Catalyst for reverse water gas shift and integrated fischer-tropsch process

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; a co-catalyst metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium and zirconium, present in an amount ranging from 0.5 to 20 wt% of the catalyst, based on the total weight of the catalyst; and optionally at least one of platinum, palladium or gold, present in an amount ranging from 0.05 to 10 wt% of the catalyst, based on the total weight of the catalyst.

Description

[0001] Background of this disclosure 1. Field This disclosure generally relates to a reverse water-gas shift catalyst, its preparation method, and a method for carrying out a reverse water-gas shift reaction. This disclosure also relates to integrating a method for carrying out a reverse water-gas shift reaction with a method for carrying out a Fischer-Tropsch reaction.

[0002] 2. Technical Background Reverse water-gas shift reaction (rWGS) is an advantageous 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 formula (1).

[0003] Reaction formula (1) This can be used, for example, to change the CO:H2 ratio of a gas mixture for further processing. The resulting carbon monoxide and hydrogen are valuable feedstocks for many chemical processes, such as the well-known Fischer-Tropsch (FT) process as shown in reaction (2).

[0004] Reaction formula (2) However, the rWGS reaction is not dominant in all cases. For example, the competing reaction is the Sabatil reaction (reaction (3)), which reduces the carbon monoxide yield and favors methane production, which is not an active feedstock for FT.

[0005] Reaction formula (3) At lower reaction temperatures, the strongly exothermic Sabatier reaction is thermodynamically superior to the endothermic rWGS reaction. Therefore, minimizing methanation in the rWGS process, especially at low temperatures, can be a significant challenge.

[0006] Similarly, carbon monoxide products from rWGS can be hydrogenated to methane as shown in reaction (4).

[0007] Reaction formula (4) The hydrogenation of carbon monoxide to methane is also an exothermic reaction, and therefore it is dominant at lower temperatures. The stoichiometry of the reaction requires a hydrogen-to-carbon monoxide ratio of at least 3:1. This means that using a large excess of hydrogen to drive the equilibrium toward carbon monoxide (see reaction (1)) is not always ideal, as it carries the risk of hydrogenating the carbon monoxide product to form methane.

[0008] Combining reactions (3) and (4), further undesirable side reactions may occur. These side reactions can 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 predominate at higher temperatures, just like the rWGS reaction.

[0009] Therefore, since the carbon production side reaction (reactions (5)-(7)) is also endothermic and predominates at higher temperatures, operating at higher temperatures to favor the desired carbon monoxide product may severely affect catalyst lifetime through carbon deposition.

[0010] Given the multiple reactions and competing thermodynamics at play, there remains a need in the field for new rWGS catalysts and methods, especially those integrated with the Fischer-Tropsch process. Summary of the Invention

[0011] In one aspect, this disclosure provides a supported reverse water gas shift catalyst, comprising: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst.

[0012] In one aspect, this disclosure provides a supported reverse water gas shift catalyst, comprising: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold, present in an amount ranging from 0.05 to 10% by weight of the catalyst based on the total weight of the catalyst.

[0013] In another aspect, this disclosure provides a method for preparing the catalyst as described herein, the method comprising: A carrier is provided, wherein the carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide; The carrier is brought into contact with one or more liquids, each of which contains one or more compounds containing a co-catalyst metal dispersed in a solvent, and optionally one or more compounds containing platinum, palladium, or gold, wherein the co-catalyst metal is selected from gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium. Allowing the solvent to evaporate to provide a catalyst precursor; and The catalyst precursor is calcined.

[0014] In another respect, this disclosure provides catalysts as described herein, prepared by the methods described herein.

[0015] In another aspect, this disclosure provides a method for carrying out a reverse water-gas shift reaction, the method comprising contacting a catalyst as described herein with a feed stream containing CO2 and H2 at a temperature in the range of 250-900°C to provide a product stream containing CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0016] In one aspect, this disclosure provides a method for performing integrated Fischer-Tropsch method, the method comprising: Provide a first feed stream containing H2 and CO2; The reverse water gas shift catalyst is contacted with the first feed stream at a first temperature in the range of 250-900°C and a first pressure to carry out the reverse water gas shift reaction, so as to provide a first product stream containing CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream containing H2 and at least a portion of the first product stream at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons, The aforementioned countercurrent gas shift catalyst is a supported countercurrent gas shift catalyst, which comprises: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst. Attached Figure Description

[0017] The accompanying drawings are included to provide a further understanding of the methods of this disclosure, and are incorporated in 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 drawings illustrate one or more embodiments of this disclosure and, together with the specification, serve to explain the principles and operation of this disclosure.

