Palladium, platinum and gold catalysts and integrated fischer-tropsch process for reverse water gas shift

Abstract

The present disclosure relates generally to reverse water gas shift processes, integrated Fischer-Tropsch processes, and supported reverse water gas shift catalysts for performing these processes. The catalyst described herein comprises a support which is a ceria support, a titanium oxide support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titanium oxide, alumina, and zirconia; at least one of platinum, palladium and gold present in an amount ranging from 0.05 to 10 wt% of the catalyst, based on the total weight of the catalyst; and manganese present in an amount ranging from 0.5 to 20 wt% of the catalyst, based on the total weight of the catalyst.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to International Patent Application Nos. PCT / CN2022 / 102685 filed on June 30, 2022, PCT / CN2022 / 102763 filed on June 30, 2022, PCT / CN2022 / 102976 filed on June 30, 2022, and PCT / CN2022 / 102812 filed on June 30, 2022, each of which is hereby incorporated by reference in its entirety.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] 1. Field

[0005] The present disclosure generally relates to reverse water gas shift catalysts, methods of making the same, and methods of performing the reverse water gas shift reaction. The present disclosure also relates to integrating the method of performing the reverse water gas shift reaction with the method of performing the Fischer-Tropsch reaction. 2. Technical Background

[0006] The reverse water gas shift reaction (rWGS) is a favorable route to obtain carbon monoxide from carbon dioxide for further chemical processing. rWGS converts carbon dioxide and hydrogen into carbon monoxide and water, as shown in reaction equation (1).

[0007] ΔH 0 298 =42.1 kJmol -1 Reaction (1)

[0008] This can be used, for example, to change the CO:H ratio of a gas mixture. 2 The carbon monoxide and hydrogen thus formed are valuable raw materials for many chemical processes, for example, the well-known Fischer-Tropsch (FT) process as shown in reaction equation (2).

[0009] ΔH 0 298 =-152 kJmol -1 Reaction (2)

[0010] However, the rWGS reaction is not dominant in all cases. For example, the competing reaction is the Sabatier reaction (Equation (3)), which reduces the carbon monoxide yield and favors the production of methane, which is not an active feedstock for FT.

[0011] ΔH 0 298 =-165 kJmol -1Reaction (3)

[0012] At lower reaction temperatures, the strongly exothermic Sabatier reaction is thermodynamically preferred over the endothermic rWGS reaction. Therefore, minimizing methanogenesis during rWGS processes, especially at low temperatures, can be a significant challenge.

[0013] Similarly, the carbon monoxide product from rWGS can be hydrogenated to methane as shown in reaction (4).

[0014] ΔH 0 298 =-206.5 kJmol -1 Reaction (4)

[0015] The hydrogenation of carbon monoxide to methane is also an exothermic reaction and therefore also predominates at lower temperatures. The stoichiometry of the reaction requires a hydrogen to carbon monoxide ratio of at least 3:1. This means that it is not always desirable to carry out the rWGS reaction with a large excess of hydrogen to drive the equilibrium towards carbon monoxide (see reaction (1)) because it risks hydrogenating the carbon monoxide product to form methane.

[0016] In combination with reactions (3) and (4), further undesirable side reactions may occur. These side reactions may form undesirable carbon deposits on the surface of the catalyst used to promote rWGS. Examples of these carbon-producing side reactions are shown in reactions (5), (6) and (7). All three reactions are endothermic and are dominant at higher temperatures, just like the rWGS reaction.

[0017] ΔH 0 298 =131 kJmol -1 Reaction (5)

[0018] ΔH 0 298 =75 kJmol -1 Reaction (6)

[0019] ΔH 0 298 =171 kJmol -1 Reaction (7)

[0020] Therefore, because the carbon-producing side reactions (Equations (5)-(7)) are also endothermic and are favored at higher temperatures, operating at higher temperatures to favor the desired carbon monoxide product may severely affect catalyst life through carbon deposition.

[0021] Given the multiple reactions at play and the competing thermodynamics, there remains a need in the art for new rWGS catalysts and methods, especially rWGS catalysts and methods integrated with the Fischer-Tropsch process. SUMMARY OF THE INVENTION

[0023] In one aspect, the present disclosure provides a supported reverse water gas shift catalyst comprising:

[0024] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0025] at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0026] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0027] In another aspect, the present disclosure provides a method of making a catalyst as described herein, the method comprising:

[0028] A carrier is provided, wherein the carrier is a cerium oxide carrier, a titanium oxide carrier, an aluminum oxide carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;

[0029] contacting the support with a liquid comprising one or more compounds containing platinum, palladium or gold and one or more compounds containing manganese dispersed in a solvent;

[0030] allowing the solvent to evaporate to provide a catalyst precursor; and

[0031] The catalyst precursor is calcined.

[0032] In another aspect, the present disclosure provides a catalyst as described herein, made by a method as described herein.

[0033] In another aspect, the present disclosure provides a method of performing a reverse water gas shift reaction, the method comprising reacting a catalyst as described herein with a mixture comprising CO at a temperature in the range of 200-900°C. 2 and H 2 The feed stream is contacted to provide a 2 A product stream having a lower concentration of CO than the feed stream 2 and higher concentrations of CO.

[0034] In one aspect, the present disclosure provides a method of performing an integrated Fischer-Tropsch process, the method comprising:

[0035] Provides H 2 and CO 2 a first feed stream of

[0036] Contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a gas comprising CO and H 2 A first product stream having a lower concentration of CO than the first feed stream 2 and higher concentrations of CO;

[0037] The Fischer-Tropsch catalyst is mixed with a mixture comprising H at a second temperature and a second pressure. 2 and contacting a second feed stream of CO from at least a portion of the first product stream to provide a feed stream comprising C 5+ a second product stream of hydrocarbons,

[0038] The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising:

[0039] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0040] at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0041] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0042] BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The accompanying drawings are included to provide a further understanding of the method of the present disclosure, and are incorporated into and constitute a part of this specification. The drawings are not necessarily drawn to scale, and the dimensions of various elements may be distorted for clarity. The accompanying drawings illustrate one or more embodiments of the present disclosure and, together with the description, serve to explain the principles and operations of the present disclosure.

[0044] Figure 1 is a schematic diagram of the reverse water gas shift reaction as described herein.

[0045] Figure 2 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0046] Figure 3 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0047] Figure 4 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0048] Figure 5 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0049] Figure 6 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0050] Figure 7 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0051] Figure 8 is a graph of carbon dioxide conversion for rWGS catalysts as described herein.

[0052] Fig. 9 is a graph of the carbon molar selectivity to methane for rWGS catalysts as described herein.

[0053] Fig.10 is a graph of carbon dioxide conversion for rWGS catalysts as described herein.

[0054] Fig.11 is a graph of conversion of carbon molar selectivity to methane for rWGS catalysts as described herein.

[0055] Fig.12 is a graph of carbon dioxide conversion for rWGS catalysts as described herein.

[0056] Fig.13 is a graph of conversion of carbon molar selectivity to methane for rWGS catalysts as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0058] As described above, the reverse water gas shift reaction reacts carbon dioxide with hydrogen to form carbon monoxide and water, and can be used to provide a feedstock containing carbon monoxide and hydrogen, commonly referred to as "syngas", for use in processes such as the Fischer-Tropsch process. However, the Sabatier reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction. The Sabatier reaction and CO methanation are exothermic and are dominant at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and are dominant at higher temperatures. Therefore, despite these complications, there is still a need for rWGS catalysts that can provide good performance. Here, the inventors have provided a supported reverse water gas shift catalyst comprising a metal oxide support, at least one of platinum, palladium and gold, and manganese, which can meet the requirements required for a commercially available rWGS method. In addition, the inventors have found that the rWGS method is particularly advantageous for integration with the Fischer-Tropsch process by using a supported reverse water gas shift catalyst, the supported reverse water gas shift catalyst comprising a metal oxide support, at least one of platinum, palladium and gold, and manganese.

[0059] Reverse Water Gas Shift Catalyst

[0060] In one aspect, the present disclosure provides a supported reverse water gas shift catalyst, for example, for use in a rWGS process integrated with a FT process. The supported reverse water gas shift catalyst comprises a carrier, which is a cerium oxide carrier, a titanium oxide carrier, an aluminum oxide carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; at least one of platinum, palladium, and 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; and manganese, present in an amount in the range of 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0061] As described above, the reverse water gas shift catalyst of the present disclosure is a supported catalyst. In various embodiments described elsewhere herein, the support constitutes at least 70 wt %, such as at least 75 wt %, or 80 wt %, or 85 wt %, or 90 wt % of the catalyst, based on oxide.

[0062] In various embodiments as described separately herein, the carrier is a cerium oxide carrier. As used herein, a "cerium oxide" carrier is a carrier presenting at least a surface layer (e.g., a thickness of 50 microns) of cerium oxide calculated as at least 50% by weight based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the cerium oxide carrier comprises at least 60% by weight of cerium oxide, such as at least 70% by weight of cerium oxide or at least 80% by weight of cerium oxide. In some such embodiments, at least the surface layer of the cerium oxide carrier comprises at least 90% by weight of cerium oxide. For example, in some embodiments, at least the surface layer of the cerium oxide carrier comprises at least 95% by weight of cerium oxide or at least 98% by weight of cerium oxide. In various examples, the cerium oxide carrier contains substantially distributed cerium oxide, such as based on oxide, at least 50% by weight of the cerium oxide carrier is cerium oxide. For example, in various embodiments, the cerium oxide carrier comprises at least 60% by weight of cerium oxide, such as at least 70% by weight of cerium oxide or at least 80% by weight of cerium oxide. In various embodiments, the ceria support comprises at least 90 wt% ceria, such as at least 95 wt% ceria, or at least 98 wt% ceria. In some embodiments, the ceria support may further comprise additional metals or metal oxides.

[0063] In various embodiments as described elsewhere herein, the carrier is a titanium oxide carrier. As used herein, a "titania" carrier is a carrier that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% titanium oxide based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the titanium oxide carrier comprises at least 60% titanium oxide, such as at least 70% titanium oxide, or at least 80% titanium oxide. In some such embodiments, at least the surface layer of the titanium oxide carrier comprises at least 90% titanium oxide. For example, in some embodiments, at least the surface layer of the titanium oxide carrier comprises at least 95% titanium oxide or at least 98% titanium oxide. In various examples, the titanium oxide carrier contains substantially distributed titanium oxide, such as based on oxide, at least 50% by weight of the titanium oxide carrier is titanium oxide. For example, in various embodiments, the titanium oxide carrier comprises at least 60% titanium oxide, such as at least 70% titanium oxide, or at least 80% titanium oxide. In various embodiments, the titania support comprises at least 90 wt% titania, such as at least 95 wt% titania, or at least 98 wt% titania. In some embodiments, the titania support may further comprise additional metals or metal oxides.

[0064] In various embodiments as described elsewhere herein, the support is an alumina support. As used herein, an "alumina" support is a support that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% by weight of alumina based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the alumina support comprises at least 60% by weight of alumina, such as at least 70% by weight of alumina, or at least 80% by weight of alumina. In some such embodiments, at least the surface layer of the alumina support comprises at least 90% by weight of alumina. For example, in some embodiments, at least the surface layer of the alumina support comprises at least 95% by weight of alumina or at least 98% by weight of alumina. In various examples, the alumina support contains substantially distributed alumina, such as at least 50% by weight of the alumina support is alumina based on oxide. For example, in various embodiments, the alumina support comprises at least 60% by weight of alumina, such as at least 70% by weight of alumina, or at least 80% by weight of alumina. In various embodiments, the alumina support comprises at least 90 wt% alumina, such as at least 95 wt% alumina, or at least 98 wt% alumina. In some embodiments, the alumina support may further comprise additional metals or metal oxides.

[0065] In various embodiments as described elsewhere herein, the carrier is a zirconia carrier. As used herein, a "zirconia" carrier is a carrier that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% zirconia based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the zirconia carrier comprises at least 60% zirconia, such as at least 70% zirconia, or at least 80% zirconia. In some such embodiments, at least the surface layer of the zirconia carrier comprises at least 90% zirconia. For example, in some embodiments, at least the surface layer of the zirconia carrier comprises at least 95% zirconia or at least 98% zirconia. In various examples, the zirconia carrier contains substantially distributed zirconia, such as at least 50% zirconia based on oxide. For example, in various embodiments, the zirconia carrier comprises at least 60% zirconia, such as at least 70% zirconia, or at least 80% zirconia. In various embodiments, the zirconia support comprises at least 90 wt% zirconia, such as at least 95 wt% zirconia, or at least 98 wt% zirconia. In some embodiments, the zirconia support may further comprise additional metals or metal oxides.

[0066] In various embodiments as described separately herein, the carrier is a mixed oxide carrier. These can be provided, for example, by admixing a variety of the above-mentioned oxides and being formed into a carrier comprising both. For example, in some embodiments, the mixed oxide carrier is a mixture of two or more metal oxides such as cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. In some embodiments, based on oxide, at least the surface layer of the carrier comprises a total of at least 50% by weight of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. In some embodiments, at least the surface layer of the mixed oxide carrier comprises a total of at least 60% by weight, for example, at least 70% by weight or at least 80% by weight of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. In some embodiments, at least the surface layer of the mixed oxide carrier comprises at least 90% by weight, for example, at least 95% by weight or at least 98% by weight of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. In various examples, the mixed oxide carrier contains oxides that are substantially distributed, for example, at least 50% by weight of the mixed oxide carrier is two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide. In various embodiments, the mixed oxide support comprises a total of at least 60 wt%, such as at least 70 wt%, or at least 80 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide. In various embodiments, the mixed oxide support comprises a total of at least 90 wt%, such as at least 95 wt%, or at least 98 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide. In some embodiments, the mixed oxide support may further comprise additional metals or metal oxides.

[0067] The inventors have discovered that cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide can provide good performance in the absence of significant amounts of other metals in the support. For example, in various embodiments of the present disclosure as described elsewhere herein, the support does not contain more than 2 wt. %, such as more than 1 wt. %, or more than 0.5 wt. % of the total amount of the additional metal, based on the oxide.

[0068] However, the inventors have noted that in many cases, performance can be desirably affected by including other metals in the support. Therefore, in other embodiments as described elsewhere herein, the support includes at least one additional metal. In various embodiments, the total amount of at least one additional metal is in the range of 0.5-20 wt %, such as 1-20 wt %, or 2-20 wt %, or 0.5-15 wt %, or 1-15 wt %, or 2-15 wt %, or 0.5-10 wt %, or 1-10 wt %, or 2-10 wt %, or 0.5-5 wt %, or 1-5 wt %, based on the oxide.

[0069] The carrier suitable for use herein can be provided with a certain range of pore volume. One of ordinary skill in the art will select a pore volume suitable for the desired catalytic method. For example, in various embodiments as described separately herein, the pore volume is at least 0.05 mL / g, for example at least 0.1 mL / g. In various embodiments as described separately herein, the pore volume is at most 1.5 mL / g, for example at most 1 mL / g. In various embodiments of the disclosure as described herein, the pore volume is in the range of 0.05-1.5 mL / g, for example 0.1 mL / g to 1 mL / g. The pore volume is measured by mercury porosimetry, for example as measured according to ASTM D4284-12.

[0070] As described above, the supported reverse water gas shift catalyst of the present disclosure comprises at least one of platinum, palladium and gold. For example, in various embodiments as described elsewhere herein, platinum is present in the catalyst. For the purposes of the present disclosure, the amount of platinum present is calculated as the weight percentage of platinum atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which the platinum may be present. Platinum can be present in the catalyst in various forms; most commonly, platinum is present primarily as a metal, a metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, platinum is present in the catalyst in an amount ranging from 0.05 to 10 weight %, for example, in a range of 0.1 to 10 weight %, or 0.5 to 10 weight %, 1 to 10 weight %, or 2 to 10 weight %, or 5 to 10 weight %, based on the total weight of the catalyst. For example, in some embodiments, platinum is present in the catalyst in an amount ranging from 0.05 to 7 wt %, such as 0.1 to 7 wt %, or 0.5 to 7 wt %, or 1 to 7 wt %, or 2 to 7 wt %, based on the total weight of the catalyst. In some embodiments, platinum is present in the catalyst in an amount ranging from 0.05 to 5 wt %, such as 0.1 to 5 wt %, or 0.5 to 5 wt %, or 1 to 5 wt %, or 2 to 5 wt %, based on the total weight of the catalyst. For example, in some embodiments of the present disclosure as described herein, platinum is present in the catalyst in an amount ranging from 0.05 to 2 wt %, such as 0.1 to 2 wt %, or 0.3 to 2 wt %, or 0.5 to 2 wt %, based on the total weight of the catalyst. In some embodiments, platinum is present in the catalyst in an amount of 0.05 to 1.5 wt %, such as 0.1 to 1.5 wt %, or 0.3 to 1.5 wt %, or 0.5 to 1.5 wt %, based on the total weight of the catalyst. In some embodiments, platinum is present in an amount in the range of 0.05 to 1 wt %, such as 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst. In some embodiments, platinum is present in an amount in the range of 0.05 to 0.8 wt %, such as 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0071] In various embodiments as described elsewhere herein, palladium is present in the catalyst. For the purposes of the present disclosure, the amount of palladium present is calculated as the weight percentage of palladium atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which the palladium may be present. Palladium can be present in the catalyst in various forms; most commonly, palladium is present primarily as a metal, a metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, palladium is present in the catalyst in an amount ranging from 0.05 to 10% by weight, such as from 0.1 to 10% by weight, or from 0.5 to 10% by weight, 1 to 10% by weight, or from 2 to 10% by weight, or from 5 to 10% by weight, based on the total weight of the catalyst. For example, in some embodiments, palladium is present in the catalyst in an amount ranging from 0.05 to 7% by weight, such as from 0.1 to 7% by weight, or from 0.5 to 7% by weight, or from 1 to 7% by weight, or from 2 to 7% by weight, based on the total weight of the catalyst. In some embodiments, palladium is present in the catalyst in an amount ranging from 0.05 to 5 wt %, for example, from 0.1 to 5 wt %, or from 0.5 to 5 wt %, or from 1 to 5 wt %, or from 2 to 5 wt %, based on the total weight of the catalyst. For example, in some embodiments of the disclosure as described herein, palladium is present in the catalyst in an amount ranging from 0.05 to 2 wt %, for example, from 0.1 to 2 wt %, or from 0.3 to 2 wt %, or from 0.5 to 2 wt %, based on the total weight of the catalyst. In some embodiments, palladium is present in the catalyst in an amount ranging from 0.05 to 1.5 wt %, for example, from 0.1 to 1.5 wt %, or from 0.3 to 1.5 wt %, or from 0.5 to 1.5 wt %, based on the total weight of the catalyst. In some embodiments, palladium is present in an amount ranging from 0.05 to 1 wt %, such as 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst. In some embodiments, palladium is present in an amount ranging from 0.05 to 0.8 wt %, such as 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0072] For example, in various embodiments as described elsewhere herein, gold is present in the catalyst. For the purposes of the present disclosure, the amount of gold present is calculated as the weight percentage of gold atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which the gold may be present. Gold can be present in the catalyst in various forms; most commonly, gold is present primarily as a metal, a metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, gold is present in the catalyst in an amount ranging from 0.05 to 10% by weight, such as from 0.1 to 10% by weight, or from 0.5 to 10% by weight, 1 to 10% by weight, or from 2 to 10% by weight, or from 5 to 10% by weight, based on the total weight of the catalyst. For example, in some embodiments, gold is present in the catalyst in an amount ranging from 0.05 to 7% by weight, such as from 0.1 to 7% by weight, or from 0.5 to 7% by weight, or from 1 to 7% by weight, or from 2 to 7% by weight, based on the total weight of the catalyst. In some embodiments, gold is present in the catalyst in an amount ranging from 0.05 to 5 wt %, such as 0.1 to 5 wt %, or 0.5 to 5 wt %, or 1 to 5 wt %, or 2 to 5 wt %, based on the total weight of the catalyst. For example, in some embodiments of the disclosure as described herein, gold is present in the catalyst in an amount ranging from 0.05 to 2 wt %, such as 0.1 to 2 wt %, or 0.3 to 2 wt %, or 0.5 to 2 wt %, based on the total weight of the catalyst. In some embodiments, gold is present in the catalyst in an amount ranging from 0.05 to 1.5 wt %, such as 0.1 to 1.5 wt %, or 0.3 to 1.5 wt %, or 0.5 to 1.5 wt %, based on the total weight of the catalyst. In some embodiments, gold is present in an amount ranging from 0.05 to 1 wt %, such as 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst. In some embodiments, gold is present in an amount ranging from 0.05 to 0.8 wt %, such as 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0073] As described above, the supported reverse water gas shift catalyst of the present disclosure also includes manganese. The inventors have determined that including manganese in the catalyst can provide improved performance, as described in the following examples. For the purposes of the present disclosure, the amount of manganese present is calculated as the weight percentage of manganese atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which manganese may be present. Manganese can be present in the catalyst in various forms; most commonly, manganese is present primarily as a metal oxide, a metal, or a combination thereof. In various embodiments of the present disclosure as described elsewhere herein, manganese is present in the catalyst in an amount ranging from 0.5 to 20 weight %, based on the total weight of the catalyst. For example, in various embodiments, manganese is present in the catalyst in an amount ranging from 0.5 to 15 weight %, or 0.5 to 12 weight %, or 0.5 to 10 weight %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in the catalyst in an amount ranging from 1 to 20 wt %, for example, 1 to 15 wt %, or 1 to 12 wt %, or 1 to 10 wt %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in an amount ranging from 2 to 20 wt %, for example, 2 to 15 wt %, or 2 to 12 wt %, or 2 to 10 wt %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in an amount ranging from 4 to 20 wt %, for example, 4 to 15 wt %, or 4 to 12 wt %, or 4 to 10 wt %, based on the total weight of the catalyst.

