes of making the same, and processes for performing reverse water-gas shift reactions. The present disclosure also relates to integrating processes for performing reverse water-gas shift reactions with processes for performing Fischer-Tropsch reactions. 2. Technical Background The reverse water-gas shift reaction (rWGS) is an advantageous route to obtain carbon monoxide from carbon dioxide for further chemical processing. The rWGS converts carbon dioxide and hydrogen to carbon monoxide and water, as shown in Equation (1) . This can be used, for example, to modify the CO: H2 ratio of a gas mixture for further processing. The carbon monoxide and hydrogen so formed is a valuable feedstock for a number of chemical processes, for example, the well-known Fischer-Tropsch (FT) process, shown in Equation (2) . However, the rWGS reaction is not favored in all circumstances. For example, acompeting reaction is the Sabatier reaction (Equation (3) ) , which decreases carbon monoxide yield in favor of methane production, which is not an active feedstock for FT. The strongly exothermic Sabatier reaction is thermodynamically favored over the endothermic rWGS reaction at lower reaction temperatures. As such, minimizing the methanation during rWGS, especially at low temperatures, can become a significant challenge. Similarly, the carbon monoxide product from rWGS can be hydrogenated to methane, as shown in Equation (4) . Hydrogenation of carbon monoxide to methane is also an exothermic reaction, so it too is favored at lower temperatures. The stoichiometry of the reaction requires at least a 3: 1 ratio  of hydrogen to carbon monoxide. This means that performing the rWGS reaction with a large excess of hydrogen to drive the equilibrium toward carbon monoxide (see Equation (1)) is not always ideal because it runs the risk of hydrogenating the carbon monoxide product to form methane. Coupled with Equations (3) and (4) , further undesirable side reactions can occur. These side reactions can form undesirable carbon deposits on the surface of catalysts used to promote rWGS. Examples of these carbon-producing side reactions are shown in Equations (5) , (6) , and (7) . All three of these reactions are endothermic and are favored at higher temperatures, just like the rWGS reaction. Accordingly, because the carbon-producing side reactions (Equations (5) - (7) ) are also endothermic and are favored at higher temperatures, operation at higher temperatures to favor the desired carbon monoxide product can severely impact catalyst lifetime through the deposition of carbon. Given the multiple reactions and competing thermodynamics at play, there remains a need in the art for new rWGS catalysts and processes, especially for integration with Fischer-Tropsch processes. SUMMARY In one aspect, the present disclosure provides for a supported reverse water-gas shift catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; a promoter metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst; and optionally, at least one of platinum, palladium, or gold present in an amount in the range of 0.05 to 10 wt%of the catalyst, based on the total weight of the catalyst. In one aspect, the present disclosure provides for a supported reverse water-gas shift catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; a promoter metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst; and at least one of platinum, palladium, or gold present in an amount in the range of 0.05 to 10 wt%of the catalyst, based on the total weight of the catalyst. In another aspect, the present disclosure provides for a method of making the catalyst as described herein, the method comprising: providing a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide; contacting the support with one or more liquids each comprising one or more promoter metal-contain