[0018] Figure 1 This is a schematic diagram of the reverse water-gas shift reaction as described in this article.

[0019] Figure 2 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article.

[0020] Figure 3 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article.

[0021] Figure 4 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article.

[0022] Figure 5 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article.

[0023] Figure 6 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article.

[0024] Figure 7 This is a schematic diagram of the method for performing the integrated Fehling-Tropsch method as described in this article. Detailed Implementation

[0025] As described above, the reverse water-gas shift reaction (rWGS) 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 processes such as the Fischer-Tropsch process. However, the Sabatil reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction. The Sabatil reaction and CO methanation are exothermic and predominant at lower temperatures, while rWGS and the carbon-producing side reactions are endothermic and predominant at higher temperatures. Therefore, there remains a need for rWGS catalysts that can provide good performance despite these complexities. Here, the inventors have provided a supported rWGS catalyst comprising a metal oxide support, a cocatalyst metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, and optionally at least one of platinum, palladium, and gold. Furthermore, the inventors have found that the rWGS method is particularly advantageous for integration with the Fischer-Tropsch process using a supported rWGS catalyst as described herein.

[0026] Counter-current gas shift catalyst In one aspect, this disclosure provides a supported reverse water-gas shift catalyst comprising: a support, which is a cerium oxide support, a titanium oxide support, an alumina support, a zirconium oxide support, or a mixed oxide support comprising two or more of cerium oxide, titanium oxide, alumina, and zirconium oxide; a co-catalyst metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount ranging from 0.5% to 20% by weight of the catalyst based on the total weight of the catalyst; and optionally at least one of platinum, palladium, or gold, present in an amount ranging from 0.05% to 10% by weight of the catalyst based on the total weight of the catalyst.

[0027] In another aspect, this disclosure provides a supported reverse water-gas shift catalyst comprising: a support, which is a cerium oxide support, a titanium oxide support, an alumina support, a zirconium oxide support, or a mixed oxide support comprising two or more of cerium oxide, titanium oxide, alumina, and zirconium oxide; a co-catalyst metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, present in an amount ranging from 0.5% to 20% by weight of the catalyst based on the total weight of the catalyst; and at least one of platinum, palladium, or gold, present in an amount ranging from 0.05% to 10% by weight of the catalyst based on the total weight of the catalyst.

[0028] As described above, the reverse water gas shift catalyst of this disclosure is a supported catalyst. In various embodiments described separately herein, the support constitutes at least 70% by weight of the catalyst, for example, at least 75% by weight, or 80% by weight, or 85% by weight, or 90% by weight, based on oxides.

[0029] In various embodiments as described separately herein, the support is a cerium oxide support. As used herein, a "cerium oxide" support is a support exhibiting at least a surface layer (e.g., 50 micrometers thick) of at least 50 wt% cerium oxide based on oxides. In various embodiments of this disclosure as described herein, the at least 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. In some such embodiments, the at least surface layer of the cerium oxide support comprises at least 90 wt% cerium oxide. For example, in some embodiments, the at least surface layer of the cerium oxide support comprises at least 95 wt% cerium oxide or at least 98 wt% cerium oxide. In various instances, the cerium oxide support contains substantially diffuse cerium oxide, for example, at least 50 wt% of the cerium oxide support is cerium oxide based on oxides. For example, in various embodiments, 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. In various embodiments, the cerium oxide support comprises at least 90% by weight of cerium oxide, such as at least 95% by weight or at least 98% by weight of cerium oxide. In some embodiments, the cerium oxide support may further comprise additional metals or metal oxides.