[0074] Platinum, palladium and / or gold and manganese can be provided in various weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of platinum, palladium and / or gold to manganese present in the catalyst is at least 0.05:1. For example, in various embodiments, the weight ratio of platinum, palladium and / or gold to manganese is at least 0.1:1. In various embodiments of the present disclosure as described herein, the weight ratio of platinum, palladium and / or gold to manganese present in the catalyst is at most 1:1. For example, the weight ratio of platinum, palladium and / or gold to manganese is at most 0.5:1. For example, in various embodiments, the weight ratio of platinum, palladium and / or gold to manganese present in the catalyst is in the range of 0.05:1 to 1:1. For example, the weight ratio of platinum, palladium and / or gold to manganese ranges from 0.05:1 to 0.5:1, or 0.05:1 to 0.3:1, or 0.07:1 to 1:1, or 0.07:1 to 0.5:1, or 0.07:1 to 0.3:1, or 0.1:1 to 1:1, or 0.1:1 to 0.5:1, or 0.1:1 to 0.3:1.

[0075] The inventors have determined that suitable reverse water gas shift catalysts can be formed by one or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide as carriers and platinum, palladium and / or gold combined with manganese contained in / on the catalyst. As will be understood by those of ordinary skill in the art, the amount of cerium, titanium, aluminum, zirconium, platinum, palladium, gold and manganese can be quantified based on metals, regardless of the form in which these metals may exist. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of the metal in the catalyst (i.e., based on metal), without including oxygen or non-metallic counterions in the calculation. Therefore, in various embodiments of the present disclosure as described herein, based on metal, the total amount of cerium, titanium, aluminum, zirconium, manganese, platinum, palladium and gold in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight or at least 98% by weight. For example, in some specific embodiments, based on metal, the total amount of cerium, manganese, platinum, palladium and gold in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight or at least 98% by weight. In other embodiments, the total amount of titanium, manganese, platinum, palladium and gold in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight, or at least 98% by weight, based on the metal. In other embodiments, the total amount of aluminum, manganese, platinum, palladium and gold in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight, or at least 98% by weight, based on the metal. In other embodiments, the total amount of zirconium, manganese, platinum, palladium and gold in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight, or at least 98% by weight, based on the metal.

[0076] As described above, the catalyst as described herein is mainly composed of cerium, titanium, aluminum, zirconium, manganese, platinum, palladium and / or gold. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has an additional metal content of no more than 10% by weight. The additional metal can be any metal other than platinum, palladium, gold, manganese, cerium, titanium, aluminum or zirconium. For example, the additional metal can be selected from alkali metals, alkaline earth metals, rare earth metals, coin metals or other transition metals. For example, in various embodiments, based on the total weight of the catalyst, the catalyst has an additional metal content of no more than 5% by weight, or no more than 2% by weight, or no more than 1% by weight. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has a copper content of no more than 10% by weight. For example, in various embodiments, based on the total weight of the catalyst, the catalyst has a copper content of no more than 5% by weight, or no more than 2% by weight, or no more than 1% by weight. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has an alkali metal content of no more than 10% by weight. For example, in various embodiments, the catalyst has an alkali metal content of no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has an alkaline earth metal content of no more than 10 wt %, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has an alkaline earth metal content of no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, based on the total weight of the catalyst.

[0077] As described above, the supported catalyst comprises manganese and at least one of platinum, palladium and gold. Depending on the synthesis method, these species, which are usually present mainly in metallic form and / or oxide form, can be disposed at various different locations on the support. For example, they can be found in the pores of the support and on the outer surface of the support. They can be found substantially throughout the support, such as when a large amount of impregnation liquid is used, or only in the surface layer of the support, such as when the impregnation liquid does not penetrate into the entire support, such as when the incipient wetness impregnation technique is used.

[0078] Without intending to be bound by theory, it is believed that the active forms of platinum, palladium and gold are generally in substantially metallic form. As described below, since platinum, palladium and gold may exist substantially in oxide form after catalyst preparation and during transportation and storage, it is generally desirable to activate the catalyst by contacting the catalyst with a reducing agent (e.g., hydrogen gas) so as to convert most of such oxides into metallic form. However, one of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a variety of palladium, platinum and gold forms in its catalysts, as these forms may be active or may be conveniently converted into active forms.

[0079] After catalyst preparation and during transportation and storage, manganese will generally be provided in the form of oxides. Without intending to be bound by theory, the inventors believe that manganese improves the catalytic activity of supported platinum, palladium and / or gold catalysts by reducing CO methanation (which affects CO selectivity) that may occur within a typical reverse water gas shift reaction temperature range. The inventors believe that the improved activity can be attributed to the interfacing of manganese with platinum, palladium and / or gold and a carrier (e.g., cerium oxide, titanium oxide, aluminum oxide, zirconium oxide or mixed oxide). The inventors envision that during the activation process of platinum, palladium and / or gold species, some manganese oxides can be converted into metallic forms. However, it will be appreciated by those of ordinary skill in the art that the present disclosure contemplates the usefulness of a variety of manganese forms in its catalyst, because these manganese forms can provide a promoting effect or can be easily converted into a form that will have a promoting effect.

[0080] Those of ordinary skill in the art will appreciate that the catalyst of the present disclosure can be provided in many forms, particularly depending on the specific form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The carrier itself can be provided as a discrete body of material, for example as a porous particle, a pellet or a shaped extrudate, wherein platinum, palladium and / or gold and manganese are arranged thereon to provide the catalyst. However, in other embodiments, the catalyst of the present disclosure itself can be formed as a layer on the substrate below. The substrate below is not particularly limited. It can be formed by, for example, a metal or a metal oxide, and itself can be provided in various forms, such as particles, pellets, shaped extrudates or monoliths. Those of ordinary skill in the art can, for example, use coating or other molding techniques to provide a carrier layer on a substrate, followed by the addition of platinum, palladium and / or gold and manganese.

[0081] Another aspect of the present disclosure provides a method for making a catalyst as described herein. As described above, the method includes providing a support, the support being 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; contacting the support with one or more liquids, each of the one or more liquids comprising one or more compounds containing platinum, palladium, or gold and / or one or more compounds containing manganese dispersed in a solvent; allowing the solvent to evaporate to provide a catalyst precursor; and calcining the catalyst precursor. Of course, one of ordinary skill in the art will appreciate that other methods may be used to make the catalyst as described herein.

[0082] In some embodiments of the disclosure as described herein, contacting the carrier with the liquid comprises adding the liquid in an amount approximately equal to the pore volume of the carrier (i.e., within 25% thereof, or within 10% thereof). In other embodiments, contacting the carrier with the liquid comprises adding the liquid in an amount greater than the pore volume of the carrier. For example, in some embodiments, the ratio of the amount of liquid to the amount of carrier on a mass basis is in the range of 0.75:1 to 5:1, such as in the range of 0.9:1 to 3:1. In some embodiments, contacting the carrier with the liquid provides a slurry.

[0083] In various embodiments of the present disclosure as described herein, solvent evaporation is allowed to proceed at ambient temperature. In various embodiments, solvent evaporation is allowed to proceed for a drying time at an elevated temperature. One of ordinary skill in the art will be able to select appropriate equipment or instruments to allow solvent evaporation, and such equipment or instruments are not particularly limited. In addition, one of ordinary skill in the art will appreciate that the elevated temperature at which solvent evaporation is allowed depends on the boiling point of the solvent. Therefore, one of ordinary skill in the art will be able to select an appropriate elevated temperature. For example, in some embodiments, the elevated temperature is in the range of 50-150° C., for example, in the range of 50-120° C., or 50-100° C., or 100-150° C., or 100-120° C. In some embodiments, the drying time is in the range of 1 to 48 hours, for example, in the range of 10 to 36 hours, or 12 to 24 hours. For example, in a particular embodiment, the drying time is about 24 hours. In some embodiments, solvent evaporation is allowed to proceed for a drying time at a vacuum and elevated temperature, as described herein. In some embodiments, the solvent is allowed to evaporate at elevated temperature, for example in the range of 30-100°C in a stirred dry bath.

[0084] In some embodiments of the present disclosure as described herein, the calcined catalyst precursor is subjected to a calcination time in a furnace at a calcination temperature. For example, in some embodiments, the calcination time is in the range of 0.5 to 24 hours, or 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours. In some embodiments, the calcination temperature is in the range of 100-600° C., such as in the range of 120-500° C.

[0085] As described above, the method for manufacturing a catalyst as described herein includes contacting a carrier with one or more liquids, each of which includes one or more compounds containing platinum, palladium or gold and / or one or more compounds containing manganese dispersed in a solvent. The compound containing platinum, palladium, gold and manganese is not particularly limited, and a person of ordinary skill in the art will be able to select a suitable compound soluble in a solvent. For example, in some embodiments of the disclosure as described herein, the compound containing platinum, palladium, gold and manganese can be selected from metal salts (such as nitrates and acetates). The solvent is also not particularly limited, and a person of ordinary skill in the art will be able to select a suitable solvent that can be absorbed by the carrier. For example, in some embodiments of the disclosure as described herein, the solvent is water. As will be understood by a person of ordinary skill in the art, these metal species are conveniently provided in the same liquid, so that only a step of contacting the carrier with the liquid is required. However, other schemes are also possible.

[0086] In another aspect, the present disclosure provides a catalyst as described herein prepared by a method as described herein.

[0087] Reverse Water Gas Shift Reaction

[0088] Another aspect of the present invention provides a method for performing a reverse water gas shift reaction. As described above, the method comprises reacting a catalyst as described herein with a mixture containing CO at a temperature in the range of 200-900°C. 2 and H 2 The feed stream is contacted to provide a 2 A product stream having a lower concentration of CO than the feed stream 2 and higher concentrations of CO. Figure 1 An example of such a method is shown schematically in Figure 1 In the method 100 herein, the method comprises providing a reaction zone, such as a reactor 110, with a mixture containing H 2 and CO 2 The reverse water gas shift reaction is carried out by reacting a feed stream 111 of CO. As described herein, the reverse water gas shift catalyst 113 is contacted with the feed stream 111 at a temperature in the range of 200-900° C. to provide a feed stream comprising CO and H. 2 The product stream 112 has a lower concentration of CO than the feed stream. 2 and higher concentrations of CO.

[0089] As used herein, "feed stream" is used to refer to the total material input to a process step, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single inlet or through multiple inlets. For example, the H of a feed stream 2The CO and CO can be in a single physical stream (e.g., in a single conduit to reactor 110) or in multiple physical streams (e.g., for CO and H 2 Separate inlet for fresh CO and H 2 an inlet for recirculating CO and / or H 2 Similarly, "product stream" is used to refer to the total material output from a process step, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single outlet or through multiple outlets.

[0090] In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO selectivity of at least 95%, for example, or at least 96%. As used herein, the "selectivity" for a given reaction product is the amount of feed (here, CO) converted to the product (CO for "CO selectivity"). 2 ). The inventors have determined that the catalysts of the present invention can provide excellent CO selectivity even when operated at lower temperatures than many conventional reverse water gas shift catalysts, despite the competing potential of the Sabatier reaction and CO methanation. For example, in some embodiments as described elsewhere herein, the reverse water gas shift reaction has a CO selectivity of at least 98%, for example, or at least 99%.

[0091] It is noteworthy that even at relatively low temperatures in the range of 200-900°C, the catalysts described herein can be operated to provide carbon monoxide with only a minimal degree of methane formation. For example, in various embodiments of the present disclosure as otherwise described herein, the reverse water gas shift reaction has a methane selectivity of no more than 5%, such as no more than 4%. For example, in some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 2%, such as no more than 1%. In some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, such as no more than 0.2%.

[0092] The inventors have determined that the catalysts described herein can provide desirably high CO selectivity and desirably low methane selectivity at commercially relevant conversions. "Conversion" as used herein is the mole fraction of the feed that is reacted (whether reacted to desirable products or undesirable species). In various embodiments of the disclosure as described herein, the reverse water gas shift reaction has a CO conversion of at least 5%, e.g., at least 10%, or 20%. 2 For example, in some embodiments, the reverse water gas shift reaction has a CO conversion of at least 30%, such as at least 40%, or 50%, or 60%. 2In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO conversion rate of no more than 90%, such as no more than 80% or no more than 70%. 2 For example, in some embodiments, the reverse water gas shift reaction has a CO conversion rate of no more than 65%, such as no more than 60%. 2 For example, in various embodiments as described elsewhere herein, CO 2 The conversion rate is in the range of 10-90%, such as 10-80%, or 10-70%, or 10-60%, or 10-65%, or 20-90%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30-90%, or 30-80%, or 30-70%, or 30-60%, or 30-65%, or 40-90%, or 40-80%, or 40-70%, or 40-60%, or 40-65%. Based on the disclosure herein, one of ordinary skill in the art will operate at a conversion level that provides a desired product. Of course, in other embodiments, such as when in a stacked bed or mixed bed system, the CO 2 The conversion rates can be even higher than those described here.

[0093] Advantageously, the methods described herein can be carried out at temperatures lower than those used in many conventional reverse water gas shift methods. As described above, the various methods of the present disclosure can be carried out at temperatures in the range of 200-900°C. For example, in some embodiments, the method for carrying out the reverse water gas shift reaction is carried out at a temperature in the range of 200-850°C, for example, in the range of 200-800°C, or 200-750°C, or 200-700°C, or 200-650°C, or 200-600°C. In some embodiments, the method for carrying out the reverse water gas shift reaction is carried out at a temperature in the range of 250-900°C, for example, in the range of 250-850°C, or 250-800°C, or 250-700°C, or 250-650°C, or 250-600°C. In some embodiments of the disclosure as described herein, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 300-900° C., for example, in the range of 300-850° C., or 300-800° C., or 300-750° C., or 300-700° C., or 300-650° C., or 300-600° C. In some embodiments of the disclosure as described herein, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 350-900° C., for example, in the range of 350-850° C., or 350-800° C., or 350-750° C., or 350-700° C., or 350-650° C., or 350-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 400-900° C., for example, in the range of 400-850° C., or 400-800° C., or 400-750° C., or 400-700° C., or 400-650° C., or 400-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 450-900° C., for example, in the range of 450-850° C., or 450-800° C., or 450-750° C., or 450-700° C., or 450-650° C., or 450-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 500-900° C., for example, in the range of 500-850° C., or 500-800° C., or 500-750° C., or 500-700° C., or 500-650° C., or 500-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a temperature in the range of 550-900° C., for example, in the range of 550-850° C., or 550-800° C., or 550-750° C., or 550-700° C., or 550-650° C., or 550-600° C.

[0094] In some embodiments, the reverse water gas shift reaction is carried out at a temperature in the range of 200-500° C., e.g., 200-450° C., or 200-400° C., or 200-350° C., or 250-500° C., or 250-450° C., or 250-400° C., or 250-350° C. The inventors have noted that operation at these temperatures can provide lower energy requirements.

[0095] As described above, the feed stream comprises CO 2 and H 2 Advantageously, the inventors have recognized that both can be derived from renewable or otherwise environmentally responsible sources. For example, at least a portion of H 2 It may be so-called "green" hydrogen, produced, for example, by water electrolysis using renewable electricity (such as wind, solar or hydroelectric power). In other embodiments, at least part of the H 2 It can come from so-called "blue" sources, such as from a natural gas reforming process with carbon capture. Of course, other sources of hydrogen can be used in part or in whole. For example, in some embodiments, the H 2 At least a portion of the hydrogen is gray, black, brown, pink, turquoise, yellow, and / or white hydrogen. 2 can be captured usually from the environment, or more directly from the formation of CO 2 In some embodiments, at least part of the CO is captured during the process (especially in areas where emissions are difficult to abate), so that the products subsequently made from the CO are at least carbon neutral. 2 from direct air capture, or from manufacturing plants such as bioethanol plants (e.g. fermentation of CO 2 ), steel mills or cement plants. Thus, the rWGS reaction can not only be carbon neutral, but in some cases can be a net consumer of carbon dioxide. These benefits make the rWGS reaction particularly attractive for decarbonizing transportation fuels (for the automotive and aviation sectors), since the carbon monoxide produced in the reaction can be easily used to synthesize liquid hydrocarbon fuels by recognized techniques.

[0096] The feed stream contains H 2 and CO 2 (e.g., provided to the reaction zone in a single physical stream or multiple physical streams). As used herein, a feed stream includes all feeds to the process, whether provided as a gas mixture or as gases provided separately to the reaction zone. In various embodiments as otherwise described herein, H in the feed stream 2 CO 2 The molar ratio of H to NH is at least 0.1:1, such as at least 0.5:1. In some embodiments, the feed stream H 2CO 2 The molar ratio of H in the feed stream is at least 0.9:1, such as at least 1:1 or at least 1.5:1. 2 CO 2 The molar ratio of H in the feed stream is at least 2:1, such as at least 2.5:1. 2 CO 2 The molar ratio of H in the feed stream is no more than 100:1, such as no more than 75:1, or 50:1. 2 CO 2 The molar ratio of H to NH is no more than 20:1, such as no more than 15:1, or 10:1. For example, in some embodiments, the feed stream H 2 CO 2 The molar ratio of H in the feed stream is in the range of 0.5:1 to 10:1. Based on the disclosure herein, one of ordinary skill in the art will provide the desired H in the feed stream. 2 :CO 2 A ratio of H to provide a desired conversion and selectivity; if consistent with the desired conversion and selectivity, an excess of H may be provided. 2 to flow through the system and provide a desired H 2 to CO ratio of the product stream.

[0097] Other gases may also be included in the feed stream. For example, in some embodiments, the feed stream further comprises CO. In some embodiments of the present disclosure as otherwise described herein, the feed stream further comprises one or more inert gases. For example, in some embodiments, the feed stream further comprises nitrogen and / or methane.

[0098] As will be appreciated by those of ordinary skill in the art, the methods described herein can be carried out at various pressures. In various embodiments of the present disclosure, the method for carrying out reverse water-gas shift reaction is carried out at a pressure of 1 to 100 bar. For example, the method is carried out at a pressure of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 70 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar.

[0099] As will be appreciated by one of ordinary skill in the art, the methods described herein can be performed at various GHSVs (gas hourly space velocities). Thus, the GHSV for performing the reverse water gas shift reaction is not particularly limited. For example, in some embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is performed at 1,000 to 2,000,000 h 2 . -1 In various embodiments, the method for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is carried out at a GHSV of 1,000 to 50,000 h -1 , or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1 , or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h -1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

[0100] The rWGS catalyst described herein is based in part on platinum, palladium and / or gold. It will generally be desirable, for example, to activate the rWGS catalyst before contacting the feed stream. Thus, in some embodiments of the present disclosure as described herein, the method includes activating the rWGS catalyst before contacting the catalyst with the feed stream. For example, in some embodiments, activating the catalyst includes contacting the catalyst with a reducing stream comprising a reducing gas (e.g., hydrogen). In various embodiments of the present disclosure, the reducing stream comprises hydrogen in an amount of at least 25 mol%, such as at least 50 mol%, or 75 mol%, or 90 mol%. One of ordinary skill in the art will determine conditions suitable for activating the rWGS catalyst. Therefore, one of ordinary skill in the art will be able to select appropriate temperature, pressure, and time to activate the rWGS catalyst. For example, in various embodiments, the activation catalyst is carried out at a temperature in the range of 200° C. to 800° C. In some embodiments, activating the catalyst is carried out at a temperature in the range of 250° C. to 800° C., or 300° C. to 800° C., or 200° C. to 700° C., or 250° C. to 800° C., or 300° C. to 700° C. In some embodiments of the disclosure as described herein, activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or at least 50% reduced).