[0030] In various embodiments as described separately herein, the support is a titanium oxide support. As used herein, a "titanium oxide" support is a support exhibiting at least a surface layer (e.g., 50 micrometers thick) of at least 50 wt% titanium oxide based on oxides. In various embodiments of this disclosure as described herein, the at least surface layer of the titanium oxide support comprises at least 60 wt% titanium oxide, such as at least 70 wt% or at least 80 wt% titanium oxide. In some such embodiments, the at least surface layer of the titanium oxide support comprises at least 90 wt% titanium oxide. For example, in some embodiments, the at least surface layer of the titanium oxide support comprises at least 95 wt% or at least 98 wt% titanium oxide. In various instances, the titanium oxide support contains substantially diffuse titanium oxide, for example, at least 50 wt% of the titanium oxide support is titanium oxide based on oxides. For example, in various embodiments, the titanium oxide support comprises at least 60 wt% titanium oxide, such as at least 70 wt% or at least 80 wt% titanium oxide. In various embodiments, the titanium oxide support comprises at least 90% by weight of titanium oxide, such as at least 95% by weight or at least 98% by weight. In some embodiments, the titanium oxide support may further comprise additional metals or metal oxides.

[0031] In various embodiments as described separately herein, the carrier is an alumina carrier. As used herein, an "alumina" carrier is a carrier exhibiting at least a surface layer (e.g., 50 micrometers thick) of at least 50 wt% alumina based on oxides. In various embodiments of this disclosure as described herein, the at least surface layer of the alumina carrier comprises at least 60 wt% alumina, such as at least 70 wt% or at least 80 wt% alumina. In some such embodiments, the at least surface layer of the alumina carrier comprises at least 90 wt% alumina. For example, in some embodiments, the at least surface layer of the alumina carrier comprises at least 95 wt% or at least 98 wt% alumina. In various instances, the alumina carrier contains substantially diffuse alumina, for example, at least 50 wt% of the alumina carrier is alumina based on oxides. For example, in various embodiments, the alumina carrier comprises at least 60 wt% alumina, such as at least 70 wt% or at least 80 wt% alumina. In various embodiments, the alumina support comprises at least 90% by weight of alumina, such as at least 95% by weight or at least 98% by weight of alumina. In some embodiments, the alumina support may further comprise additional metals or metal oxides.

[0032] In various embodiments as described separately herein, the support is a zirconia support. As used herein, a "zirconia" support is a support exhibiting at least a surface layer (e.g., 50 micrometers thick) of at least 50 wt% zirconia based on oxides. In various embodiments of this disclosure as described herein, the at least surface layer of the zirconia support comprises at least 60 wt% zirconia, such as at least 70 wt% zirconia, or at least 80 wt% zirconia. In some such embodiments, the at least surface layer of the zirconia support comprises at least 90 wt% zirconia. For example, in some embodiments, the at least surface layer of the zirconia support comprises at least 95 wt% zirconia or at least 98 wt% zirconia. In various instances, the zirconia support contains substantially diffuse zirconia, for example, at least 50 wt% of the zirconia support is zirconia based on oxides. For example, in various embodiments, the zirconia support comprises at least 60 wt% zirconia, such as at least 70 wt% zirconia, or at least 80 wt% zirconia. In various embodiments, the zirconia support comprises at least 90% by weight of zirconia, such as at least 95% by weight or at least 98% by weight of zirconia. In some embodiments, the zirconia support may further comprise additional metals or metal oxides.

[0033] In various embodiments as described separately herein, the support is a mixed oxide support. These can be provided, for example, by doping multiple of the aforementioned oxides and forming a support comprising both. For example, in some embodiments, the mixed oxide support 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 oxides, at least the surface layer of the support comprises a total of at least 50% by weight of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In some embodiments, at least the surface layer of the mixed oxide support comprises a total of at least 60% by weight, for example, at least 70% by weight, or at least 80% by weight of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In some embodiments, at least the surface layer of the mixed oxide support comprises at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In various instances, the mixed oxide support contains substantially distributed oxides, for example, at least 50% by weight of the mixed oxide support is two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In various embodiments, the mixed oxide support comprises a total of at least 60% by weight, for example, at least 70% by weight, or at least 80% by weight, two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In various embodiments, the mixed oxide support comprises a total of at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight, two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In some embodiments, the mixed oxide support may further comprise additional metals or metal oxides.

[0034] 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 this disclosure as described separately herein, the support does not contain more than 2% by weight of additional metals, for example, more than 1% by weight or more than 0.5% by weight, based on oxides.

[0035] However, the inventors have noted that in many cases, performance can be desirablely affected by including other metals in the carrier. Therefore, in other embodiments as described separately herein, the carrier contains at least one additional metal. In various embodiments, the total amount of the at least one additional metal, based on oxides, is in the range of 0.5-20% by weight, for example 1-20% by weight, or 2-20% by weight, or 0.5-15% by weight, or 1-15% by weight, or 2-15% by weight, or 0.5-10% by weight, or 1-10% by weight, or 2-10% by weight, or 0.5-5% by weight, or 1-5% by weight.