[0101] The present inventors have discovered that contacting a rWGS catalyst as described herein with a feed stream can provide a product stream having advantageously high CO selectivity and low methane selectivity. As described above, the amount of CO in the product stream can be further controlled by the rWGS reaction conditions. However, in general, the method for conducting the rWGS reaction as described herein provides a product stream comprising H 2 and CO, wherein the product stream has a lower concentration of CO than the feed stream 2 and higher concentrations of CO, which is consistent with the degree of conversion described herein. For example, in various embodiments, the product stream comprises no more than 95 mol % CO 2 , or not more than 90 mol % CO 2 In some embodiments, the product stream comprises no more than 85 mol % CO 2 , or not more than 80 mol % CO 2 In other examples, the product stream comprises no more than 75 mol %, or no more than 70 mol % CO 2 However, as described above, the inventors have determined that it may be desirable to operate the process at an intermediate degree of conversion to provide a desirably high CO selectivity and a desirably low methane selectivity. Thus, in various embodiments as otherwise described herein, the product stream comprises an amount of CO 2 and CO.

[0102] Other gases may also be included in the product stream. In some embodiments of the present disclosure as described elsewhere herein, the product stream further comprises one or more inert gases. These inert gases may be included in the feed stream or provided from a source other than the feed stream. For example, in some embodiments, the product stream further comprises nitrogen and / or methane.

[0103] It depends in particular on the degree of conversion, CO selectivity, H 2 and CO 2 Depending on the relative amounts of H and CO, and the reaction conditions, the product stream may include H in combination with CO in various ratios. 2 For example, in some embodiments, the H 2 The ratio of CO to CO is in the range of 0.1:1 to 100:1 (e.g., in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0104] One of ordinary skill in the art will appreciate that based on the process described herein, the product stream may comprise H 2 , CO and CO 2 and various amounts of other components. The components of the product stream can be separated and used for various purposes in the rWGS process.

[0105] For example, in various embodiments of the present disclosure as described herein, the method further comprises separating the product stream so as to recycle at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of one or more components of the product stream to the feed stream. 2 When the method can include adding CO 2 At least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the product stream is recycled to the feed stream. The product stream may also include H 2 In some embodiments, the method further comprises: 2 At least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the feed stream is recycled to the feed stream.

[0106] This type of recirculation is shown in Figure 1 (and Figure 2 Here, the method 100 includes separating at least a portion of CO from the product stream 112. 2 (stream 114) for recycling to feed stream 111. Similarly, process 100 includes separating at least a portion of H from product stream 112. 2 (stream 115) for recycling to product stream 111. Although stream 115 is depicted as entering reactor 110 through a different inlet than the rest of feed stream 111, it is considered part of the feed stream because it is part of the material input to the process step.

[0107] As mentioned above, one of the competing reactions in the reverse water gas shift reaction is the Sabatier reaction, which manufactures methane. Although in various embodiments, the reverse water gas shift method described herein can be carried out without forming a large amount of methane, in some embodiments, some methane may be formed. Therefore, in various embodiments of the method as described herein, the product stream comprises one or more light hydrocarbons. For example, in some embodiments, the product stream may comprise one or more of methane, ethane, propane, or a combination thereof. As will be appreciated by those of ordinary skill in the art, it may be desirable to operate the reverse water gas shift reaction so as to provide a higher amount of light hydrocarbons in the product feed. For example, such light hydrocarbons may be inert in the further processing of the product stream, and therefore may be acceptable at higher amounts. Those of ordinary skill in the art will be able to select appropriate reaction conditions (e.g., temperature, pressure, feed stream composition) to provide a product stream comprising methane in a desired amount. For example, in various embodiments as described separately herein, the product stream comprises no more than 20 mol %, or no more than 15 mol % of methane. As described above, when a lower amount of methane is desired in the product stream, the catalyst of the present disclosure can provide very low methane selectivity. Thus, in various embodiments as described elsewhere herein, the product stream comprises no more than 10 mol % of methane. For example, in various embodiments, the product stream comprises no more than 5 mol %, or 1 mol %, or 0.5 mol %, or no more than 0.1 mol % of methane. Typically, light hydrocarbons (e.g., C 1 -C 5 For example, in various embodiments as otherwise described herein, the product stream comprises no more than 20 mol% light hydrocarbons (e.g., no more than 15 mol%, no more than 10 mol%, no more than 5 mol%, no more than 1 mol%, no more than 0.5 mol%, or no more than 0.1 mol% light hydrocarbons).

[0108] These light hydrocarbons (e.g., C 1 -C 5The light hydrocarbons) can be separated and used for other purposes. For example, in various embodiments, the method further includes separating at least a portion of one or more light hydrocarbons from the product stream to provide a light hydrocarbon stream. Figure 1 In the method 100, at least a portion of one or more light hydrocarbons is separated from the product stream 112 to provide a light hydrocarbon stream 116. The light hydrocarbon stream can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be combusted to provide heat or other energy (e.g., electricity for electrolysis) for use in the rWGS process or other processes.

[0109] Of course, as will be appreciated by one of ordinary skill in the art, the light hydrocarbon stream may also be used in other processes. For example, as will be appreciated by one of ordinary skill in the art, some rWGS catalysts may have reforming capabilities. Without being bound by theory, the inventors hypothesize that one explanation for the low methane production observed using the rWGS catalysts described herein is that methane is formed but then immediately reformed to CO and H. 2 Thus, in some embodiments as described herein, light hydrocarbons of the process stream are recycled to the feed stream for the rWGS reaction. These light hydrocarbons can be separated and used for other purposes. For example, in various embodiments, the method further includes separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream. For example, in Figure 2 In the method 100, at least a portion of one or more light hydrocarbons is separated from the first product stream 112 to provide a light hydrocarbon stream 118. The light hydrocarbon stream can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be burned to provide heat or other energy (e.g., electricity for electrolysis) for an integrated process or other processes. Of course, as will be appreciated by those of ordinary skill in the art, the light hydrocarbon stream can also be used in other processes.

[0110] Integrated Fischer-Tropsch process

[0111] In some embodiments as described herein, the supported reverse water gas can be used in a rWGS process integrated with a FT process. Embodiments related to the reverse water gas shift portion of the integrated FT process are as described above in the previous section. For example, the feed stream of the rWGS process corresponds to the first feed stream in the integrated FT process, and the product stream of the rWGS process corresponds to the first product stream in the integrated FT process.

[0112] Another aspect of the present disclosure provides a method for performing an integrated Fischer-Tropsch process (i.e., integrated with an rWGS process). The method comprises providing a 2 and CO 2a first feed stream of; contacting a reverse water gas shift catalyst as described herein with the first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a gas comprising CO and H 2 A first product stream having a lower concentration of CO than the first feed stream 2 and higher concentrations of CO. Figure 2 An example of such a method is shown schematically in Figure 2 In the method 100, the method 100 includes providing a first reaction zone, such as a reactor 110, with a mixture containing H 2 and CO 2 The reverse water gas shift reaction is carried out by reacting a first feed stream 111 of CO. As described herein, the reverse water gas shift catalyst 113 is contacted with the feed stream 111 at a first temperature in the range of 200-900° C. and at a first pressure to provide a first feed stream comprising CO and H. 2 The first product stream 112 has a lower concentration of CO than the first feed stream. 2 and a higher concentration of CO. The method of this aspect of the present disclosure also includes reacting the Fischer-Tropsch catalyst with a gas comprising H at a second temperature and a second pressure. 2 and contacting a second feed stream containing at least a portion of the CO of the first product stream to provide a 5+ A second product stream of hydrocarbons. Figure 2 In the process 100, at least a portion of the CO of the first product stream 112 is contained in the second feed stream 121, which is contacted with the Fischer-Tropsch catalyst 123 in the second reaction zone (e.g., reactor 120). This provides a catalyst containing C 5+ A second product stream 122 of hydrocarbons.

[0113] The inventors have discovered that contacting a rWGS catalyst as described herein with a first feed stream can provide a first product stream having advantageously high CO selectivity and low methane selectivity. As described above, the amount of CO in the first product stream can be further controlled by the rWGS reaction conditions.

[0114] However, as noted above, the present inventors have determined that it may be desirable to operate the process at an intermediate degree of conversion to provide a desirably high CO selectivity and a desirably low methane selectivity. In addition, the present inventors have noted that it may be advantageous to operate the downstream Fischer-Tropsch process at relatively high inert levels, and thus contemplate the use of significant amounts of CO 2 Thus, in various embodiments as otherwise described herein, the first product stream comprises an amount of CO 2In various embodiments, the first product stream comprises 5-95 mol % CO 2 %, for example, 5-90 mol%, or 5-85 mol%, or 5-80 mol%, or 5-75 mol%, or 5-70 mol%, or 10-95 mol%, or 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% of CO 2 .

[0115] In addition, as described below, Fischer-Tropsch catalysts generally require activation by a reducing gas. As will be appreciated by those skilled in the art, different Fischer-Tropsch catalysts require different activation conditions (e.g., gas composition, temperature, pressure, time). For example, an iron-based Fischer-Tropsch catalyst requires activation by H 2 and CO activation, while the cobalt-based Fischer-Tropsch catalyst only requires H 2 Therefore, H from the first product stream 2 and CO or only H 2 can be used to perform the activation. Thus, in various embodiments as otherwise described herein, the method comprises separating at least a portion of H from the first product stream. 2 and CO (desirably in a ratio of at least 1:1 or at least 3:1) and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. In various other embodiments as otherwise described herein, the method includes separating at least a portion of H from the first product stream. 2 and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 2 In the method, stream 125 separates H 2 or H 2 and CO and direct it to reactor 120. This separation need not be continuous; rather, it need only be performed for a period of time required to provide the reducing gas to the Fischer-Tropsch catalyst for activation. Of course, as will be appreciated by those skilled in the art, H 2 Or other sources of CO provide reducing gas to the Fischer-Tropsch catalyst for activation.

[0116] As indicated above, water is a product of the reverse water gas shift reaction. Thus, the first product stream will typically contain water. In many cases, it may be desirable to reduce the amount of water provided to the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream. Figure 2 In the embodiment of the present invention, the water removal zone 116 is used to remove water and provide an aqueous stream 117. It will be understood by those of ordinary skill in the art that various methods can be used to remove water from the first product stream. For example, the first product stream can be contacted with a water removal agent to remove water therefrom. For example, a molecular sieve guard bed can be used to remove water from the first product stream; water can be recovered from the molecular sieves of the guard bed, for example, by heating and vacuum. In other embodiments, a separator (knockout vessel) can be used. However, the use of a separator can in some cases sufficiently cool the first product stream so that it is desirable to reheat it for introduction into the Fischer-Tropsch process step. The water removed from the first product stream can be used as, for example, feed water for the electrolysis process described herein.

[0117] As described above, the reverse water gas shift process can be provided at a variety of temperatures. In some cases, these temperatures can be relatively close to the temperature of the subsequent Fischer-Tropsch step (typically 150-400°C, such as 200-350°C, or other temperatures as described below). In other cases, the reverse water gas shift process can be carried out at a temperature significantly higher than the temperature of the Fischer-Tropsch step. The inventors have noted that it may be desirable to provide heat exchange with a relatively hot first product stream in order to cool the first product stream to a temperature more suitable for the Fischer-Tropsch step and to provide heat to the integrated process elsewhere. For example, in various embodiments of the method as otherwise described herein, the method further includes exchanging heat between at least a portion of the first product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the first product stream and heating at least a portion of the first feed stream. In Figure 3 An example of such a method is shown schematically in Figure 3 In the process 200, the first reactor 210, the first feed stream 211, the first product stream 212, the reverse water gas shift catalyst 213, the second reactor 220, the second feed stream 221, the second product stream 222 and the Fischer-Tropsch catalyst 223 are generally as described above. Here, the process 200 includes exchanging heat between at least a portion of the first product stream 212 and at least a portion of the first feed stream 211 in the first heat exchange zone 230, thereby cooling at least a portion of the first product stream 212 and heating at least a portion of the first feed stream 211. It will be appreciated by those of ordinary skill in the art that a variety of heat exchangers may be used for this purpose.

[0118] Of course, any excess heat in the first product stream can additionally or alternatively be used for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the first product stream and the steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone. This is shown in FIG. Figure 3 Here, after heat exchange with the first feed stream 211, the first product stream 212 is directed to the steam generating zone 232 to cool the first product stream 212 and provide heat to the steam generating zone 232. Steam can be generated from the provided heat, and electricity can be generated from the steam. For example, in Figure 3 In the embodiment of the present invention, the electric current 264 is provided by generating electricity using the steam generated in the steam generating area 232. Of course, as will be appreciated by one of ordinary skill in the art, the steam generated in the steam generating area can be used for other processes. In various embodiments, the steam can be used to heat the first feed stream. For example, in Figure 3 In the embodiment of the present invention, the steam stream 266 generated in the steam generating zone 232 is directed to the heat exchange zone 290 to heat the first feed stream 211.

[0119] As described above, at least a portion of the CO of the first product stream is included in the second feed stream for reaction in the Fischer-Tropsch process. For example, in various embodiments as described elsewhere herein, at least 25% of the CO of the first product stream, for example, at least 50% of the CO of the first product stream, at least 75% of the CO, or at least 90% of the CO is included in the second feed stream. Of course, as described above, a portion of the CO of the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0120] In some embodiments, substantially all of the CO in the second feed stream is from the first product stream. However, in other embodiments, the CO can be provided to the second feed stream from other sources (fossil-derived or other). For example, in various embodiments, CO is provided to the second feed stream from a CO source other than the first product stream. Figure 3 In the embodiment of the present invention, a CO stream 226a from some other source is included in the second feed stream 221. A person skilled in the art will understand that CO can be provided from a variety of sources, such as gasification, reforming or electrochemical CO. 2 Reduction. In addition, as described in more detail below, CO can be recycled from the second product stream to the second feed stream; and / or can be provided by reaction of a light hydrocarbon stream, such as by partial oxidation or reforming (e.g., steam reforming and / or autothermal reforming).

[0121] As described above, the second feed stream comprises H 2It is worth noting that the first product stream will generally contain H 2 , such as unreacted H from the first feed stream 2 In various embodiments, the first product stream comprises H 2 wherein the second feed stream comprises H of the first product stream 2 For example, in various embodiments as described elsewhere herein, the H of the first product stream is 2 At least 25% of the H 2 At least 50% of H 2 At least 75% of H 2 At least 90% of the H of the first product stream is contained in the second feed stream. Of course, as described above, 2 A portion of the catalyst may be used for other purposes, such as catalyst activation as described herein.

[0122] In some embodiments, substantially all of the H in the second feed stream is 2 In fact, one of ordinary skill in the art can provide more H in the first feed stream than required for the reverse water gas shift reaction. 2 , in order to provide an excess of H in the first product stream 2 , the desired amount of H can then be provided to the second feed stream 2 However, in other embodiments, H may be provided to the second feed stream from other sources. 2 For example, in various embodiments, H 2 The source provides H to the second feed stream 2 .exist Figure 3 In some other sources, H 2 Stream 226b is included in the second feed stream 221. One of ordinary skill in the art will appreciate that H can be provided from a variety of sources. 2 , such as gasification, reforming or H 2 O electrolysis (including the electrolysis described herein). In addition, as described in more detail below, H 2 Recycling may be performed from the second product stream to the second feed stream.

[0123] Based on the disclosure herein, one of ordinary skill in the art can adjust the H in the second feed stream. 2 The relative amounts of H and CO can be adjusted to provide the desired ratio. For example, more or less of the H of the first feed stream can be included in the second feed stream. 2 and / or more or less H from electrolysis 2Similarly, more or less CO of the first feed stream and more or less CO from other sources (eg, partial oxidation and reforming as described below) may be included in the second feed stream.

[0124] As noted above, it may be desirable to conduct the Fischer-Tropsch process step in the presence of significant levels of inerts. One such inert is CO 2 - may be from the reverse water gas shift, for example via the first product stream. Thus, in various embodiments as otherwise described herein, the second feed stream comprises CO of the first product stream. 2 For example, in various embodiments, the CO of the first product stream 2 At least 10% of the CO in the first product stream, for example 2 At least 25% of CO 2 At least 50% of CO 2 At least 75% of CO 2 Of the total CO contained in the second feed stream, at least 90% of the CO contained in the second feed stream. Of course, in other embodiments, the second feed stream may not contain any significant amount of CO of the first product stream. 2 Thus, in various embodiments, the second feed stream does not contain a significant amount of CO from the first product stream. 2 Although it may often be desirable to 2 Recycled to the first feed stream for use in the reverse water gas shift reaction, as described in more detail below, the unreacted CO 2 Recycling may be performed from the second product stream to the first feed stream.

[0125] Additionally or alternatively, however, it may be desirable to include additional inert content in the second feed stream, whether CO 2 Still other inerts such as nitrogen and methane. For example, in various embodiments, one or more inerts (e.g., CO 2 , nitrogen and / or methane). Figure 3 In the second feed stream 221, an inert material stream 226c from some other source is included. It will be appreciated by those skilled in the art that inerts can be provided from a variety of sources. In addition, as described in more detail below, inerts can be recycled from the second product stream to the second feed stream.

[0126] As noted above, it may be desirable to conduct the Fischer-Tropsch process step in the presence of an inert. Thus, in various embodiments as otherwise described herein, the portion of the first product stream included in the second feed stream has a CO content of between 10 and 95 mole %. 2%, for example 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% of CO 2 The range of CO 2 content.

[0127] As described above, other gases may also be included in the second feed stream. For example, as described above, it may be desirable to have a significant amount of inerts (i.e., other than H 2 The Fischer-Tropsch process step is carried out in the presence of a component of CO or CO. For example, in various embodiments, the second feed stream comprises up to 80 mol% of one or more inerts, such as one or more inerts in the range of 3-80 mol%, or 5-80 mol%, or 10-80 mol%, or 15-80 mol%, or 30-80 mol%. In various embodiments, the second feed stream comprises up to 70 mol% inerts, up to 60 mol% inerts, or up to 50 mol% inerts, such as 3-70 mol%, or 5-70 mol%, or 10-70 mol%, or 15-70 mol%, or 30-70 mol%, or 3-60 mol%, or 5-60 mol%, or 10-60 mol%, or 15-60 mol%, or 30-60 mol%, or 3-50 mol%, or 5-50 mol%, or 10-50 mol%, or 15-50 mol%, or 30-50 mol% inerts. In various embodiments, the second feed stream comprises up to 80% of one or more selected from CO 2 , methane and nitrogen, such as up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%. In various embodiments, the second feed stream comprises up to 80 mol% CO 2 , such as up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%.

[0128] One of ordinary skill in the art can adjust the portion of the first product stream included in the second feed stream to provide a desired H 2For example, in various embodiments, the portion of the first product stream included in the second feed stream has a H:CO ratio in the range of 0.5:1 to 10:1, such as in the range of 1:1 to 2.5:1. 2 Of course, regardless of the H :CO ratio of the portion of the first product stream contained in the second feed stream, 2 Regardless of the ratio of H:CO, one of ordinary skill in the art can add H as needed as described above. 2 or CO to provide the desired overall ratio in the second feed stream.

[0129] As described above, the second feed stream contains H 2 and CO, and the second feed stream comprises all the feeds to the Fischer-Tropsch reactor, whether the second feed stream is provided as a mixture of feeds or as a separate feed provided to the reaction zone. In various embodiments of the disclosure as described herein, the second feed stream has a H ratio in the range of 0.5:1 to 6:1 2 In some embodiments, the second feed stream has a H:CO ratio in the range of 1:1 to 3:1, or 1:1 to 2.5:1. 2 In some embodiments, the second feed stream has a H:CO ratio of at least 1.4:1. 2 For example, in some embodiments, the second feed stream has an H:CO ratio in the range of 1.4:1 to 3:1, or 1.4:1 to 2:1. 2 Based on the disclosure herein, one of ordinary skill in the art will provide a ratio of H in the second feed stream. 2 The desired ratio of O:CO provides satisfactory conversion and selectivity in the Fischer-Tropsch process.

[0130] As described above, it may be desirable to reduce the amount of water introduced into the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, e.g., or no more than 2 mol%, or no more than 0.5 mol%.

[0131] As noted above, it may be desirable to conduct the Fischer-Tropsch process in the presence of relatively small amounts of water. Thus, in various embodiments, the second feed stream has a water content of no more than 10 mol%, for example, or no more than 2 mol%, or no more than 0.5 mol%.

[0132] The method described herein comprises contacting a Fischer-Tropsch catalyst with a second feed stream as described herein. There is no particular limitation on the Fischer-Tropsch catalyst used in the method as described herein, and one of ordinary skill in the art will be able to select a catalyst suitable for their desired Fischer-Tropsch product. In some embodiments, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0133] For example, in some embodiments of the present disclosure as described herein, the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount in the range of 5-25 wt % calculated as Co(0). "Calculated as Co(0)" and similar terms refer to the use of the weight of the cobalt atoms / ions themselves in the calculation, rather than the total amount of any compounds or polynuclear ions in which those cobalt atoms / ions may be bound. For example, in various embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 7-25 wt %, or 10-25 wt %, or 5-20 wt %, or 7-20 wt %, or 10-20 wt %, calculated as Co(0). As will be appreciated by those of ordinary skill in the art, cobalt-based catalysts are typically provided to the reaction zone in the form of cobalt oxide on a support; the cobalt may be activated by in situ reduction (e.g., with H 2 ) to provide an active catalyst species with a significant concentration of Co(0).

[0134] In some embodiments, the Fischer-Tropsch catalyst comprises iron, for example, in an amount in the range of 5-95 wt % calculated as Fe(0). For example, in various embodiments, the Fischer-Tropsch catalyst comprises iron in an amount in the range of 10-95 wt %, or 25-95 wt %, or 50-95 wt %, or 5-85 wt %, or 10-85 wt %, or 25-85 wt %, or 50-85 wt %, or 5-75 wt %, or 10-75 wt %, or 25-75 wt % calculated as Fe(0). As will be appreciated by those of ordinary skill in the art, iron-based catalysts are typically provided to the reaction zone in the form of metallic iron or iron oxide, optionally on a support; iron may be activated (e.g., by reacting with H 2 and CO) to provide an active catalyst species having a significant concentration of iron carbide.

[0135] In various embodiments of the present disclosure as described herein, especially when the catalyst is a cobalt-based catalyst, the Fischer-Tropsch catalyst further comprises manganese. For example, in various embodiments, the Fischer-Tropsch catalyst comprises manganese in an amount of up to 15 wt %, such as up to 12 wt %, or up to 10 wt %, or up to 7 wt %, calculated as Mn(0). In certain such embodiments, the catalyst material comprises manganese in an amount of 0.1-15 wt %, such as 0.1-10 wt %, or 0.1-5 wt %, 0.5-15 wt %, or 0.5-10 wt %, or 0.5-5 wt %, calculated as Mn(0). Of course, in other embodiments, manganese is substantially absent (e.g., there is less than 0.1 wt % or less than 0.5 wt % manganese).

[0136] The Fischer-Tropsch catalyst suitable for the method as described herein can be in various forms and is not particularly limited. For example, the Fischer-Tropsch catalyst can be a supported or unsupported catalyst. Although the form of the catalyst is not particularly limited, in various desirable embodiments, the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide and zinc oxide. For example, in various embodiments, the support comprises at least one of titanium oxide, aluminum oxide and silicon oxide. In some embodiments of the present disclosure as described herein, the support is a titanium dioxide support.

[0137] Those of ordinary skill in the art will appreciate that the Fischer-Tropsch catalysts of the present disclosure may be provided in many forms, particularly depending on the particular form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The support for the Fischer-Tropsch catalyst may itself be provided as a discrete body of material, for example as a porous particle, pellet or shaped extrudate, wherein the metal is provided thereon to provide the Fischer-Tropsch catalyst. However, in other embodiments, the Fischer-Tropsch catalyst of the present disclosure may itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths. Those of ordinary skill in the art will select an appropriate Fischer-Tropsch catalyst for a particular reactor system.

[0138] As with rWGS catalysts, Fischer-Tropsch catalysts are typically activated prior to use, for example to provide cobalt(0) species on cobalt-based catalysts, or iron carbide species on iron-based catalysts. Such activation may be performed prior to contacting the Fischer-Tropsch catalyst with the second feed stream.

[0139] For example, in some embodiments, the Fischer-Tropsch catalyst is activated by contact with a reducing gas. For example, hydrogen can be a particularly suitable gas for activating a Fischer-Tropsch catalyst, such as when the activation is a reduction to a metal (0) species, such as for many cobalt-based catalysts. In various embodiments of the present disclosure as otherwise described herein, the reducing gas comprises H from the first product stream. 2 For example, in some embodiments, the method further comprises separating at least a portion of the first product stream H 2 and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 2 In the process 100 schematically shown in FIG. 1 , at least a portion of the hydrogen stream 125 is separated from the first product stream 112 and contacted with the Fischer-Tropsch catalyst 123 to activate it. In other embodiments, the H present in the second feed stream 2 Can be used to activate the catalyst. As will be appreciated by those skilled in the art, the activation temperature may vary depending on the Fischer-Tropsch catalyst used. Therefore, those skilled in the art will be able to select an appropriate temperature for activating the catalyst, for example in the range of 200-400°C.

[0140] In various embodiments, the Fischer-Tropsch catalyst is reacted with H 2 and CO for activation. This may be particularly suitable when the activation provides for conversion to carbides, such as for many iron-based catalysts. In various embodiments of the present disclosure as described elsewhere herein, the reducing gas comprises H from the first product stream. 2 and at least a portion of CO. For example, in some embodiments, the method further comprises separating at least a portion of the first product stream H 2 and at least a portion of CO and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 3 In the process 200 schematically shown in FIG. 2 , at least a portion of H is separated from the first product stream 212. 2 and CO stream 227 and contacted with Fischer-Tropsch catalyst 223 to activate it. In other embodiments, H present in the second feed stream 2 and CO can be used to activate the catalyst. The activation temperature can vary, for example, in the range of 200-400°C.

[0141] As described above, the method includes contacting the Fischer-Tropsch catalyst with the second feed stream at a second temperature and a second pressure. One of ordinary skill in the art will select appropriate reaction conditions in conjunction with the specific feed and catalyst for providing the desired Fischer-Tropsch process. In some embodiments of the present disclosure as described herein, the second temperature is in the range of 150-400°C. For example, in various embodiments, the second temperature is in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C. In some specific embodiments, the second temperature is in the range of 200-350°C.

[0142] It is noteworthy that in many embodiments, the first temperature and the second temperature can be relatively close to each other. The inventors have noted that the reverse water gas shift catalyst described herein can provide suitable activity and CO selectivity even at relatively low temperatures. Therefore, the first product stream can be provided with a temperature suitable for or at least close to that suitable for the Fischer-Tropsch reaction step. This can desirably provide improved process integration. For example, in various embodiments, the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

[0143] However, in other embodiments, the first temperature and the second temperature are not too close to each other. The inventors have noted that in many cases, the desired reverse water gas shift process temperature will be significantly higher than the desired Fischer-Tropsch temperature. For example, in various embodiments, the first temperature is at least 100°C higher than the second temperature, such as at least 150°C higher than the second temperature, or at least 200°C higher than the second temperature. The excess heat in the first product stream can be used for a variety of purposes, such as for preheating at least a portion of the first feed stream or generating steam for power generation, as described above.

[0144] In some embodiments of the present disclosure as described herein, the second pressure is in the range of 10-50 bar. For example, in various embodiments, the second pressure is in the range of 20-50 bar, or 25-50 bar, or 10-40 bar, or 20-40 bar, or 25-40 bar, or 10-35 bar, or 20-35 bar, or 25-35 bar. In some embodiments, the second pressure is in the range of 20-50 bar.

[0145] As will be appreciated by those of ordinary skill in the art, the Fischer-Tropsch process described herein can be performed at various GHSV (gas hourly space velocity) values. Thus, there is no particular limitation on the GHSV at which the Fischer-Tropsch reaction is performed. For example, in some embodiments of the present disclosure, the process of performing the Fischer-Tropsch reaction is performed at 1,000 to 2,000,000 h -1 In various embodiments, the process for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the process of carrying out the Fischer-Tropsch reaction is carried out at a GHSV of 1,000 to 50,000 h. -1 , or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1 , or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h -1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

[0146] The Fischer-Tropsch process is commonly used to prepare C 5+ Hydrocarbons, such as unsubstituted C 5+ Hydrocarbons (such as alkanes and alkenes) and oxygen-containing C 5+ Hydrocarbons (such as C 5+ alcohols, aldehydes, ketones, carboxylic acids). In various embodiments of the present disclosure as described herein, the Fischer-Tropsch catalyst is contacted with the second feed stream to provide a second product stream with at least 30%, such as at least 50%, or at least 70% C5+ Selectivity (i.e. for all C 5+ For example, in some embodiments, C 5+ The selectivity for alkanes is at least 30%, such as at least 50%, or at least 70%. 5+ Alkanes and C 5+ The selectivity to alcohol is at least 30%, such as at least 50%, or at least 70%.

[0147] Additional components may be present in the second product stream. For example, in some embodiments, the second product stream comprises water, which is another product of the Fischer-Tropsch reaction. One or more light hydrocarbons (i.e., C 1 -C 4 ) as a by-product. CO and / or H 2 , such as unreacted CO and / or H from the second feed stream 2 There may also be CO 2 or other inerts as described herein. Such components of the second product stream may be separated and / or recycled in a variety of ways.

[0148] For example, in various embodiments, the method further comprises separating at least a portion of the water from the second product stream. This is schematically shown in Figure 4 In. Figure 4 In an embodiment, the reverse water gas shift catalyst 313 and the Fischer-Tropsch catalyst 323 are provided in separate beds in the same reactor. Thus, the first reaction zone 310 is the volume of the reactor 305 including the bed 314 containing the reverse water gas shift catalyst 313, and the second reaction zone 320 is the volume of the reactor 305 including the bed 324 containing the Fischer-Tropsch catalyst 323. The first feed stream 311 is contacted with the reverse water gas shift catalyst 313 to provide a first product stream 312, which is directly fed to the Fischer-Tropsch catalyst 323 as a second feed stream 321 to provide a second product stream 322. Here, the method also optionally includes separating at least a portion of the water (e.g., at least 50%, at least 75%, or at least 90%) from the second product stream 322 to provide a water-containing stream 334.

[0149] Light hydrocarbons, while generally not a desired portion of a Fischer-Tropsch product for use as a fuel or lubricant, can themselves be used for many purposes. Thus, in various embodiments, the method further comprises separating at least a portion of the C 1 -C 4 The light hydrocarbon stream can be recycled, for example, to the first feed stream or the second feed stream. Figure 3In the method 200, the light hydrocarbons can be provided as part of the recycle stream 236, which becomes part of the second feed stream 221. Figure 4 In the method 300, the light hydrocarbons can be provided as part of a recycle stream 336, which becomes part of the first feed stream 311. Figure 5 In the method 400 , light hydrocarbons are recycled to the first feed stream 411 via the recycle stream 442 .

[0150] The light hydrocarbon stream has other uses. For example, in some embodiments, the method further comprises oxidizing at least a portion of the light hydrocarbon stream to provide a 2 The invention relates to a partially oxidized (pOX) stream of the invention and comprising at least a portion of the pOX stream in the first feed stream and / or the second feed stream. Figure 5 An example of such a process is schematically shown in , wherein process 400, first feed stream 411, first product stream 412, reverse water gas shift catalyst 413, second feed stream 421, second product stream 422, and Fischer-Tropsch catalyst 423 can be as described elsewhere herein. Here, the process includes oxidizing at least a portion of light hydrocarbon stream 450 in partial oxidation reaction zone 452 to provide a stream containing CO and / or CO 2 The pOX stream is prepared by mixing the pOX stream 454 with the first feed stream 411 and / or the second feed stream 421.

[0151] Other methods can be used to provide CO and / or CO from light hydrocarbon streams. 2 For example, reforming technologies such as steam reforming and autothermal reforming can be used to provide CO by reacting hydrocarbons with water. Therefore, in various embodiments, the method further comprises reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon stream to provide a CO and / or CO 2 The reforming stream of the present invention is provided, and at least a portion of the reforming stream is included in the first feed stream and / or the second feed stream. The water separated from the first and / or second product stream can be provided as part of the feed to the reforming described herein.

[0152] In addition, the light hydrocarbon stream can be burned to provide thermal energy, which can be used to heat various process streams, or to generate electricity. Thus, in various embodiments, the method includes burning at least a portion of the light hydrocarbon stream to provide energy, such as thermal energy or electrical energy. For example, in Figure 5 In the method 400, a portion of the light hydrocarbon stream 450 is combusted in a power generation area (here, in a generator 470) to generate electricity 472. In various embodiments, the thermal energy can be used to provide the required heat load for the reverse water gas shift process. For example, in Figure 5 In the method 400 of , a portion of the light hydrocarbon stream 450 is burned in the power generation zone (here, in the heat generator 480) to produce a heat stream 482. The heat stream 482 is directed to the heat exchange zone 490 to heat the first feed stream 411. Thermal energy can be similarly provided to the Fischer-Tropsch reaction. And as will be understood by those of ordinary skill in the art, other treatments of the light hydrocarbon stream (e.g., partial oxidation) can also provide energy, which can be used, for example, as described herein.

[0153] As with the first product stream, heat can be exchanged from the second product stream to provide heat to, for example, a feed stream or a steam generating zone. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the first feed stream. Figure 4 In the method 300, in the second heat exchange zone 330, heat is exchanged between at least a portion of the second product stream 322 and the first feed stream 311, thereby cooling the second product stream 322 and heating the first feed stream 311. Of course, heat can also be exchanged from the second product stream to the second feed stream. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the second feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the second feed stream. Figure 5 In the method 400, heat is exchanged between at least a portion of the second product stream 422 and the second feed stream 421 in the second heat exchange zone 430, thereby cooling the second product stream 422 and heating the second feed stream 421. One of ordinary skill in the art will appreciate that a variety of heat exchangers may be used for this purpose.

[0154] Of course, any excess heat in the second product stream can additionally or alternatively be used for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and the steam generating zone, thereby cooling at least a portion of the second product stream and providing heat to the steam generating zone. This is shown in FIG. Figure 4 Here, after heat exchange with the first feed stream 311, the second product stream 322 is directed to the steam generating zone 332 to cool the second product stream 322 and provide heat to the steam generating zone 332. Steam can be generated from the provided heat, and electricity can be generated from the steam (not shown here).

[0155] It may be desirable to recycle hydrogen from the second product stream to, for example, the first feed stream and / or the second feed stream. For example, in various embodiments, the method includes recycling the H of the second product stream to the first feed stream and / or the second feed stream. 2At least a portion of is recycled to the second feed stream. Figure 3 In the method of 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H of the second product stream is recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the process includes recycling H of the second product stream. 2 At least a portion of is recycled to the first feed stream 311. For example, Figure 4 In the method, the H of the second product stream can be 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H of the second product stream is recycled to the first feed stream 311 via the recycle stream 336. 2 At least 75%, such as at least 90%, of the feed stream is recycled to the first feed stream or the second feed stream.

[0156] In some cases, for example, in the presence of H other than the first product stream 2 The source provides H to the second feed stream 2 When H from the second product stream 2 H which may constitute the first feed stream 2 The majority of the first feed stream, for example H 2 At least 90%, at least 95%, or at least 98% of Figure 5 Here, the primary H 2 The input is through stream 440, which becomes part of the second feed stream 421. The H of the second product stream 2 Contained in recycle stream 442 , it becomes part of first feed stream 411 .

[0157] Similarly, it may be desirable to recycle the CO of the second product stream to, for example, the first feed stream and / or the second feed stream. For example, in various embodiments, the method includes recycling at least a portion of the CO of the second product stream to the second feed stream. Figure 3 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO of the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the method includes recycling at least a portion of the CO of the second product stream to the first feed stream. For example, in Figure 4In the method of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336. In various embodiments, at least 25%, such as at least 50%, of the CO of the second product stream is recycled to the first feed stream or the second feed stream. In various embodiments, at least 75%, such as at least 90% of the CO of the second product stream is recycled to the first feed stream or the second feed stream.

[0158] In many cases, the CO and H of the second product stream will be recycled. 2 .

[0159] In addition, when one or more inerts are used in the Fischer-Tropsch process steps, it may be desirable to recycle these inerts. For example, in various embodiments, the method includes recycling at least a portion of the inerts of the second product stream to the second feed stream. Figure 3 In the process of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inerts of the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the process includes recycling at least a portion of the inerts of the second product stream to the first feed stream. For example, in Figure 4 In the method of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inerts of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336. In various embodiments, at least 25%, such as at least 50%, of the inerts of the second product stream are recycled to the first feed stream or the second feed stream. In various embodiments, at least 75%, such as at least 90% of the inerts of the second product stream are recycled to the first feed stream or the second feed stream. In various embodiments, the purge stream can be combined with the recycle stream to prevent uncontrolled accumulation of inerts in the recycle stream (not shown here).

[0160] Specifically, due to CO 2 is a carbon source for the reverse water gas shift process step, it may be particularly desirable to convert CO 2 is recycled to the first feed stream. Thus, in various embodiments, the process includes converting the CO of the second product stream to 2 At least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the Figure 4 In the method, the CO of the second product stream 2 At least a portion (eg, at least 50%, at least 75%, or at least 90%) of the NH 2 O 2 may be recycled to the first feed stream 311 via the recycle stream 336 .

[0161] In some cases, for example, in the presence of CO other than the first product stream 2 The source provides CO to the second feed stream 2 When CO from the second product stream 2 CO that can constitute the first feed stream 2 The majority of the first feed stream, for example CO 2 At least 90%, at least 95%, or at least 98% of Figure 5 Here, the primary CO 2 The input is through stream 440, which becomes part of the second feed stream 421. The CO of the second product stream 2 Contained in recycle stream 442 , it becomes part of first feed stream 411 .

[0162] As described above, the Fischer-Tropsch process provides a 5+ A second product stream of hydrocarbons (e.g., unsubstituted hydrocarbons such as alkanes and olefins, and / or oxygenated hydrocarbons such as alcohols). Thus, in various embodiments, the second product stream is composed of C 5+ At least a portion of the hydrocarbons provides one or more products. 5+ Hydrocarbons can be used as the basis for various fuels, such as gasoline, diesel, and aviation fuel. Other products, such as waxes and lubricants, can also be made. And olefins and oxygenates can be used as feedstocks in various other processes.

[0163] A person skilled in the art will use conventional post-processing techniques to remove the C 5+ The product of the hydrocarbon is converted into a desirable product such as a desirable fuel. For example, in various embodiments, the method further comprises hydrotreating the C 5+ At least a portion of the hydrocarbons. As will be understood by one of ordinary skill in the art, hydroprocessing is the treatment of a hydrocarbon stream with hydrogen in the presence of a suitable catalyst. A variety of hydroprocessing techniques are known and one of ordinary skill in the art will apply them herein. For example, in Figure 4 In the method 300, the second product stream 322 is hydrotreated in the hydrotreating reactor 350 to provide a hydrotreated product stream 352.

[0164] As mentioned above, CO 2 and H 2 are substantial inputs to the claimed methods. Advantageously, the inventors have recognized that each of these inputs may be derived from renewable or otherwise environmentally responsible sources.

[0165] CO 2 can be captured usually from the environment, or more directly from the formation of CO 2The CO2 in the first feed stream and / or the second feed stream may be captured during the process (especially in areas where emissions are difficult to abate). This may result in the final hydrocarbon product being substantially carbon neutral or having a lower carbon intensity. Therefore, in some embodiments of the present disclosure as described herein, the CO2 in the first feed stream and / or the second feed stream may be captured during the process (especially in areas where emissions are difficult to abate). 2 At least a portion of the CO in the first feed stream and / or the second feed stream is from a renewable source. 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO2 in the first feed stream and / or the second feed stream is from direct air capture. 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO generated by a production plant such as a bioethanol plant (e.g., fermentation) 2 ), steel mills or cement plants. Therefore, the rWGS-Fischer-Tropsch integrated process of the present disclosure as described herein can not only be carbon neutral, but in some cases can be a net consumer of carbon dioxide. These benefits make the integrated process particularly attractive for decarbonizing transportation fuels (for the automotive and aviation sectors), because the carbon monoxide produced in the rWGS reaction can be easily used to synthesize liquid hydrocarbon fuels by the Fischer-Tropsch process by recognized techniques.