[0036] The supports used herein can be provided with a range of pore volumes. Those skilled in the art will select a pore volume suitable for the desired catalytic method. For example, in various embodiments further described herein, the pore volume is at least 0.05 mL / g, such as at least 0.1 mL / g. In various embodiments further described herein, the pore volume is at most 1.5 mL / g, such as at most 1 mL / g. In various embodiments of this disclosure as described herein, the pore volume is in the range of 0.05-1.5 mL / g, such as from 0.1 mL / g to 1 mL / g. The pore volume is measured by the mercury porosity method, for example, according to ASTM D4284-12.

[0037] As described above, the supported reverse water-gas shift catalyst of this disclosure comprises a co-catalyst metal selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium. In some embodiments, the co-catalyst metal is selected from one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium. The inventors have determined that the inclusion of a co-catalyst metal in the catalyst can improve the CO selectivity of the rWGS reaction, as described in the examples below. For the purposes of this disclosure, the amount of co-catalyst metal present is calculated as a weight percentage of co-catalyst atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which the co-catalyst metal may be present. The co-catalyst metal can be present in the catalyst in various forms; most commonly, the co-catalyst metal is present primarily as a metal oxide, a metal, or a combination thereof.

[0038] In various embodiments of this disclosure as further described herein, gallium is present in the catalyst in an amount ranging from 0.5% to 20% by weight, based on the total weight of the catalyst. For example, in various embodiments, gallium is present in the catalyst in an amount ranging from 0.5% to 15%, or 0.5% to 12%, or 0.5% to 10% by weight, based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, gallium is present in the catalyst in an amount ranging from 1% to 20% by weight (e.g., from 1% to 15%, or 1% to 12%, or 1% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, gallium is present in an amount ranging from 2% to 20% by weight (e.g., from 2% to 15%, or 2% to 12%, or 2% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, gallium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0039] In various embodiments of this disclosure as described herein, indium is present in the catalyst in an amount ranging from 0.5% to 20% by weight, based on the total weight of the catalyst. For example, in various embodiments, indium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, or 0.5% to 12% by weight, or 0.5% to 10% by weight, based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, indium is present in the catalyst in an amount ranging from 1% to 20% by weight (e.g., 1% to 15% by weight, or 1% to 12% by weight, or 1% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, indium is present in an amount ranging from 2% to 20% by weight (e.g., 2% to 15% by weight, or 2% to 12% by weight, or 2% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, indium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0040] In various embodiments of this disclosure as described separately herein, lanthanum is present in the catalyst in an amount ranging from 0.5 to 20 wt% based on the total weight of the catalyst. For example, in various embodiments, lanthanum is present in the catalyst in an amount ranging from 0.5 to 15 wt%, or 0.5 to 12 wt%, or 0.5 to 10 wt% based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, lanthanum is present in the catalyst in an amount ranging from 1 to 20 wt% (e.g., 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 this disclosure as described herein, lanthanum is present in an amount ranging from 2 to 20 wt% (e.g., 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 this disclosure as described herein, lanthanum is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0041] In various embodiments of this disclosure as further described herein, titanium is present in the catalyst in an amount ranging from 0.5% to 20% by weight, based on the total weight of the catalyst. For example, in various embodiments, titanium is present in the catalyst in an amount ranging from 0.5% to 15%, or 0.5% to 12%, or 0.5% to 10% by weight, based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, titanium is present in the catalyst in an amount ranging from 1% to 20% by weight (e.g., 1% to 15%, or 1% to 12%, or 1% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, titanium is present in an amount ranging from 2% to 20% by weight (e.g., 2% to 15%, or 2% to 12%, or 2% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, titanium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0042] In various embodiments of this disclosure as described herein, niobium is present in the catalyst in an amount ranging from 0.5% to 20% by weight, based on the total weight of the catalyst. For example, in various embodiments, niobium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, or 0.5% to 12% by weight, or 0.5% to 10% by weight, based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, niobium is present in the catalyst in an amount ranging from 1% to 20% by weight (e.g., 1% to 15% by weight, or 1% to 12% by weight, or 1% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, niobium is present in an amount ranging from 2% to 20% by weight (e.g., 2% to 15% by weight, or 2% to 12% by weight, or 2% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, niobium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0043] In various embodiments of this disclosure as described herein, vanadium is present in the catalyst in an amount ranging from 0.5 to 20 wt% based on the total weight of the catalyst. For example, in various embodiments, vanadium is present in the catalyst in an amount ranging from 0.5 to 15 wt%, or 0.5 to 12 wt%, or 0.5 to 10 wt% based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, vanadium is present in the catalyst in an amount ranging from 1 to 20 wt% (e.g., 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 this disclosure as described herein, vanadium is present in an amount ranging from 2 to 20 wt% (e.g., 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 this disclosure as described herein, vanadium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0044] In various embodiments of this disclosure as described herein, zirconium is present in the catalyst in an amount ranging from 0.5% to 20% by weight, based on the total weight of the catalyst. For example, in various embodiments, zirconium is present in the catalyst in an amount ranging from 0.5% to 15%, or 0.5% to 12%, or 0.5% to 10% by weight, based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, zirconium is present in the catalyst in an amount ranging from 1% to 20% by weight (e.g., 1% to 15%, or 1% to 12%, or 1% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, zirconium is present in an amount ranging from 2% to 20% by weight (e.g., 2% to 15%, or 2% to 12%, or 2% to 10% by weight), based on the total weight of the catalyst. In various embodiments of this disclosure as described herein, zirconium is present in an amount ranging from 4 to 20% by weight (e.g., from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight) based on the total weight of the catalyst.