[0166] Similarly, H 2 Can be provided by environmentally responsible sources. In some embodiments, the H of the first feed stream and / or the second feed stream is 2 At least a portion of the H of the first feed stream and / or the second feed stream is from a renewable source. For example, in various embodiments, the H 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the hydrogen produced by the first feed stream and / or the second feed stream may be so-called "green" hydrogen, such as produced by water electrolysis operated using renewable electricity (e.g., wind, solar, or hydroelectric power). 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the hydrogen in the first feed stream and / or the second feed stream may come from a so-called "blue" source, such as from a natural gas reforming process with carbon capture. Of course, other sources of hydrogen may be used in part or in whole. For example, in some embodiments, the H 2 At least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the hydrogen is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0167] The inventors have noted that electrolysis of water is a desirable way to provide hydrogen to the claimed process. Thus, in some embodiments, the process comprises providing at least a portion of H to the first feed stream and / or the second feed stream by electrolysis of water.2 In some embodiments, the electrolysis of water is performed at least in part using electricity from a renewable source, for example to provide so-called "green hydrogen". However, the inventors have noted that electricity can be generated as part of the claimed method, for example using heat exchange from the first or second product stream, or by burning light hydrocarbons as described above. In some embodiments, the electrolysis of water is performed at least in part using electricity generated according to the methods described herein. For example, in Figure 3 In method 200, water 262 separated from the first product stream is electrolyzed in electrolyzer 260 using electricity 264 generated from steam produced in steam generating zone 232 by heat exchange from the first product stream. 2 is provided to the first feed stream via stream 265. In some embodiments, the O generated in the electrolysis 2 At least a portion of the Figure 7 The partial oxidation reaction zone shown in the embodiment of FIG. 4 is a partial oxidation reaction zone shown in FIG. 4. The hydrogen from the electrolysis can also be burned to provide thermal energy, for example, which can be used to heat the first feed stream.

[0168] The methods described herein can be operated in a variety of reactor systems. In some embodiments, the first reaction zone (i.e., where the reverse water gas shift process step is performed) includes a first reactor in which a reverse water gas shift catalyst is disposed, and the second reaction zone (i.e., where the Fischer-Tropsch process step is performed) includes a second reactor in which a Fischer-Tropsch catalyst is disposed. Examples of such methods are schematically shown in Figure 1 , 2 and 4. In these embodiments, the method (100, 200, 400) is carried out in a reactor system comprising a first reactor (110, 210, 410) in which a reverse water gas shift catalyst (113, 213, 413) is disposed and a second reactor (120, 220, 420) in which a Fischer-Tropsch catalyst (123, 223, 423) is disposed. The reactor used in the integrated process of the present disclosure as described herein is not particularly limited, and a person of ordinary skill in the art will be able to select an appropriate reactor.

[0169] However, other embodiments are possible. For example, in some embodiments, the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein the second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed. In some embodiments, the first reactor bed and the second reactor bed are disposed in the same reactor. Figure 4, where the reverse water gas shift catalyst 313 is disposed in a first catalyst bed 314 and the Fischer-Tropsch catalyst 323 is disposed in a second catalyst bed 324. Here, the catalyst beds 314 and 324 are in the same reactor 305 with the process gas flowing between them. Such a configuration may be particularly desirable when the first temperature and the second temperature are relatively close to each other.

[0170] In various embodiments, the method is carried out in a reactor system comprising a first catalyst container in which one or more reverse water gas shift catalysts are disposed, and wherein the second reaction zone comprises a second catalyst container in which one or more Fischer-Tropsch catalysts are disposed. These may be provided in the same reactor, as described above for the catalyst bed.

[0171] As described above, the reverse water gas shift process step and the Fischer-Tropsch process step using the platinum, palladium and / or gold catalysts described herein can be performed under similar conditions. Thus, in various embodiments, the reverse water gas shift catalyst and the Fischer-Tropsch catalyst can be provided together in the same catalyst bed, for example mixed together. Such embodiments are shown in Figure 6 Here, the method 500 is carried out in a reactor system including a reactor 505 in which a reverse water gas shift catalyst 513 and a Fischer-Tropsch catalyst 523 are mixed together in a single catalyst bed 524. Here, the first feed stream 511 and the second product stream 522 can be substantially as described herein. The first product stream and the second feed stream are understood to be a mixture of process gases within the mixed catalyst.

[0172] In the embodiments specifically described above, separate rWGS and Fischer-Tropsch catalysts are used in admixture, for example, in separate reactors, in separate zones of the same reactor, or even in the same zone of a reactor.

[0173] However, the inventors have also noted that there are certain commonalities between the rWGS catalysts described herein and certain Fischer-Tropsch catalysts. For example, as will be appreciated by one of ordinary skill in the art, manganese is a common modifier used in Fischer-Tropsch catalysts, particularly those based on cobalt. The inventors have also noted that similar supports can be used for each catalyst.

[0174] Therefore, in addition to the above-mentioned configuration, the inventors have contemplated providing a single bifunctional catalyst having reverse water gas shift activity and Fischer-Tropsch activity. This bifunctional catalyst comprises rWGS active catalyst metal and Fischer-Tropsch active catalyst metal in the same body. It will be understood by those skilled in the art that both rWGS catalyst and Fischer-Tropsch catalyst are supported catalysts, such as metal oxide supported catalysts. Therefore, in various embodiments of the present disclosure, rWGS active catalyst metal and Fischer-Tropsch active catalyst metal can be disposed together on the same carrier to provide a bifunctional catalyst. For example, in some embodiments, the carrier of the bifunctional catalyst itself is provided as a discrete body of material, such as a porous particle, pellet or shaped extrudate, wherein the rWGS active catalyst metal and the FT active catalyst metal are disposed thereon to provide a bifunctional catalyst. The rWGS active catalyst metal and the FT active catalyst metal can be uniformly distributed throughout the carrier, or can be distributed in discrete regions throughout the carrier. However, in other embodiments, the bifunctional catalyst of the present disclosure itself can be formed as a layer on the substrate below. For example, in some embodiments, the bifunctional catalyst is formed by a rWGS active catalyst metal layer and a FT active catalyst metal layer on the substrate below. The rWGS-active catalyst metal and the FT-active catalyst metal may be uniformly distributed on the underlying substrate. In other embodiments, the rWGS-active catalyst metal and the FT-active catalyst metal may be in discrete regions on the underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths.

[0175] The bifunctional catalyst comprises a support material, an rWGS active catalyst metal as described herein, and a Fischer-Tropsch active catalyst metal as described herein. For example, the bifunctional catalyst comprises a support as a metal oxide support as described herein, at least one of platinum, palladium and gold, manganese, and at least one of cobalt, iron, rhodium and ruthenium. In some embodiments of the present disclosure, the bifunctional catalyst comprises a support as a metal oxide support as described herein, at least one of platinum, palladium and gold, manganese, and cobalt. In some embodiments of the present disclosure, the bifunctional catalyst comprises a support comprising at least one of titanium oxide, zirconium oxide, cerium oxide or aluminum oxide, at least one of platinum, palladium and gold, manganese, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, at least one of platinum, palladium and gold, manganese, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, platinum, manganese, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, palladium, manganese, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, gold, manganese, and cobalt. For example, in some embodiments, the bifunctional catalyst comprises a titanium oxide support, at least one of platinum, palladium, and gold present in an amount ranging from 0.05 to 10% by weight, manganese present in an amount ranging from 0.5 to 20% by weight, and cobalt present in an amount ranging from 7-25% by weight. In some embodiments, the bifunctional catalyst comprises a titanium oxide support. Platinum present in an amount ranging from 0.05 to 10% by weight, manganese present in an amount ranging from 0.5 to 20% by weight, and cobalt present in an amount ranging from 7-25% by weight. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, palladium present in an amount ranging from 0.05 to 10% by weight, manganese present in an amount ranging from 0.5 to 20% by weight, and cobalt present in an amount ranging from 7-25% by weight. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, gold present in an amount ranging from 0.05 to 10% by weight, manganese present in an amount ranging from 0.5 to 20% by weight, and cobalt present in an amount ranging from 7-25% by weight.

[0176] The ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is not particularly limited, and one of ordinary skill in the art will be able to select an appropriate ratio. For example, in some embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.1: 1. In various embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.2: 1, or 0.5, or 1: 1.

[0177] Such catalysts can be used for Figure 6 In those embodiments described, one of ordinary skill in the art will select reaction conditions that provide an appropriate balance of reverse water gas shift activity and Fischer-Tropsch activity.

[0178] Figure 7 is a schematic depiction of another integrated process according to the present disclosure. Here, the reverse water gas shift and Fischer-Tropsch steps are integrated with partial oxidation of light hydrocarbons to provide CO and H to the Fischer-Tropsch step. 2 ; electrolysis to provide H for the reverse water gas shift process step 2 and O for partial oxidation 2 ; and various recycles and optional feeds, as described throughout this specification.

[0179] One of ordinary skill in the art will be able to provide the materials and perform the methods described herein based on the above general disclosure and with reference to the following examples. Example

[0180] The following examples illustrate specific embodiments of the catalysts and methods of the present disclosure and various uses thereof. They are set forth for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0181] Example 1. Modeling

[0182] The inventors have modeled various equilibrium conditions for the reverse water gas shift reaction. The predicted carbon dioxide conversion rate and product composition of the rWGS reaction (reaction formula 1) competing with the Sabatier reaction (reaction formula 3) and the CO methanation reaction (reaction formula 4) are calculated based on the temperature range of 400-800° C. for thermodynamic equilibrium. From the modeling, carbon monoxide selectivity increases at temperatures above 600° C., while methane selectivity decreases at higher temperatures.

[0183] It is clear from these results that the Sabatier reaction (equation (3)) and CO methanation (equation (4)) side reactions are exothermic and dominate at lower temperatures, while the rWGS reaction (equation (1)) is endothermic and dominates at higher temperatures. However, other carbon-producing side reactions that are not considered in the examples described may occur at high temperatures. Therefore, the inventors have studied catalysts that operate at moderate temperatures. These catalysts are discussed in more detail below.

[0184] Example 2 Catalyst Preparation

[0185] The catalysts were prepared using a conventional impregnation method before testing their feasibility for the reverse water gas shift reaction. The supports used are described in Table 1.

[0186] Table 1.

[0187] Chemicals supplier Pore ​​volume Cerium(IV) Oxide Sigma-Aldrich 0.1mL / g γ-Alumina Saint Gobain 0.83mL / g Titanium Dioxide P-25Aeroxide Evonik 0.5mL / g

[0188] To prepare the catalyst, a solution of active metal (e.g., Pd, Pt or Au) and tetrahydrated manganese acetate (99.9% purity, Fisher Chemicals) was prepared in deionized water. For solutions containing platinum, a platinum (II) nitrate solution with 17.5% by weight of Pt and 99.95% purity from Umicore was used. For solutions containing palladium, a palladium (II) nitration solution with 23.9% by weight of Pd and 99.95% metal purity from Umicore was used. For solutions containing gold, gold (III) hydroxide from Sigma-Aldrich (79.1% Au was measured after reduction with hydrazine dihydrate) was used. A solution of active metal salt and manganese was added to the carrier powder. The amount of the carrier added was based on the amount of water by mass, so that the ratio of water: carrier was 3: 1. The slurry was then stirred at room temperature for 4 hours. Excess water was then evaporated using a stirred drying bath at a temperature of 60°C. The resulting catalyst precursor powder was then dried in a drying oven at 90° C. for 24 hours.

[0189] The catalyst precursor powder was then subjected to calcination by spreading it evenly in a crucible. The crucible was placed in a calcining furnace and the temperature was raised from ambient temperature to 120°C at a rate of 10°C / min. The temperature was then maintained at 120°C for 1 hour and then raised from 120°C to 500°C at a rate of 2°C / min. The temperature was maintained at 500°C for 4 hours and then cooled to ambient temperature. The resulting catalyst was then tested for feasibility for reverse water gas shift reaction.

[0190] Example 3. Performance of platinum and palladium catalysts

[0191] The catalytic performance of the catalyst prepared by the method described herein was then tested for the reverse water gas shift reaction. The catalyst was a ceria supported catalyst containing 0.25 wt%, 0.5 wt% and 2 wt% platinum or palladium, and 0 wt%, 1 wt% or 5 wt% manganese. To test the catalytic performance of these catalysts, 20 μL of catalyst diluted with SiC F100 to provide a ratio of 1:10 was loaded into a 3 mm ID ceramic tube reactor to obtain a 0.22 mL catalyst bed with a zone height of 31.1 mm. Prior to the rWGS reaction, the catalyst was activated at 590°C in an atmosphere of 97% hydrogen and 3% argon for 5 hours. Subsequently, the catalyst was incubated at a temperature of 600°C with an aqueous solution of H2O2 containing a 2:1 ratio. 2 and CO 2 The total pressure was maintained at 30 bar. For Runs 1-2, 4 and 6-8, the GHSV was maintained at 29,500 h -1 , and for Tests 3 and 5, the GHSV is 1,200,000h -1The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts is shown in Table 2. In Table 2 and Tables 3-7 below, the amount of platinum, palladium and / or manganese present in the catalyst is shown in brackets. These figures are in weight percent and are based on the total weight of the catalyst. For example, CeO 2 Pt(0.5)Mn(1) corresponds to a material with 0.5 wt% Pt, 1 wt% Mn and 98.5 wt% CeO 2 catalyst.

[0192] Table 2.

[0193]

[0194] Catalysts comprising 0.5 wt. % of platinum or palladium exhibit very high CO selectivity, wherein the addition of manganese to the catalyst leads to an increase in catalyst activity and CO selectivity.

[0195] To further investigate these catalysts, CeO was also measured at different temperatures and pressures. 2 Pd(0.5)Mn(5),CeO 2 Pd(0.5)Mn(1),CeO 2 Pt(0.5)Mn(1) and CeO 2 Pt(0.5)Mn(5) catalyst. Tests 9-20 were performed at 2:1 H 2 :CO 2 Molar ratio and 16,000h -1 GHSV, and Test 21 was conducted at 2:1 H 2 :CO 2 Molar ratio and 1,200,000h -1 These results are shown in Table 3.

[0196] Table 3.

[0197]

[0198] As shown in Table 3, the catalysts exhibited excellent CO selectivity that was consistent over the range of process conditions tested. The high selectivity for CO demonstrated in the above tests provides an effluent stream suitable for integration with other processes.

[0199] Example 4. Effect of manganese on ceria-supported platinum catalyst

[0200] In order to study the effect of manganese on supported reverse water gas shift catalysts, manganese-containing and manganese-free ceria supported platinum catalysts were measured. Platinum was present in the catalyst at a concentration of 0.1 wt%, 0.5 wt%, or 1 wt%, with and without manganese present at 5 wt%. Ceria itself was also measured, as well as a 5 wt% manganese catalyst on ceria without platinum. These catalysts were prepared by the methods described herein. In order to test the catalytic performance of these catalysts, a Meryer quartz reactor was used, which contained 0.1 g of catalyst at a density of about 2 g / mL of catalyst. The total flow rate was 37.7 mL / min (CO 2 The partial pressure is 9.6 mol % H 2 The partial pressure of different H 2 :CO 2 The catalysts were then subjected to 34,560 h of heating at two different temperatures at a pressure of 1 bar. -1 At a GHSV of 1.5 mmol / l, H 2 and CO 2 The rWGS reaction was carried out by contacting the feed stream of . The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 4.

[0201] Table 4.

[0202]

[0203] Table 4 shows that one way to increase catalyst activity is by increasing the platinum loading. However, this is accompanied by a decrease in CO selectivity. When up to 5 wt % manganese is placed on the supported catalyst without platinum, CO can be recovered to greater than 99% under the conditions tested, although there is a loss in activity. However, when 0.1 wt % to 1 wt % platinum is added to the 5 wt % manganese on ceria catalyst, CO selectivity and CO are observed as demonstrated in Table 4. 2 Improvement in conversion. Some loss of catalyst activity is accompanied by a large increase in CO selectivity. However, without being bound by theory, the inventors believe that conversion may be reduced due to less methanation occurring.

[0204] To further investigate the effect of ceria-supported manganese catalysts with 0.5 wt % or 1 wt % platinum present with and without 5 wt % manganese, they were incubated at two different temperatures with a catalyst having high H 2 :CO 2 The tests were conducted at a pressure of 1 bar and 2250 h -1 Table 5 reports these results.

[0205] Table 5.

[0206]

[0207] Table 5 shows that the presence of Mn in the catalyst can 2 :CO 2 As shown in Table 5, when using catalysts having manganese and platinum or palladium supported on ceria, it was observed that the CO selectivity remained robust, with values ​​greater than 99% observed.

[0208] Example 5. Effect of carrier on catalyst performance

[0209] The effect of the support on the catalyst performance was also evaluated by evaluating platinum and manganese supported catalysts on various catalytic supports (ceria, alumina and titania). These catalysts contained 0.5 wt% platinum and 5 wt% manganese. As in the previous examples, these catalysts were prepared by the methods described herein. The reactor setup and catalyst activation described in Example 4 were also used here. Subsequently, these catalysts were reacted with H in a molar ratio of 3:1 at two different temperatures. 2 and CO 2 The feed stream is at a pressure of 1 bar and 34,560h -1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 6.

[0210] Table 6.

[0211]

[0212] Table 6 shows that the manganese effect is still viable on a range of supports for platinum catalysts. Adding 5 wt% manganese to various metal oxide supports (alumina, praseodymium-doped ceria, titania, and ceria) loaded with 0.5 wt% platinum increased CO selectivity despite reduced catalyst activity. As described above with respect to the results shown in Table 4, without being bound by theory, the inventors believe that the conversion may have decreased due to less methanation occurring.

[0213] Example 6. Methane selectivity of ceria-supported platinum catalyst

[0214] The catalysts prepared by the methods described herein were then tested for methane selectivity for the reverse water gas shift reaction. These catalysts were ceria supported catalysts containing 0.5 wt % platinum and 0 wt %, 1 wt % or 5 wt % manganese. The catalysts were reacted with a mixture containing 6 vol % H 2 and 2 vol% CO 2 The feed stream is contacted with the GHSV of 1200h -1The amount of catalyst used was 50 mg. The conversion percentage of carbon dioxide and the carbon molar selectivity to methane were followed at temperatures ranging from 200°C to 700°C.

[0215] Figure 8 Shows the effect of CO 2 The equilibrium conversion of CO to CO 2 The conversion percentage and the reaction conversion rate of the following catalysts: CeO 2 Pt(0.5), CeO 2 Pt(0.5)Mn(1) and CeO- 2 Pt(0.5)Mn(5). Fig. 9 The carbon molar selectivity of methane for the three catalysts is shown. Figure 8 It can be seen that CeO 2 The presence of Pt(0.5) catalyst reduces the CO conversion relative to the equilibrium conversion at temperatures below 375 °C. 2 However, without being bound by theory, the inventors believe that the conversion rate may be reduced due to less methanation occurring, such as Fig. 9 The results show that the inclusion of 1 wt % or 5 wt % manganese can change the product selectivity, such as by reducing the selectivity for methane. Fig. 9 As shown, in the case of adding manganese to the ceria-supported platinum catalyst, the methane conversion rate dropped from 11% to 0% at 500°C.

[0216] Example 7. Methane selectivity of titanium dioxide supported platinum catalyst

[0217] The catalysts prepared by the methods described herein were then tested for methane selectivity for the reverse water gas shift reaction. These catalysts were titanium dioxide supported catalysts containing 0.5 wt % platinum and 0 wt %, 1 wt %, or 5 wt % manganese. The catalysts were mixed with a 6 vol % H 2 and 2 vol% CO 2 The feed stream is contacted with the GHSV of 1200h -1 The amount of catalyst used was 50 mg. The conversion percentage of carbon dioxide and the carbon molar selectivity to methane were followed at temperatures ranging from 200°C to 700°C.

[0218] Fig.10 It shows that the use of TiO 2 Pt(0.5) catalyst, using TiO 2 Pt(0.5)Mn(1) catalyst and the use of TiO 2 PtMn(5) catalyst for CO 2 The equilibrium conversion of CO to CO 2 conversion percentage. Fig.10The carbon molar selectivity of methane for the three catalysts is shown. Figure 8 and Fig. 9 The same effect is shown in Figure 2. The activity shifts to higher temperatures at 1 wt% manganese and shifts further at 5 wt% manganese, and the selectivity for methane decreases significantly at 1 wt% manganese and decreases to below the gas chromatography detection limit at 5 wt% manganese.