[0045] As described above, the supported reverse water-gas shift catalyst of this disclosure optionally comprises at least one of platinum, palladium, and gold. For example, in various embodiments as described separately herein, platinum is present in the catalyst. For the purposes of this disclosure, the amount of platinum present is calculated as a weight percentage of platinum atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which 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 this disclosure as described herein, platinum is present in the catalyst in an amount ranging from 0.05 to 10 wt%, for example, from 0.1 to 10 wt%, or 0.5 to 10 wt%, 1 to 10 wt%, or 2 to 10 wt%, or 5 to 10 wt%, 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%, for example, 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. In some embodiments, platinum is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, 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. For example, in some embodiments of this disclosure as described herein, platinum is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, 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. In some embodiments, platinum 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 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 ranging from 0.05 to 1 wt%, for example, 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. In some embodiments, platinum is present in the catalyst in an amount ranging from 0.05 to 0.8% by weight, for example, from 0.1 to 0.8% by weight, or from 0.3 to 0.8% by weight, or from 0.5 to 0.8% by weight, based on the total weight of the catalyst.

[0046] In various embodiments as described separately herein, palladium is present in the catalyst. For the purposes of this disclosure, the amount of palladium present is calculated as a weight percentage of palladium atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which 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 this disclosure as described herein, palladium is present in the catalyst in an amount ranging from 0.05 to 10 wt%, for example, from 0.1 to 10 wt%, or 0.5 to 10 wt%, 1 to 10 wt%, or 2 to 10 wt%, or 5 to 10 wt%, 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 wt%, for example, 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. 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 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 this 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 0.3 to 2 wt%, or 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 0.3 to 1.5 wt%, or 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%, for example, 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. In some embodiments, palladium is present in the catalyst in an amount ranging from 0.05 to 0.8 wt%, for example, from 0.1 to 0.8 wt%, or from 0.3 to 0.8 wt%, or from 0.5 to 0.8 wt%, based on the total weight of the catalyst.

[0047] In various embodiments as described separately herein, gold is present in the catalyst. For the purposes of this disclosure, the amount of gold present is calculated as a weight percentage of gold atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which palladium 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 this disclosure as described herein, gold is present in the catalyst in an amount ranging from 0.05 to 10 wt%, for example, from 0.1 to 10 wt%, or 0.5 to 10 wt%, 1 to 10 wt%, or 2 to 10 wt%, or 5 to 10 wt%, 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 wt%, for example, 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. In some embodiments, gold is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, 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. For example, in some embodiments of this disclosure as described herein, gold is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, 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. In some embodiments, gold 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 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%, for example, 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. In some embodiments, gold is present in the catalyst in an amount ranging from 0.05 to 0.8% by weight, for example, from 0.1 to 0.8% by weight, or from 0.3 to 0.8% by weight, or from 0.5 to 0.8% by weight, based on the total weight of the catalyst.