[0219] Example 8. Methane selectivity of alumina-supported platinum catalyst

[0220] The catalysts prepared by the methods described herein were then tested for methane selectivity for the reverse water gas shift reaction. These catalysts were alumina supported catalysts containing 0.5 wt % platinum and 0 wt %, 1 wt %, or 5 wt % manganese. The catalysts were mixed with a 6 vol % H 2 and 2 vol% CO 2 The feed stream is contacted with the GHSV of 1200h -1 The amount of catalyst used was 50 mg of catalyst. The conversion percentage of carbon dioxide and the carbon molar selectivity of methane were tracked at a temperature ranging from 200°C to 700°C and are shown in Fig. 9 and 10 middle.

[0221] Fig.12 Shows the use of Al 2 O 3 Pt(0.5) catalyst, using Al 2 O 3 Pt(0.5)Mn(1) catalyst and using Al 2 O 3 Pt(0.5)Mn(5) catalyst for CO 2 The equilibrium conversion of CO to CO 2 conversion percentage, and Fig.13 The carbon molar selectivity of methane for the three catalysts is shown. Figure 7-11 The same effect is shown in Figure 1. In the case of 1 wt% manganese, the activity shifts to higher temperatures and shifts further in the case of 5 wt% manganese. In addition, the selectivity for methane is significantly reduced in the case of 1 wt% manganese. In the case of 5 wt% manganese, the methane selectivity is reduced to 2%.

[0222] Example 9. Effect of catalyst activation on catalyst performance

[0223] The effect of catalyst activation on catalyst performance of catalysts prepared by the methods described herein was evaluated. A ceria supported catalyst containing 0.5 wt% platinum and 5 wt% manganese was activated in a hydrogen atmosphere at three different temperatures (400°C, 590°C and 760°C) and subsequently used in the rWGS method. 20 μL of catalyst diluted with SiC F100 to provide a ratio of 1:10 was loaded into a 3 mm ID ceramic tube reactor to give a 0.22 mL catalyst bed with a zone height of 31.1 mm. At 200,000 h -1 Using pure H at GHSV 2 The catalyst was activated. The reactor pressure was set to 10 bar, and the reactor was then heated to the desired activation temperature at a rate of 1 K / min and maintained at said temperature for 5 hours. After activation, the reactor was cooled to the temperature of the rWGS process. Four rWGS reaction temperatures were evaluated - 400°C, 500°C, 600°C and 700°C. When the rWGS reaction temperature was reached, the feed stream was introduced and the reaction pressure was set. The activated catalyst was mixed with H in a molar ratio of 2:1. 2 and CO 2 The feed stream is at a pressure of 30 bar and 1,200,000 h -1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 7.

[0224] Table 7.

[0225]

[0226] The results in Table 7 show consistent CO selectivity and CO 2 In addition, the results in Table 7 show that although the CO selectivity is high (greater than 98%) for all rWGS temperatures measured, the CO 2 Conversion increases with increasing reaction temperature. However, the use of higher activation temperatures and higher rWGS reaction temperatures appears to adversely affect catalyst activity as seen in Run 70. In summary, the results of Table 7 show that activation temperature is another variable for adjusting the resulting product stream.

[0227] Example 10. Performance of Au Catalyst

[0228] The catalytic performance of the catalyst prepared by the method described herein was then tested for the reverse water gas shift reaction. The catalyst tested was a ceria supported catalyst containing 0.5 wt % gold and 0 wt %, 1 wt %, or 5 wt % manganese. In order to test the catalytic performance of these catalysts, 20 μL of catalyst diluted with SiC F100 to provide a ratio of 1:10 was loaded into a 3 mm ID ceramic tube reactor to obtain a 0.22 mL catalyst bed with a zone height of 31.1 mm. Prior to the rWGS reaction, the catalyst was activated at 590 ° C in an atmosphere of 97% hydrogen and 3% argon for 5 hours. Subsequently, the catalyst was incubated at a temperature of 600 ° C with an H 2 and CO 2 The total pressure and GHSV were maintained at 30 bar and 29,500 h -1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts is shown in Table 8. In Table 8 and Tables 9-11 below, the amount of gold and / or manganese present in the catalyst is shown in brackets. These figures are in weight percent and are based on the total weight of the catalyst. For example, CeO 2 Au(0.5)Mn(1) corresponds to a material with 0.5 wt% Au, 1 wt% Mn and 98.5 wt% CeO 2 catalyst.

[0229] Table 8.

[0230]

[0231] The catalyst comprising 0.5 wt % gold showed very high selectivity, wherein the addition of 1 wt % and 5 wt % manganese to the catalyst resulted in an increase in catalyst activity and CO selectivity.

[0232] At 500°C and 2:1 H 2 :CO 2 Ratio, 16,000h -1 Catalysts containing 0.5 wt % gold and 0 wt % and 5 wt % manganese were tested at GHSV of 1.3 and 1.5 GHSV at two different pressures. The results are reported in Table 9.

[0233] Table 9.

[0234]

[0235] Table 9 shows that the ceria-supported manganese and gold catalysts exhibit very high CO selectivity under other operating conditions.

[0236] Example 11. Effect of manganese on ceria-supported gold catalyst

[0237] To investigate the effect of manganese on supported reverse water gas shift catalysts, ceria supported gold catalysts with and without manganese were measured at different temperatures and pressures. Gold was present in the catalyst at a concentration of 0.5 wt %, with and without manganese present at 5 wt %. These catalysts were prepared by the methods described herein. The reactor setup and catalyst activation as described in Example 10 were also used here. For the rWGS reaction, runs A8-A13 were performed at 2:1 H 2 :CO 2 Molar ratio and 29,500h -1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. These results are shown in Table 10.

[0238] Table 10.

[0239]

[0240] From the results of Tables 9 and 10, the catalysts show excellent CO selectivity, and the selectivity remains robust over the range of process conditions tested, especially at temperatures between 500° C. and 700° C. Addition of 5 wt % manganese to the catalyst results in an increase in CO selectivity, with higher total CO yields observed at 500° C. and 600° C. In tests A10 and A11 conducted at 700° C., a slight increase in CO selectivity was observed.

[0241] The supported gold catalysts showed very high CO selectivity throughout the tested conditions. 2 The Au(0.5)Mn(5) catalyst is more selective than the ceria-supported gold catalyst without manganese. This suggests that including manganese in the formulation is beneficial for CO selectivity. Most importantly, carbon monoxide selectivity does not decrease as pressure increases from 12 bar to 20 bar. This is important because methanation activity generally increases when operating at higher pressures and generally results in lower CO selectivity. In this case, operating further away from equilibrium can also be helpful.

[0242] Example 12. Au Catalyst Performance at Lower Temperatures

[0243] At lower temperatures and different H 2 :CO 2 The CeO ratio was evaluated 2 Performance of Au(0.5)Mn(5) catalysts. The catalysts were prepared by the methods described herein, and the reactor setup and catalyst activation were as described in Example 10. For the rWGS reaction, runs A14-A16 were conducted at 10 bar pressure, while run A17 was conducted at 20 bar. All runs were conducted at 16,000 h.-1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 11.

[0244] Table 11.

[0245]

[0246] Under the conditions tested in Table 11, the catalysts showed high CO selectivity. Under the conditions used, the catalysts provided an effluent stream suitable for integration with other processes.

[0247] Additional aspects of the disclosure are provided by the embodiments listed below, which may be combined in any number and in any combination that is not logically or technically inconsistent.

[0248] Embodiment 1. A supported reverse water gas shift catalyst comprising:

[0249] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0250] at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0251] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0252] Embodiment 2. The catalyst of Embodiment 1, wherein the support constitutes at least 70 wt % (e.g., at least 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %) of the catalyst on an oxide basis.

[0253] Embodiment 3. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a cerium oxide support.

[0254] Embodiment 4. The catalyst of Embodiment 3, wherein at least the surface layer of the cerium oxide support comprises at least 60 wt% cerium oxide, such as at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, based on oxide.

[0255] Embodiment 5. The catalyst of Embodiment 3, wherein at least the surface layer of the cerium oxide support comprises at least 90 wt% cerium oxide, such as at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, based on oxide.

[0256] Embodiment 6. The catalyst of any one of Embodiments 3-5, wherein the cerium oxide support comprises at least 50 wt% cerium oxide, such as at least 60 wt% cerium oxide, or at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, based on the oxide.

[0257] Embodiment 7. The catalyst of any one of Embodiments 3-5, wherein the cerium oxide support comprises at least 90 wt% cerium oxide, such as at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, based on the oxide.

[0258] Embodiment 8. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a titanium oxide support.

[0259] Embodiment 9. The catalyst of Embodiment 8, wherein at least the surface layer of the titanium oxide support comprises at least 60 wt% titanium oxide, for example at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, based on oxides.

[0260] Embodiment 10. The catalyst of Embodiment 8, wherein at least the surface layer of the titanium oxide support comprises at least 90 wt% titanium oxide, such as at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, based on oxides.

[0261] Embodiment 11. The catalyst of any one of Embodiments 8-10, wherein the titanium oxide support comprises at least 50 wt% titanium oxide, such as at least 60 wt% titanium oxide, or at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, based on the oxide.

[0262] Embodiment 12. The catalyst of any one of Embodiments 8-10, wherein the titanium oxide support comprises at least 90 wt% titanium oxide, such as at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, based on the oxide.

[0263] Embodiment 13. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is an alumina support.

[0264] Embodiment 14. The catalyst of Embodiment 13, wherein at least the surface layer of the alumina support comprises at least 60 wt% alumina, e.g., at least 70 wt% alumina, or at least 80 wt% alumina, on an oxide basis.

[0265] Embodiment 15. The catalyst of Embodiment 13, wherein at least the surface layer of the alumina support comprises at least 90 wt% alumina, e.g., at least 95 wt% alumina, or at least 98 wt% alumina, on an oxide basis.

[0266] Embodiment 16. The catalyst of any one of Embodiments 13-15, wherein the alumina support comprises at least 50 wt% alumina, e.g., at least 60 wt% alumina, or at least 70 wt% alumina, or at least 80 wt% alumina, on an oxide basis.

[0267] Embodiment 17. The catalyst of any one of Embodiments 13-15, wherein the alumina support comprises at least 90 wt% alumina, e.g., at least 95 wt% alumina, or at least 98 wt% alumina, on an oxide basis.

[0268] Embodiment 18. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a zirconia support.

[0269] Embodiment 19. The catalyst of Embodiment 18, wherein at least the surface layer of the zirconia support comprises at least 60 wt% zirconia, for example at least 70 wt% zirconia, or at least 80 wt% zirconia, based on oxides.

[0270] Embodiment 20. The catalyst of Embodiment 18, wherein at least the surface layer of the zirconia support comprises at least 90 wt% zirconia, e.g., at least 95 wt% zirconia, or at least 98 wt% zirconia, based on oxides.

[0271] Embodiment 21. The catalyst of any one of Embodiments 18-20, wherein the zirconia support comprises at least 50 wt% zirconia, such as at least 60 wt% zirconia, or at least 70 wt% zirconia, or at least 80 wt% zirconia, based on the oxide.

[0272] Embodiment 22. The catalyst of any one of Embodiments 18-21, wherein the zirconia support comprises at least 90 wt% zirconia, e.g., at least 95 wt% zirconia, or at least 98 wt% zirconia, on an oxide basis.

[0273] Embodiment 23. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a mixed oxide support having at least a surface layer comprising at least 50 wt. % of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide, based on the oxides.

[0274] Embodiment 24. The catalyst of any one of Embodiments 1-23, wherein the support does not contain more than 2 wt% of the total amount of the added metal, such as more than 1 wt% or more than 0.5 wt% of the added metal, based on the oxide.

[0275] Embodiment 25. The catalyst of any one of Embodiments 1-23, wherein the support comprises at least one additional metal.

[0276] Embodiment 26. The catalyst of Embodiment 25, wherein the total amount of the at least one additional metal is 0.5-20 wt%, for example 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, based on the oxide.

[0277] Embodiment 27. The catalyst of any one of Embodiments 1-26, wherein the support has a pore volume of at least 0.05 mL / g.

[0278] Embodiment 28. The catalyst of any one of Embodiments 1-27, wherein the support has a pore volume of at most 1.5 mL / g.

[0279] Embodiment 29. The catalyst of any one of Embodiments 1-28, wherein the support has a pore volume in the range of 0.05-1.5 mL / g.

[0280] Embodiment 30. The catalyst of any one of Embodiments 1-29, wherein platinum is present in the catalyst.

[0281] Embodiment 31. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.1 to 10 wt%, for example, ranging from 0.5 to 10 wt%, or 1 to 10 wt%, or 2 to 10 wt%, or 5 to 10 wt%, based on the total weight of the catalyst.

[0282] Embodiment 32. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 7 wt %, for example, ranging from 0.1 to 7 wt %, or 0.5 to 7 wt %, or 1 to 7 wt %, or 2 to 7 wt %, based on the total weight of the catalyst.

[0283] Embodiment 33. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, ranging from 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, or 2 to 5 wt%, based on the total weight of the catalyst.

[0284] Embodiment 34. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, ranging from 0.1 to 2 wt%, or 0.3 to 2 wt%, or 0.5 to 2 wt%, or 1 to 2 wt%, based on the total weight of the catalyst.

[0285] Embodiment 35. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 1.5 wt. %, for example, ranging from 0.1 to 1.5 wt. %, or 0.3 to 1.5 wt. %, or 0.5 to 1.5 wt. %, based on the total weight of the catalyst.

[0286] Embodiment 36. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 1 wt %, for example, ranging from 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst.

[0287] Embodiment 37. The catalyst of Embodiment 30, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 0.8 wt%, for example, ranging from 0.1 to 0.8 wt%, or 0.3 to 0.8 wt%, or 0.5 to 0.8 wt%, based on the total weight of the catalyst.

[0288] Embodiment 38. The catalyst of any one of Embodiments 1-37, wherein palladium is present in the catalyst.

[0289] Embodiment 39. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.1 to 10 wt %, for example, ranging from 0.5 to 10 wt %, or 1 to 10 wt %, or 2 to 10 wt %, or 5 to 10 wt %, based on the total weight of the catalyst.

[0290] Embodiment 40. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 7 wt %, for example, ranging from 0.1 to 7 wt %, or 0.5 to 7 wt %, or 1 to 7 wt %, or 2 to 7 wt %, based on the total weight of the catalyst.

[0291] Embodiment 41. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, ranging from 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, or 2 to 5 wt%, based on the total weight of the catalyst.

[0292] Embodiment 42. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, ranging from 0.1 to 2 wt%, or 0.3 to 2 wt%, or 0.5 to 2 wt%, based on the total weight of the catalyst.

[0293] Embodiment 43. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 1.5 wt%, for example, from 0.1 to 1.5 wt%, or from 0.3 to 1.5 wt%, or from 0.5 to 1.5 wt%, based on the total weight of the catalyst.

[0294] Embodiment 44. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 1 wt %, for example, ranging from 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst.

[0295] Embodiment 45. The catalyst of Embodiment 38, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 0.8 wt %, for example, ranging from 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0296] Embodiment 46. The catalyst of any one of Embodiments 1-45, wherein gold is present in the catalyst.

[0297] Embodiment 47. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.1 to 10 wt %, for example, ranging from 0.5 to 10 wt %, or 1 to 10 wt %, or 2 to 10 wt %, or 5 to 10 wt %, based on the total weight of the catalyst.

[0298] Embodiment 48. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 7 wt %, for example, ranging from 0.1 to 7 wt %, or 0.5 to 7 wt %, or 1 to 7 wt %, or 2 to 7 wt %, based on the total weight of the catalyst.

[0299] Embodiment 49. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, ranging from 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, or 2 to 5 wt%, based on the total weight of the catalyst.

[0300] Embodiment 50. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, ranging from 0.1 to 2 wt%, or 0.3 to 2 wt%, or 0.5 to 2 wt%, or 1 to 2 wt%, based on the total weight of the catalyst.

[0301] Embodiment 51. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 1.5 wt. %, for example, ranging from 0.1 to 1.5 wt. %, or 0.3 to 1.5 wt. %, or 0.5 to 1.5 wt. %, based on the total weight of the catalyst.

[0302] Embodiment 52. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 1 wt %, for example, ranging from 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst.

[0303] Embodiment 53. The catalyst of any one of Embodiment 46, wherein gold is present in the catalyst in an amount ranging from 0.05 to 0.8 wt %, for example, ranging from 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0304] Embodiment 54. The catalyst of any one of Embodiments 1-53, wherein manganese is present in the catalyst in an amount ranging from 0.5 to 15 wt %, for example, ranging from 0.5 to 12 wt %, or 0.5 to 10 wt %, based on the total weight of the catalyst.

[0305] Embodiment 55. The catalyst of any one of Embodiments 1-53, wherein manganese is present in the catalyst in an amount ranging from 1 to 20 wt %, for example, ranging from 1 to 15 wt %, or 1 to 12 wt %, or 1 to 10 wt %, based on the total weight of the catalyst.

[0306] Embodiment 56. The catalyst of any one of Embodiments 1-53, wherein manganese is present in the catalyst in an amount ranging from 2 to 20 weight percent, e.g., ranging from 2 to 15 weight percent, or 2 to 12 weight percent, or 2 to 10 weight percent, based on the total weight of the catalyst.

[0307] Embodiment 57. The catalyst of any one of Embodiments 1-53, wherein manganese is present in the catalyst in an amount ranging from 4 to 20 weight percent, e.g., ranging from 4 to 15 weight percent, or 4 to 12 weight percent, or 4 to 10 weight percent, based on the total weight of the catalyst.

[0308] Embodiment 58. The catalyst of any one of Embodiments 1-57, wherein the weight ratio of platinum, palladium, and / or gold to manganese is at least 0.05:1, e.g., at least 0.1:1.

[0309] Embodiment 59. The catalyst of any one of Embodiments 1-58, wherein the weight ratio of platinum, palladium and / or gold to manganese is at most 5:1, e.g., at most 2:1, or 1:1, or 0.5:1.

[0310] Embodiment 60. The catalyst of any one of Embodiments 1-59, wherein the ratio of platinum, palladium, and / or gold to manganese is in the range of 0.05:1 to 1:1 (e.g., in the range of 0.05:1 to 2:1, or 0.05:1 to 1:1, or 0.05:1 to 0.5:1, or 0.05:1 to 0.3:1, or 0.07:1 to 5:1, or 0.07:1 to 2:1, or 0.07:1 to 1:1, or 0.07:1 to 0.5:1, or 0.07:1 to 0.3:1, or 0.1:1 to 5:1, or 0.1:1 to 2:1, or 0.1:1 to 1:1, or 0.1:1 to 0.5:1, or 0.1:1 to 0.3:1).

[0311] Embodiment 61. The catalyst of any one of Embodiments 1-60, wherein the total amount of cerium, titanium, aluminum, zirconium, manganese, platinum, palladium and gold in the catalyst, on a metal basis, is at least 90 weight percent, e.g., at least 95 weight percent, or at least 98 weight percent, of the catalyst.

[0312] Embodiment 62. The catalyst of any one of Embodiments 1-61, wherein the catalyst has an additional metal (i.e., non-Mn, Pd, Pt, Au, Ce, Ti, Al, or Zr) content of no more than 10 wt.% (e.g., no more than 5 wt.%, or no more than 2 wt.%, or no more than 1 wt.%) based on the total weight of the catalyst.

[0313] Embodiment 63. The catalyst of any one of Embodiments 1-62, wherein the catalyst has a Cu content of no more than 10 wt. % (e.g., no more than 5 wt. %, or no more than 2 wt. %, or no more than 1 wt. %) based on the total weight of the catalyst.

[0314] Embodiment 64. The catalyst of any one of Embodiments 1-63, wherein the catalyst has an alkali metal content of no more than 10 wt. % (e.g., no more than 5 wt. %, or no more than 2 wt. %, or no more than 1 wt. %) based on the total weight of the catalyst.

[0315] Embodiment 65. The catalyst of any one of Embodiments 1-64, wherein the catalyst has an alkaline earth metal content of no more than 10 wt. % (e.g., no more than 5 wt. %, or no more than 2 wt. %, or no more than 1 wt. %) based on the total weight of the catalyst.

[0316] Embodiment 66. A method of making the catalyst of any one of Embodiments 1-65, the method comprising:

[0317] providing a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0318] contacting the support with one or more liquids, the one or more liquids each comprising one or more compounds containing platinum, palladium or gold and / or one or more compounds containing manganese dispersed in a solvent;

[0319] allowing the solvent to evaporate to provide a catalyst precursor; and

[0320] The catalyst precursor is calcined.