[0048] Platinum, palladium, and / or gold, and the co-catalyst metal, can be provided in various weight ratios. For example, in some embodiments of this disclosure as described herein, the weight ratio of platinum, palladium, and / or gold in the catalyst to the co-catalyst metal is at least 0.05:1. For example, in various embodiments, the weight ratio of platinum, palladium, and / or gold to the co-catalyst metal is at least 0.1:1. In various embodiments of this disclosure as described herein, the weight ratio of platinum, palladium, and / or gold in the catalyst to the co-catalyst metal is at most 1:1. For example, the weight ratio of platinum, palladium, and / or gold to the co-catalyst metal is at most 0.5:1. For example, in various embodiments, the weight ratio of platinum, palladium, and / or gold in the catalyst to the co-catalyst metal ranges from 0.05:1 to 1:1. For example, the weight ratio of platinum, palladium and / or gold to the co-catalyst metal is in the range of 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.

[0049] The inventors have determined that a suitable reverse-flow gas shift catalyst can be formed from one or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide as a support, along with a co-catalyst metal contained within / on the catalyst and optionally platinum, palladium, and / or gold. As will be understood by those skilled in the art, the amounts of cerium, titanium, aluminum, zirconium, co-catalyst metal, and platinum, palladium, and / or gold (if present) can be quantified based on the metals, regardless of the form in which these metals may be present. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of the metals in the catalyst (i.e., based on the metals), without excluding oxygen or non-metallic counterions in the calculation. Thus, in various embodiments of this disclosure as described herein, the total amount of cerium, titanium, aluminum, zirconium, and co-catalyst metal in the catalyst, based on the metals, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight of the catalyst. For example, in some specific embodiments, the total amount of cerium and co-catalyst metal in the catalyst, based on the metals, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight of the catalyst. In other embodiments, the total amount of titanium and co-catalyst metal in the catalyst, based on metal content, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In other embodiments, the total amount of aluminum and co-catalyst metal in the catalyst, based on metal content, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In other embodiments, the total amount of zirconium and co-catalyst metal in the catalyst, based on metal content, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In various embodiments of this disclosure as described herein, the total amount of cerium, titanium, aluminum, zirconium, co-catalyst metal, platinum, palladium, and gold in the catalyst, based on metal content, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. For example, in some specific embodiments, the total amount of cerium, co-catalyst metal, platinum, palladium, and gold in the catalyst, based on metal content, is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In other embodiments, based on metal content, the total amount of titanium, co-catalyst metal, platinum, palladium, and gold in the catalyst is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In other embodiments, based on metal content, the total amount of aluminum, co-catalyst metal, platinum, palladium, and gold in the catalyst is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight. In other embodiments, based on metal content, the total amount of zirconium, co-catalyst metal, platinum, palladium, and gold in the catalyst is at least 90% by weight, for example, at least 95% by weight, or at least 98% by weight.

[0050] As described above, the supported catalyst comprises a co-catalyst metal and optionally at least one of platinum, palladium, and gold. Depending on the synthesis method, these substances, which are typically present primarily in metallic and / or oxide form, can be disposed at various 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, for example, when a large amount of impregnation solution is used, or only in the surface layer of the support, for example, when the impregnation solution does not penetrate the entire support, such as when an initial wet impregnation technique is used.

[0051] Without intending to be bound by theory, it is believed that platinum and palladium are generally in their essentially metallic form when in use. As described below, since platinum and palladium can be present essentially as oxides after catalyst preparation and during transport and storage, it is generally desirable to activate the catalyst by contacting it with a reducing agent (e.g., hydrogen gas) to convert most of these oxides into their metallic form. However, those skilled in the art will understand that this disclosure contemplates the usefulness of various forms of platinum and palladium in their catalysts, as these forms can be active or readily converted to active forms.

[0052] After catalyst preparation and during transport and storage, the co-catalyst metal is typically provided in oxide form. Without intending to be theoretically bound, the inventors believe that the co-catalyst metal improves the catalytic activity of supported platinum, palladium, and / or gold catalysts by reducing CO methanation that may occur within the typical reverse water-gas shift reaction temperature range (which affects CO selectivity). The inventors believe that the improved activity can be attributed to the interfacial contact between the co-catalyst metal and the support (e.g., cerium oxide, titanium oxide, alumina, zirconium oxide, or mixed oxides). Additionally, when platinum, palladium, and gold are present in the catalyst, the inventors believe that the improved activity can be attributed to the interfacial contact between the co-catalyst metal and both the noble metal and the support. The inventors envision that some co-catalyst metal oxides can be converted to metallic forms during the activation of platinum, palladium, and / or gold compounds. However, those skilled in the art will understand that this disclosure envisions the usefulness of various co-catalyst metal forms in their catalysts, as these forms can provide a promoting effect or can be readily converted to forms that will have a promoting effect.

[0053] Those skilled in the art will understand that the catalysts of this disclosure can be provided in many forms, particularly depending on the specific form of the reactor system in which they are intended to be used, such as in a fixed bed or as a fluidized bed. The support itself can be provided as a discrete body of material, for example as porous microparticles, pellets, or shaped extrusions, with a co-catalyst metal and optionally platinum, palladium, and / or gold provided thereon to provide the catalyst. However, in other embodiments, the catalyst of this disclosure can itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It can be formed of, for example, a metal or metal oxide, and can itself be provided in various forms, such as microparticles, pellets, shaped extrusions, or monolithic materials. Those skilled in the art can provide a support layer on the substrate, for example using coating or other forming techniques, and then add the co-catalyst metal and optionally platinum, palladium, and / or gold. Of course, as those skilled in the art will understand, other embodiments may be possible.

[0054] Another aspect of this disclosure provides a method for preparing the catalyst as described herein. As described above, the method includes providing a support, which is a cerium oxide support, a titanium oxide support, an alumina support, a zirconium oxide support, or a mixed oxide support comprising two or more of cerium oxide, titanium oxide, alumina, and zirconium oxide; contacting the support with one or more liquids, each of the liquids comprising one or more compounds containing a co-catalyst metal dispersed in a solvent, and optionally one or more compounds containing platinum, palladium, or gold, wherein the co-catalyst metal is selected from gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium; allowing the solvent to evaporate to provide a catalyst precursor; and calcining the catalyst precursor. Of course, those skilled in the art will understand that other methods can be used to prepare the catalyst as described herein.

[0055] In some embodiments of this 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% or 10% of it). 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 liquid to carrier volume, based on mass, is in the range of 0.75:1 to 5:1, for example, in the range of 0.9:1 to 3:1. In some embodiments, contacting the carrier with the liquid provides a slurry.

[0056] In various embodiments of this disclosure as described herein, solvent evaporation is permitted at ambient temperature. In various embodiments, solvent evaporation is permitted at an elevated temperature for a drying time. Those skilled in the art will be able to select suitable equipment or instruments to permit solvent evaporation, and there are no particular limitations on such equipment or instruments. Furthermore, those skilled in the art will understand that the elevated temperature that permits solvent evaporation depends on the boiling point of the solvent. Therefore, those skilled 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, such as 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, such as 10 to 36 hours, or 12 to 24 hours. For example, in a particular embodiment, the drying time is approximately 24 hours. In some embodiments, solvent evaporation is permitted under vacuum and at an elevated temperature for a drying time, as described herein. In some implementations, solvent evaporation is permitted to take place at elevated temperatures, such as in a stirred dry bath in the range of 30-100°C.

[0057] In some embodiments of this disclosure as described herein, the calcined catalyst precursor is calcined in a furnace at a calcination temperature for a specified time. For example, in some embodiments, the calcination time ranges from 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 ranges from 100 to 600°C, for example, from 120 to 500°C.

[0058] As described above, the method for preparing the catalyst as described herein includes contacting a support with one or more liquids, each liquid comprising one or more compounds containing a cocatalyst metal dispersed in a solvent and optionally one or more compounds containing platinum, palladium, or gold. There are no particular limitations on the compounds containing platinum, palladium, gold, and the cocatalyst metal, and those skilled in the art will be able to select suitable compounds soluble in the solvent. For example, in some embodiments of this disclosure as described herein, the compounds containing platinum, palladium, gold, and the cocatalyst metal may be selected from metal salts (e.g., nitrates and acetates). There are also no particular limitations on the solvent, and those skilled in the art will be able to select suitable solvents that can be absorbed by the support. For example, in some embodiments of this disclosure as described herein, the solvent is water. As those skilled in the art will understand, these metals are conveniently provided in the same liquid, making only one step of contacting the support with the liquid necessary. However, other approaches are also possible.