[0321] Embodiment 67. The method of Embodiment 66, wherein contacting the support with the liquid comprises adding the liquid in an amount equal to the pore volume of the support.

[0322] Embodiment 68. The method of Embodiment 66, wherein contacting the support with the liquid comprises adding the liquid in an amount greater than the pore volume of the support.

[0323] Embodiment 69. The method of any one of Embodiments 66-68, wherein the ratio of the amount of liquid to the amount of carrier on a mass basis is in the range of 1:1 to 5:1 (e.g., in the range of 1:1 to 3:1).

[0324] Embodiment 70. The method of any one of Embodiments 66-69, wherein contacting the support with the liquid provides a slurry.

[0325] Embodiment 71. The method of any one of Embodiments 66-70, wherein the solvent is allowed to evaporate at ambient temperature.

[0326] Embodiment 72. The method of any one of Embodiments 66-70, wherein the solvent is allowed to evaporate at an elevated temperature (eg, in the range of 50-150° C.) for a drying time (eg, 24 hours).

[0327] Embodiment 73. The method of any one of Embodiments 66-70, wherein the solvent is allowed to evaporate under vacuum and elevated temperature (e.g., in the range of 50-150° C.) for a drying time (e.g., 24 hours).

[0328] Embodiment 74. The method of any one of Embodiments 66-70, wherein the solvent is allowed to evaporate at an elevated temperature (eg, in the range of 30-100° C.) in a stirred drying bath.

[0329] Embodiment 75. The method of any one of Embodiments 66-74, wherein the calcination of the catalyst precursor is carried out for a calcination time in the range of 0.5 to 24 hours (e.g., 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours).

[0330] Embodiment 76. The method of any one of Embodiments 66-75, wherein calcining the catalyst precursor is carried out at a temperature in the range of 100-600°C, such as in the range of 120-500°C.

[0331] Embodiment 77. The catalyst of any one of Embodiments 1-65, prepared by the method according to Embodiments 66-76.

[0332] Embodiment 78. A method of performing a reverse water gas shift reaction, the method comprising:

[0333] The catalyst according to any one of embodiments 1-65 and 77 is mixed with a mixture containing CO at a temperature in the range of 200-900°C. 2 and H 2 The feed stream is contacted to provide a 2 A product stream having a lower concentration of CO than the feed stream 2 and higher concentrations of CO.

[0334] Embodiment 79. The method of Embodiment 78, wherein the reverse water gas shift reaction has a CO selectivity of at least 95%, for example at least 96%.

[0335] Embodiment 80. The method of Embodiment 78, wherein the reverse water gas shift reaction has a CO selectivity of at least 98%, such as at least 99%.

[0336] Embodiment 81. The method of any one of Embodiments 78-80, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example no more than 4%.

[0337] Embodiment 82. The method of any one of Embodiments 78-80, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, such as no more than 1%.

[0338] Embodiment 83. The method of any one of Embodiments 78-80, wherein the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, such as no more than 0.2%.

[0339] Embodiment 84. The method of any one of Embodiments 78-83, having at least 5%, such as at least 10%, or 20% CO 2 Conversion rate.

[0340] Embodiment 85. The method of any one of Embodiments 78-83, having at least 30%, such as at least 40%, of CO 2 Conversion rate.

[0341] Embodiment 86. The method of any one of Embodiments 78-85, having no more than 90%, such as no more than 80%, or no more than 70% CO 2 Conversion rate.

[0342] Embodiment 87. The method of any one of Embodiments 78-85, having a CO content of not more than 65%, such as not more than 60%. 2 Conversion rate.

[0343] Embodiment 88a. The method of any one of Embodiments 78-87 is carried out at a temperature in the range of 200-850°C, for example, in the range of 200-800°C, or 200-750°C, or 200-700°C, or 200-650°C, or 200-600°C.

[0344] Embodiment 88b. The method of any one of Embodiments 78-87 is carried out at a temperature in the range of 250-900°C, for example, in the range of 250-850°C, or 250-800°C, or 250-700°C, or 250-650°C, or 250-600°C.

[0345] Embodiment 89. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 300-900°C, for example, in the range of 300-850°C, or 300-800°C, or 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.

[0346] Embodiment 90. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 350-900°C, for example, in the range of 350-850°C, or 350-800°C, or 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C.

[0347] Embodiment 91. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 400-900°C, for example, in the range of 400-850°C, or 400-800°C, or 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.

[0348] Embodiment 92. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 450-900°C, for example, in the range of 450-850°C, or 450-800°C, or 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C.

[0349] Embodiment 93. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 500-900°C, for example, in the range of 500-850°C, or 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.

[0350] Embodiment 94. The method described in any one of Embodiments 78-87 is carried out at a temperature in the range of 550-900°C, for example, in the range of 550-850°C, or 550-800°C, or 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.

[0351] Embodiment 95. The method of any one of Embodiments 78-94, wherein the H of the feed stream 2 At least a portion of the energy derived from renewable sources.

[0352] Embodiment 96. The method of any one of Embodiments 78-95, wherein the H of the feed stream 2 At least part of the hydrogen is green hydrogen.

[0353] Embodiment 97. The method of any one of Embodiments 78-96, wherein the H of the feed stream 2 At least part of it is blue hydrogen.

[0354] Embodiment 98. The method of any one of Embodiments 78-97, wherein the H of the feed stream 2 At least a portion of is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0355] Embodiment 99. The method of any one of Embodiments 78-98, wherein the CO of the feed stream 2 At least a portion of the energy derived from renewable sources.

[0356] Embodiment 100. The method of any one of Embodiments 78-99, wherein the CO of the feed stream 2 At least a portion of the gas is obtained from direct air capture.

[0357] Embodiment 101. The method of any one of Embodiments 78-100, wherein the CO of the feed stream 2 At least a portion of the CO2 is captured from a manufacturing plant, such as a bioethanol plant, a steel plant or a cement plant.

[0358] Embodiment 102. The method of any one of Embodiments 78-101, wherein H in the feed stream 2 CO 2 The molar ratio of is at least 0.1:1, such as at least 0.5:1.

[0359] Embodiment 103. The method of any one of Embodiments 78-101, wherein H in the feed stream 2 CO 2 The molar ratio of is at least 0.9:1, such as at least 1:1 or at least 1.5:1.

[0360] Embodiment 104. The method of any one of Embodiments 78-101, wherein H in the feed stream 2 CO 2 The molar ratio of is at least 2:1, such as at least 2.5:1.

[0361] Embodiment 105. The method of any one of Embodiments 78-104, wherein H in the feed stream 2 CO 2 The molar ratio of is no more than 100:1, such as no more than 75:1, or 50:1.

[0362] Embodiment 106. The method of any one of Embodiments 78-104, wherein H in the feed stream 2 CO 2 The molar ratio of is no more than 20:1, such as no more than 15:1, or 10:1.

[0363] Embodiment 107. The method of any one of Embodiments 78-104, wherein H in the feed stream 2 CO 2 The molar ratio is in the range of 0.5:1 to 10:1.

[0364] Embodiment 108. The method of any one of Embodiments 78-107, carried out at a pressure in the range of 1 to 100 bar, for example in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 80 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar.

[0365] Embodiment 109. The method of any one of Embodiments 78-108, wherein the -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0366] Embodiment 110. The method of any one of Embodiments 78-109, wherein the product stream comprises no more than 95 mol % CO 2 (e.g. no more than 90 mol % CO 2 ).

[0367] Embodiment 111. The method of any one of Embodiments 78-109, wherein the product stream comprises no more than 85 mol % CO 2 (e.g. no more than 80 mol % CO 2 ).

[0368] Embodiment 112. The method of any one of Embodiments 78-109, wherein the product stream comprises no more than 75 mol % CO 2 (e.g. no more than 70 mol % CO 2 ).

[0369] Embodiment 113. The method of any one of Embodiments 78-112, wherein the product stream further comprises CO2 , and wherein the method further comprises converting the CO of the product stream 2 At least a portion of is recycled to the feed stream.

[0370] Embodiment 114. The method of any one of Embodiments 78-113, wherein the product stream further comprises hydrogen, and wherein the method further comprises recycling at least a portion of the hydrogen of the product stream to the feed stream.

[0371] Embodiment 115. The method of any one of Embodiments 78-114, wherein the H in the product stream 2 The ratio of CO to CO is in the range of 0.1:1 to 100:1 (e.g., in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0372] Embodiment 116. The method of any one of Embodiments 78-115, wherein the product stream comprises no more than 20 mol% methane, e.g., no more than 15 mol% methane.

[0373] Embodiment 117. The method of any one of Embodiments 78-115, wherein the product stream contains no more than 10 mol% methane, for example, no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

[0374] Embodiment 118. The method of any one of Embodiments 78-117, wherein the method comprises activating the catalyst prior to contacting the catalyst with the feed stream.

[0375] Embodiment 119. The method of Embodiment 118, wherein activating the catalyst comprises contacting the catalyst with a reducing feed stream comprising a reducing gas (eg, hydrogen).

[0376] Embodiment 120. The method of Embodiment 118 or Embodiment 119, wherein the reducing feed stream comprises hydrogen in an amount of at least 25 mol % (e.g., at least 50 mol %, or 75 mol %, or 90 mol %).

[0377] Embodiment 121. The method of any one of Embodiments 118-120, wherein activation of the catalyst is carried out at a temperature in the range of 200°C to 800°C (e.g., in the range of 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C).

[0378] Embodiment 122. The method of any one of Embodiments 118-121, wherein activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or 50% reduced).

[0379] Embodiment 123. A method of performing an integrated Fischer-Tropsch process, the method comprising:

[0380] Provides H 2 and CO 2 a first feed stream of

[0381] Contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a gas comprising CO and H 2 A first product stream having a lower concentration of CO than the feed stream 2 and higher concentrations of CO;

[0382] The Fischer-Tropsch catalyst is reacted with a mixture containing H at a second temperature and a second pressure. 2 and contacting a second feed stream containing at least a portion of the CO of the first product stream to provide a 5+ a second product stream of hydrocarbons,

[0383] The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising:

[0384] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0385] at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0386] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0387] Embodiment 124. The method of Embodiment 123, wherein H in the first feed stream 2 CO 2 The molar ratio of is at least 0.1:1, such as at least 0.5:1.

[0388] Embodiment 125. The method of Embodiment 123, wherein H in the first feed stream 2 CO 2The molar ratio of is at least 0.9:1, such as at least 1:1 or at least 1.5:1.

[0389] Embodiment 126. The method of Embodiment 123, wherein H in the first feed stream 2 CO 2 The molar ratio of is at least 2:1, such as at least 2.5:1.

[0390] Embodiment 127. The method of any one of Embodiments 1-126, wherein H in the first feed stream 2 CO 2 The molar ratio of is no more than 100:1, such as no more than 75:1, or 50:1.

[0391] Embodiment 128. The method of any one of Embodiments 1-126, wherein H in the first feed stream 2 CO 2 The molar ratio of is no more than 20:1, such as no more than 15:1, or 10:1.

[0392] Embodiment 129. The method of any one of Embodiments 1-128, wherein H in the first feed stream 2 CO 2 The molar ratio is in the range of 0.5:1 to 10:1.

[0393] Embodiment 130. A method according to any one of Embodiments 1-129, wherein the first feed stream further comprises CO.

[0394] Embodiment 131. A method according to any one of Embodiments 1-130, wherein the first feed stream further comprises one or more inert gases (e.g., nitrogen and / or methane).

[0395] Embodiment 132. The method of any one of Embodiments 1-131, wherein the reverse water gas shift reaction has a CO selectivity of at least 70%, such as at least 80%.

[0396] Embodiment 133. The method of any one of Embodiments 1-131, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, such as at least 90%.

[0397] Embodiment 134. The method of any one of Embodiments 1-133, wherein the reverse water gas shift reaction has a CO selectivity of at least 95%, such as at least 96%.

[0398] Embodiment 135. The method of any one of Embodiments 1-133, wherein the reverse water gas shift reaction has a CO selectivity of at least 98%, for example or at least 99%.

[0399] Embodiment 136. The method of any one of Embodiments 1-135, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example no more than 4%.

[0400] Embodiment 137. The method of any one of Embodiments 1-135, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, for example no more than 1%.

[0401] Embodiment 138. The method of any one of Embodiments 1-135, wherein the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0402] Embodiment 139. The method of any one of Embodiments 1-138, wherein the reverse water gas shift reaction has at least 5%, such as at least 10%, or 20% CO 2 Conversion rate.

[0403] Embodiment 140. The method of any one of Embodiments 1-138, wherein the reverse water gas shift reaction has at least 30%, such as at least 40%, of CO 2 Conversion rate.

[0404] Embodiment 141. The method of any one of Embodiments 1-140, wherein the reverse water gas shift reaction has no more than 90%, such as no more than 80%, or no more than 70% CO 2 Conversion rate.

[0405] Embodiment 142. The method of any one of Embodiments 1-140, wherein the reverse water gas shift reaction has a CO 2 Conversion rate.

[0406] Embodiment 143. A method according to any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 200-850°C, for example, in the range of 200-850°C, or 200-750°C, or 200-700°C, or 200-650°C, or 200-600°C.

[0407] Embodiment 144. The method of any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 250-900°C, for example, in the range of 250-850°C, or 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C.

[0408] Embodiment 145. The method described in any one of Embodiments 1-142, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 300-900°C, for example, in the range of 300-850°C, or 300-800°C, or 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.

[0409] Embodiment 146. The method of any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 350-900°C, for example, in the range of 350-850°C, or 350-800°C, or 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C.

[0410] Embodiment 147. The method described in any one of Embodiments 1-142, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 400-900°C, for example, in the range of 400-850°C, or 400-800°C, or 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.

[0411] Embodiment 148. The method of any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 450-900°C, for example, in the range of 450-850°C, or 450-800°C, or 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C.

[0412] Embodiment 149. The method described in any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 500-900°C, for example, in the range of 500-850°C, or 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.

[0413] Embodiment 150. The method of any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 550-900°C, for example, in the range of 550-850°C, or 550-800°C, or 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.

[0414] Embodiment 151. A method according to any one of Embodiments 1-142, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, for example, 250-450°C, or 250-400°C, or 250-350°C.

[0415] Embodiment 152. A method according to any one of embodiments 1-151, wherein the reverse water gas shift reaction is carried out at a pressure in the range of 1 to 100 bar (for example, in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 80 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar).

[0416] Embodiment 153. The method of any one of Embodiments 1-152, wherein the reverse water gas shift reaction is carried out at 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0417] Embodiment 154. The method of any one of Embodiments 1-153, wherein the method comprises activating the reverse water gas shift catalyst, for example, before contacting the reverse water gas shift catalyst with the first feed stream.

[0418] Embodiment 155. The method of Embodiment 154, wherein activating the rWGS catalyst comprises contacting the rWGS catalyst with a reducing feed stream comprising a reducing gas (eg, hydrogen).

[0419] Embodiment 156. The method of Embodiment 154 or Embodiment 155, wherein the reducing feed stream comprises hydrogen in an amount of at least 25 mol % (e.g., at least 50 mol %, or 75 mol %, or 90 mol %).

[0420] Embodiment 157. The method of any one of Embodiments 154-156, wherein activation of the rWGS catalyst is carried out at a temperature in the range of 200°C to 800°C (for example, in the range of 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C).

[0421] Embodiment 158. The method of any one of Embodiments 154-157, wherein activation of the rWGS catalyst provides a catalyst that is at least 10% reduced (eg, at least 25%, or 50% reduced).

[0422] Embodiment 159. The method of any one of Embodiments 1-158, wherein the first product stream comprises no more than 95 mol % CO 2 (e.g. no more than 90 mol % CO 2 ).

[0423] Embodiment 160. The method of any one of Embodiments 1-158, wherein the first product stream comprises no more than 85 mol % CO 2 (e.g. no more than 80 mol % CO 2 ).

[0424] Embodiment 161. The method of any one of Embodiments 1-158, wherein the first product stream comprises no more than 75 mol % CO 2 (e.g. no more than 70 mol % CO 2 ).

[0425] Embodiment 162. The method of any one of Embodiments 1-158, wherein the first product stream comprises 5-95 mol % CO 2%, for example, 5-90 mol%, or 5-85 mol%, or 5-80 mol%, or 5-75 mol%, or 5-70 mol%, or 10-95 mol%, or 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% of CO 2 .

[0426] Embodiment 163. The method of any one of Embodiments 1-162, wherein the first product stream contains no more than 20 mol% methane, for example, no more than 15 mol% methane.

[0427] Embodiment 164. The method of any one of Embodiments 1-162, wherein the first product feed stream contains no more than 10 mol% methane, for example, no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

[0428] Embodiment 165. The method of any one of Embodiments 1-164, wherein H in the first product stream 2 The ratio of O:CO is at most 100:1, for example at most 50:1, or at most 25:1, or at most 10:1.

[0429] Embodiment 166. The method of any one of Embodiments 1-164, wherein H in the first product stream 2 The ratio of CO to CO is in the range of 0.1:1 to 100:1 (e.g., in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0430] Embodiment 167. The method of any one of Embodiments 1-166, wherein the method further comprises separating the first product stream so as to recycle at least a portion of one or more components of the first product stream to the first feed stream.

[0431] Embodiment 168. The method of any one of Embodiments 1-167, wherein the method further comprises separating the first product stream so as to separate the CO 2At least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the feed stream is recycled to the first feed stream.

[0432] Embodiment 169. The method of any one of Embodiments 1-168, wherein the method further comprises separating the first product stream to separate H 2 At least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the feed stream is recycled to the first feed stream.

[0433] Embodiment 170. The method of any one of Embodiments 1-169, wherein the method comprises separating H from the first product stream. 2 and / or at least a portion of CO and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst.

[0434] Embodiment 171. The method of any one of Embodiments 1-170, wherein the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream.

[0435] Embodiment 172. The method of any one of Embodiments 1-171, wherein the first product stream comprises one or more light hydrocarbons (e.g., methane, ethane, propane).

[0436] Embodiment 173. The method of Embodiment 172 further comprises separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream.

[0437] Embodiment 174. The method of any one of Embodiments 1-173, wherein the method further comprises exchanging heat between at least a portion of the first product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the first product stream and heating at least a portion of the first feed stream.

[0438] Embodiment 175. The method of any one of Embodiments 1-174, wherein the method further comprises exchanging heat between at least a portion of the first product stream and a steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone.

[0439] Embodiment 176. The method of Embodiment 175, further comprising generating steam from the heat provided to the steam generating zone, and generating electricity from the steam.

[0440] Embodiment 177. The method of Embodiment 175 or 176, wherein the steam is used to heat the first feed stream and / or the second feed stream.

[0441] Embodiment 178. The method of any one of Embodiments 1-177, wherein at least 25% of the CO of the first product stream, for example, at least 50% of the CO, at least 75% of the CO, or at least 90% of the CO of the first product stream is contained in the second feed stream.

[0442] Embodiment 179. The method of any one of Embodiments 1-178, wherein CO is provided to the second feed stream from a CO source other than the first product stream.

[0443] Embodiment 180. The method of any one of Embodiments 1-179, wherein the first product stream comprises H 2 , and wherein the second feed stream comprises H of the first product stream 2 at least a portion of.

[0444] Embodiment 181. The method of any one of Embodiments 1-180, wherein the H of the first product stream is 2 At least 25% of the H 2 At least 50% of H 2 At least 75% of H 2 At least 90% of the total weight of the catalyst is contained in the second feed stream.

[0445] Embodiment 182. The method of any one of Embodiments 1-181, wherein H is provided to the second feed stream from a hydrogen source other than the first product stream. 2 .

[0446] Embodiment 183. The method of any one of Embodiments 1-182, wherein the second feed stream comprises at least a portion of the CO of the first product stream. 2 .

[0447] Embodiment 184. The method of any one of Embodiments 1-183, wherein the CO of the first product stream 2 at least 10% of the CO of the first product stream, for example 2 At least 25% of CO 2 At least 50% of CO 2 At least 75% of CO 2 At least 90% of the total mass fraction is contained in the second feed stream.

[0448] Embodiment 185. The method of any one of Embodiments 1-183, wherein the second feed stream does not contain a significant amount of CO of the first product stream. 2 .

[0449] Embodiment 186. The method of any one of Embodiments 1-185, wherein the portion of the first product stream contained in the second feed stream has an H ratio in the range of 0.5:1 to 10:1, such as in the range of 1:1 to 3:1. 2 :CO ratio.

[0450] Embodiment 187. The method of any one of Embodiments 1-186, wherein the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, for example, or no more than 2 mol%, or no more than 0.5 mol%.

[0451] Embodiment 188. The method of any one of Embodiments 1-187, wherein the portion of the first product stream contained in the second feed stream has a CO content of between 10 and 95 mol %. 2 %, for example 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% of CO 2 The range of CO 2 content.

[0452] Embodiment 189. The method of any one of Embodiments 1-188, wherein the second feed stream has an H ratio in the range of 0.5:1 to 6:1. 2 :CO ratio.

[0453] Embodiment 190. The method of any one of Embodiments 1-188, wherein the second feed stream has an H ratio in the range of 1:1 to 3:1, for example, 1:1 to 2.5:1. 2 :CO ratio.

[0454] Embodiment 191. The method of any one of Embodiments 1-188, wherein the second feed stream has an H ratio of at least 1.4:1, for example, in the range of 1.4:1 to 3:1, or 1.4:1 to 2.5:1. 2 :CO ratio.

[0455] Embodiment 192. The method of any one of Embodiments 1-191, wherein the second feed stream comprises up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% of one or more inerts.

[0456] Embodiment 193. The method of any one of Embodiments 1-191, wherein the second feed stream comprises up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% of one or more selected from CO 2 , methane and nitrogen.

[0457] Embodiment 194. The method of any one of Embodiments 1-193, wherein the second feed stream comprises up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% CO 2 .

[0458] Embodiment 195. The method of any one of Embodiments 1-194, wherein the second feed stream has a water content of no more than 10 mol%, eg, or no more than 2 mol%, or no more than 0.5 mol%.

[0459] Embodiment 196. The method of any one of Embodiments 1-195, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0460] Embodiment 197. The method of any one of Embodiments 1-195, wherein the Fischer-Tropsch catalyst contains cobalt in an amount in the range of 5-25 wt%, calculated as Co(0), for example 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt%.

[0461] Embodiment 198. The method of any one of Embodiments 1-195, wherein the Fischer-Tropsch catalyst contains iron in an amount in the range of 5-95 wt%, calculated as Fe(0), for example 10-95 wt%, or 25-95 wt%, or 50-95 wt%, or 5-85 wt%, or 10-85 wt%, or 25-85 wt%, or 50-85 wt%, or 5-75 wt%, or 10-75 wt%, or 25-75 wt%.

[0462] Embodiment 199. The method of any one of Embodiments 196-198, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0463] Embodiment 200. The method of Embodiment 199, wherein manganese is present in an amount of up to 15 wt%, calculated as Mn(0), such as up to 12 wt%, or up to 10 wt%, or up to 7 wt%, or in a range of 0.1-15 wt%, such as 0.1-10 wt%, or 0.1-5 wt%, 0.5-15 wt%, or 0.5-10 wt%, or 0.5-5 wt%.

[0464] Embodiment 201. The method of any one of Embodiments 1-200, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the carrier comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide, and zinc oxide.

[0465] Embodiment 202. The method of any one of Embodiments 1-200, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0466] Embodiment 203. The method of any one of Embodiments 1-200, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titanium dioxide support.

[0467] Embodiment 204. The method of any one of Embodiments 1-203, wherein the Fischer-Tropsch catalyst is activated by contact with a reducing gas, such as hydrogen.

[0468] Embodiment 205. The method of Embodiment 204, wherein the reducing gas comprises at least a portion of the hydrogen from the first product feed stream.

[0469] Embodiment 206. The method of any one of Embodiments 1-203, wherein the Fischer-Tropsch catalyst is reacted with H 2 Activated by contact with CO.

[0470] Embodiment 207. The method of Embodiment 206, wherein the reducing gas comprises H from the first product stream.2 and at least a portion of CO.

[0471] Embodiment 208. The method of any one of Embodiments 204-206, wherein the activation is performed at a temperature in the range of 200-400°C.

[0472] Embodiment 209. The method of any one of Embodiments 1-208, wherein the second temperature is in the range of 150-400°C (for example, in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0473] Embodiment 210. The method of any one of Embodiments 1-209, wherein the second temperature is in the range of 200-350°C.

[0474] Embodiment 211. The method of any one of Embodiments 1-210, wherein the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

[0475] Embodiment 212. The method of any one of Embodiments 1-210, wherein the first temperature is at least 100°C higher than the second temperature, for example at least 150°C higher than the second temperature, or at least 200°C higher than the second temperature.

[0476] Embodiment 213. The method of any one of Embodiments 1-212, wherein the second pressure is in the range of 10-50 bar (e.g., 20-50 bar, or 25-50 bar, or 10-40 bar, or 20-40 bar, or 25-40 bar, or 10-35 bar, or 20-35 bar, or 25-35 bar).

[0477] Embodiment 214. The method of any one of Embodiments 1-213, wherein the second pressure is in the range of 20-50 bar.

[0478] Embodiment 215. The method of any one of Embodiments 1-214, wherein the Fischer-Tropsch reaction is carried out at a temperature of 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h-1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0479] Embodiment 216. The method of any one of Embodiments 1-215, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% C 5+ Selective.

[0480] Embodiment 217. The method of any one of Embodiments 1-216, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ The selectivity of alkanes is carried out.

[0481] Embodiment 218. The method of any one of Embodiments 1-217, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ Alkanes and C 5+ The selectivity of alcohol is carried out.

[0482] Embodiment 219. The method of any one of Embodiments 1-218, further comprising separating at least a portion of the water from the second product stream.

[0483] Embodiment 220. The method of any one of Embodiments 1-219, further comprising separating at least a portion of C from the second product stream. 1 -C 4 Hydrocarbons to provide a light hydrocarbon stream.

[0484] Embodiment 221. The method of Embodiment 220 further comprises including at least a portion of a light hydrocarbon stream in the first feed stream and / or the second feed stream.

[0485] Embodiment 222. The method of Embodiment 220 or Embodiment 221 further comprises oxidizing at least a portion of the light hydrocarbon stream to provide a 2 A pOX stream is provided and at least a portion of the pOX stream is included in the first feed stream and / or the second feed stream.

[0486] Embodiment 223. The method of any one of Embodiments 220-222, further comprising reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon stream to provide a 2 and including at least a portion of the reformed stream in the first feed stream and / or the second feed stream.

[0487] Embodiment 224. The method of Embodiment 222 or Embodiment 223, wherein the oxidation or reforming provides energy, thermal energy or electrical energy.

[0488] Embodiment 225. The method of any one of Embodiments 220-224 further comprises combusting at least a portion of the light hydrocarbon stream to provide energy, such as heat or electricity.

[0489] Embodiment 226. The method of Embodiment 225, wherein thermal energy is provided and the thermal energy is used to heat the first feed stream.

[0490] Embodiment 227. The method of any one of Embodiments 1-226, wherein the method further comprises exchanging heat between at least a portion of the second product stream and a steam generating zone, thereby cooling at least a portion of the first feed stream and providing heat to the steam generating zone.

[0491] Embodiment 228. The method of Embodiment 227 further comprises generating steam from heat provided to the steam generating zone, and generating electricity from the steam.

[0492] Embodiment 229. The method of Embodiment 227 or 228, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0493] Embodiment 230. The method of any one of Embodiments 1-229, wherein the method further comprises exchanging heat between at least a portion of the second product stream and at least a portion of the second feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the second feed stream.

[0494] Embodiment 231. The method of any one of Embodiments 1-230 further comprises: 2 At least a portion of is recycled to the second feed stream.

[0495] Embodiment 232. The method of any one of Embodiments 1-231, further comprising: 2 At least a portion of is recycled to the first feed stream.

[0496] Embodiment 233. The method of Embodiment 232 further comprises: 2 The source provides H to the second feed stream 2 .

[0497] Embodiment 234. The method of Embodiment 233, wherein the H from the second product stream 2 The H that constitutes the first feed stream 2 The majority of the first feed stream, for example H 2 At least 90%, at least 95%, or at least 98% of the total amount of the poly(vinyl alcohol) contained in the poly(vinyl alcohol) product.

[0498] Embodiment 235. The method of any one of Embodiments 1-234, further comprising recycling at least a portion of the CO of the second product stream to the second feed stream.

[0499] Embodiment 236. The method of any one of Embodiments 1-235 further comprises recycling at least a portion of the CO of the second product stream to the first feed stream.

[0500] Embodiment 237 The method of any one of Embodiments 1-236, further comprising recycling at least a portion of the inerts of the second product stream to the second feed stream.

[0501] Embodiment 238 The method of any one of Embodiments 1-237, further comprising recycling at least a portion of the inerts of the second product stream to the first feed stream.

[0502] Embodiment 239. The method of any one of Embodiments 1-238 further comprises: 2 At least a portion of is recycled to the first feed stream.

[0503] Embodiment 240. The method of Embodiment 239 further comprises: 2 The source provides CO to the second feed stream 2 .

[0504] Embodiment 241. The method of Embodiment 240, wherein the CO from the second product stream 2 CO constituting the first feed stream 2 The majority of the first feed stream, for example CO 2 At least 90%, at least 95%, or at least 98% of the total amount of the poly(vinyl alcohol) contained in the poly(vinyl alcohol) product.

[0505] Embodiment 242. The method of any one of Embodiments 1-241, wherein the C of the second product stream 5+At least a portion of the hydrocarbons provides one or more products.

[0506] Embodiment 243. The method of Embodiment 242, wherein the one or more products include fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants, and waxes.

[0507] Embodiment 244. The method of any one of Embodiments 1-243, further comprising hydrotreating the C of the second product stream. 5+ at least a portion of a hydrocarbon.

[0508] Embodiment 245. The method of any one of Embodiments 1-244, wherein the CO of the first feed stream and / or the second feed stream is 2 At least a portion of the energy derived from renewable sources.

[0509] Embodiment 246. The method of any one of Embodiments 1-245, wherein the CO of the first feed stream and / or the second feed stream is 2 At least a portion of the gas is obtained from direct air capture.

[0510] Embodiment 247. The method of any one of Embodiments 1-246, wherein the CO of the first feed stream and / or the second feed stream is 2 At least a portion of the CO2 is captured from a manufacturing plant such as a bioethanol plant, a steel plant or a cement plant.

[0511] Embodiment 248. The method of any one of Embodiments 1-247, wherein the H of the first feed stream or the second feed stream is 2 At least a portion of the energy derived from renewable sources.

[0512] Embodiment 249. The method of any one of Embodiments 1-248, wherein the H of the first feed stream or the second feed stream is 2 At least part of the hydrogen is green hydrogen.

[0513] Embodiment 250. The method of any one of Embodiments 1-249, wherein the H of the first feed stream or the second feed stream is 2 At least part of it is blue hydrogen.

[0514] Embodiment 251. The method of any one of Embodiments 1-250, wherein the H of the first feed stream or the second feed stream is 2 At least a portion of is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0515] Embodiment 252. The method of any one of Embodiments 1-251, further comprising providing at least a portion of H to the first feed stream and / or the second feed stream by electrolysis of water. 2 .

[0516] Embodiment 253. The method of Embodiment 252, wherein the electrolysis of water is performed at least in part using electricity from a renewable source.

[0517] Embodiment 254. The method of Embodiment 252 or Embodiment 253, wherein the electrolysis of water is carried out at least in part using electricity generated by steam produced by heat exchange from the first product stream and / or the second product stream or by combustion of a light hydrocarbon stream.

[0518] Embodiment 255. The method of any one of Embodiments 252-254 further comprises: 2 At least a portion of is provided to partial oxidation.

[0519] Embodiment 256. The method of any one of Embodiments 1-255, wherein the method is carried out in a reactor system comprising a first reactor in which a reverse water gas shift catalyst is disposed and a second reactor in which a Fischer-Tropsch catalyst is disposed.

[0520] Embodiment 257. The method of any one of Embodiments 1-255, wherein the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein a second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0521] Embodiment 258. The method described in Embodiment 257, wherein the first reactor bed and the second reactor bed are arranged in the same reactor.

[0522] Embodiment 259. The method of any one of Embodiments 1-255, wherein the method is performed in a reactor system comprising a first catalyst container having one or more reverse water gas shift catalysts disposed therein, and wherein the second reaction zone comprises a second catalyst container having one or more Fischer-Tropsch catalysts disposed therein.

[0523] Embodiment 260. The method of Embodiment 259, wherein the one or more first catalyst containers and the one or more second catalyst containers are disposed in the same reactor.

[0524] Embodiment 261. The method of any one of Embodiments 1-260, wherein the method is carried out in a reactor system comprising a reactor comprising a reverse water gas shift catalyst and a Fischer-Tropsch catalyst, for example, disposed therein in admixture.

[0525] The details shown herein are presented as examples only and for the purpose of illustrative discussion of the preferred embodiments of the present invention, and are presented in order to provide the most useful and easily understood descriptions of the principles and concepts of the various embodiments of the present invention. In this regard, no attempt is made to show the structural details of the present invention in more detail than is required for a basic understanding of the present invention. The description in conjunction with the drawings and / or embodiments makes it clear to those skilled in the art how several forms of the present invention can be embodied in practice. Thus, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, equipment or configurations, and therefore can certainly vary. It should also be understood that the terms used herein are only used for the purpose of describing specific aspects, and are not intended to be restrictive unless specifically defined herein.

[0526] The terms "a", "an", "the" and similar referents used in the context of describing the present invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of numerical ranges herein is intended merely to serve as a shorthand process for individually referring to each individual value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into this specification as if it were individually referenced herein. It will be further understood that the endpoints of each range are significant both relative to the other endpoint and independently of the other endpoint.

[0527] Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order of steps. The use of any and all embodiments or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the present invention, rather than to limit the scope of the present invention otherwise claimed. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the present invention.

[0528] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise", "comprising", etc. should be interpreted in an inclusive sense and not in an exclusive or exhaustive sense; that is, in the sense of "including but not limited to". Words using the singular or plural number also include the plural and singular, respectively. In addition, when used in this application, the words "herein", "above", and "below" and words of similar meaning shall refer to this application as a whole and not to any particular parts of this application.

[0529] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of the elements, steps, ingredients, or components specifically stated therein. As used herein, the transitional terms "comprise" or "comprises" are meant to include, but are not limited to, and allow for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of excludes any elements, steps, ingredients, or components that are not specified. The transitional phrase "consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiment.

[0530] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0531] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0532] The grouping of the alternative elements of the present invention disclosed herein or embodiments should not be construed as limiting. Each group member can be mentioned and claimed individually or in any combination with other members of the group or other elements found herein. For reasons of convenience and / or patentability, it is contemplated that one or more members in the group may be included in the group or deleted from the group. When any such inclusion or deletion occurs, this specification is considered to contain the group modified, thereby satisfying the written specifications of all Markush groups used in the appended claims.

[0533] Some embodiments of the present invention are described herein, including the best mode of implementing the present invention known to the inventor. Of course, after reading the foregoing description, changes in the embodiments described will become apparent to those of ordinary skill in the art. The inventor expects those skilled in the art to appropriately adopt these changes, and the inventor intends to practice the present invention in a manner different from that specifically described herein. Therefore, the present invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, the present invention encompasses any combination of the above-mentioned elements in all possible variations thereof.

[0534] In addition, it should be understood that the embodiments of the present invention disclosed herein illustrate the principles of the present invention. Other modifications that may be adopted are within the scope of the present invention. Therefore, by way of example and not limitation, alternative configurations of the present invention may be utilized according to the teachings herein. Therefore, the present invention is not limited to what is precisely shown and described.

Claims

1. A method for performing a reverse water gas shift reaction, the method comprising: contacting a supported reverse water gas shift catalyst with a feed stream comprising CO2 and H2 at a temperature in the range of 200-900°C to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream; The catalyst comprises: a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia; at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

2. The method of claim 1, wherein the reverse water gas shift reaction has a CO selectivity of at least 95%, such as at least 96%.

3. The method of claim 1, wherein the reverse water gas shift reaction has a methane selectivity of not more than 5%, such as not more than 4%.

4. The method of claim 1, having a CO2 conversion of at least 30%, such as at least 40%.

5. The method of claim 1, having a CO2 conversion of no more than 90%, such as no more than 80%, or no more than 70%.

6. The method of claim 1, carried out at a temperature in the range of 550-800°C, such as in the range of 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.

7. The process of claim 1, wherein the molar ratio of H2 to CO2 in the feed stream is in the range of 0.5:1 to 10:

1.

8. The method of claim 1, wherein the product stream comprises no more than 75 mol % CO2 (e.g., no more than 70 mol % CO2).

9. The process of claim 1, wherein the product stream further comprises CO2, and wherein the process further comprises recycling at least a portion of the CO2 of the product stream to the feed stream.

10. The process of claim 1, wherein the product stream further comprises hydrogen, and wherein the process further comprises recycling at least a portion of the hydrogen of the product stream to the feed stream.

11. The process of claim 1, wherein the product stream comprises no more than 20 mole % methane, such as no more than 15 mole % methane.

12. The process of claim 1, wherein the product stream comprises no more than 10 mol% methane, such as no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

13. A method for performing an integrated Fischer-Tropsch process, the method comprising: Providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream; contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a product comprising C 5+ a second product stream of hydrocarbons, The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising: a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia; at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

14. The process of claim 13, wherein the support comprises at least 70% by weight of the catalyst, calculated on an oxide basis.

15. The method of claim 13, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 2 wt. %, based on the total weight of the catalyst.

16. The method of claim 13, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 2 wt %, based on the total weight of the catalyst.

17. The method of claim 13, wherein gold is present in the catalyst in an amount ranging from 0.05 to 2 weight percent based on the total weight of the catalyst.

18. The method of claim 13, wherein manganese is present in the catalyst in an amount ranging from 2 to 20 weight percent based on the total weight of the catalyst.

19. The method of claim 13, wherein the ratio of platinum, palladium and / or gold to manganese is in the range of 0.05:1 to 1:

1.

20. The process of claim 13, wherein the molar ratio of H2 to CO2 in the first feed stream ranges from 0.5:1 to 10:

1.

21. The method of claim 13, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%.

22. The method of claim 13, wherein the method comprises activating the reverse water gas shift catalyst with a reducing feed stream comprising a reducing gas.

23. The process of claim 13, wherein the first product stream comprises no more than 75 mol% CO2.

24. The process of claim 13, wherein the first product stream comprises no more than 5 mol% methane.

25. The process of claim 13, wherein at least 25% of the CO of the first product stream is contained in the second feed stream.

26. The process of claim 13, wherein the first product stream comprises H2, and wherein at least 25% of the H2 of the first product stream is contained in the second feed stream.

27. The process of claim 13, wherein at least 10% of the CO2 of the first product stream is contained in the second feed stream.

28. The process of claim 13, wherein the second feed stream does not contain a significant amount of CO2 of the first product stream.

29. The process of claim 13, wherein the second feed stream has a H2:CO ratio in the range of 0.5:1 to 6:

1.

30. The method of claim 13, wherein the second temperature is in the range of 200-350°C.

31. The method of claim 13, wherein the first temperature is at least 100°C higher than the second temperature.

32. The process of claim 13, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide a second product stream having a carbon content of at least 30%. 5+ The selectivity of alkanes is carried out.

33. The method of claim 13, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

34. The method of claim 13, wherein the method further comprises exchanging heat between at least a portion of the second product stream and at least a portion of the second feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the second feed stream.

35. The method of claim 13, further comprising recycling at least a portion of the H2 of the second product stream to the second feed stream.

36. The process of claim 13, further comprising recycling at least a portion of the H2 of the second product stream to the first feed stream, wherein the H2 from the second product stream constitutes at least 90% of the H2 of the first feed stream.

37. The process of claim 13, further comprising recycling at least a portion of the CO of the second product stream to the second feed stream or the first feed stream.

38. The method of claim 13, further comprising recycling at least a portion of the CO2 of the second product stream to the first feed stream, wherein the CO2 from the second product stream constitutes at least 90% of the CO2 of the first feed stream.

39. A supported reverse water gas shift catalyst comprising: a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia; at least one of platinum, palladium, and gold, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

40. The catalyst of claim 39, wherein at least the surface layer of the ceria support comprises at least 90 wt% ceria, such as at least 95 wt% ceria, or at least 98 wt% ceria, based on oxide.

41. The catalyst of claim 39, wherein the total amount of cerium, titanium, aluminum, zirconium, manganese, platinum, palladium and gold in the catalyst, based on the metals, is at least 90 wt %, e.g., at least 95 wt %, or at least 98 wt % of the catalyst.

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