[0059] In another respect, this disclosure provides catalysts prepared by the methods described herein.

[0060] Reverse water gas shift reaction Another aspect of the present invention provides a method for performing a reverse water-gas shift reaction. As described above, the method includes contacting a catalyst, as described herein, with a feed stream containing CO2 and H2 at a temperature in the range of 250-900°C to provide a product stream containing CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream. Figure 1 The diagram illustrates an instance of this type of method. Figure 1 In this embodiment, method 100 includes performing a reverse water-gas shift reaction by supplying a feed stream 111 containing H2 and CO2 to a reaction zone, such as reactor 110. As described herein, a reverse water-gas shift catalyst 113 is contacted with the feed stream 111 at a temperature in the range of 250-900°C to provide a product stream 112 containing CO and H2. The product stream has a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0061] As used herein, “feed stream” refers to the total material input to a process step, whether provided in a single physical stream or multiple physical streams, and whether provided through a single inlet or multiple inlets. For example, H2 and CO in the feed stream may be provided to the reverse water-gas shift catalyst in a single physical stream (e.g., in a single pipe to reactor 110) or in multiple physical streams (e.g., a separate inlet for CO and H2, or one inlet for fresh CO and H2 and another inlet for recycled CO and / or H2). Similarly, “product stream” refers to the total material output from a process step, whether provided in a single physical stream or multiple physical streams, and whether provided through a single outlet or multiple outlets.

[0062] For example, in various embodiments of this disclosure as described herein, the reverse-flow gas shift reaction has a CO selectivity of at least 50%, for example, at least 50%. In various embodiments, the reverse-flow gas shift reaction has a CO selectivity of at least 70%, for example, at least 80%. In various embodiments, the reverse-flow gas shift reaction has a CO selectivity of at least 85%, for example, or at least 90%. In various embodiments, the reverse-flow gas shift reaction has a CO selectivity of at least 95%, for example, or at least 96%. As used herein, “selectivity” for a given reaction product is the mole fraction of feed converted (here, CO2 converted to a product other than CO2) to the identified product (CO for “CO selectivity”). The inventors have determined that the catalyst of the present invention can provide excellent CO selectivity even when operating at temperatures lower than many conventional reverse-flow gas shift catalysts (e.g., below 900°C), despite competing potential from the Sabatier reaction and CO methanation. For example, in various embodiments of this disclosure as described herein, the reverse water-gas shift reaction has a CO selectivity in the range of 50-99% by weight, for example 60-99%, or 70-99%, or 80-99%, or 90-99%, or 95-99%. In various embodiments, the reverse water-gas shift reaction has a CO selectivity in the range of 50-90%, for example 60-90%, or 70-90%, or 50-80%, or 60-80%, or 50-70%.

[0063] It is noteworthy that even at relatively low temperatures in the range of 250-900°C, the catalyst described herein can be operated to provide carbon monoxide with only a very small degree of methane formation. For example, in various embodiments of this disclosure as described herein, the reverse-flow gas shift reaction has a methane selectivity of no more than 40%, for example, no more than 35%, or 30%, or 25%, or 20%. For example, in various embodiments of this disclosure as described herein, the reverse-flow gas shift reaction has a methane selectivity of no more than 15%, for example, no more than 12%, or 10%, or 8%. For example, in various embodiments of this disclosure as further described herein, the reverse-flow gas shift reaction has a methane selectivity of no more than 5%, for example, no more than 4%. For example, in some embodiments, the reverse-flow gas shift reaction has a methane selectivity of no more than 2%, for example, no more than 1%. In some embodiments, the reverse-flow gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0064] The inventors have determined that the catalysts described herein can provide desirable high CO selectivity and desirable low methane selectivity at commercially relevant conversion rates. As used herein, "conversion rate" refers to the mole fraction of the feed to the reaction (whether reacting to a desirable product or an undesirable one). In various embodiments of this disclosure as described herein, the countercurrent gas shift reaction has a CO2 conversion rate of at least 5%, for example, at least 10%, or 20%. For example, in some embodiments, the countercurrent gas shift reaction has a CO2 conversion rate of at least 30%, for example, at least 40%, or 50%, or 60%. In various embodiments of this disclosure as described herein, the countercurrent gas shift reaction has a CO2 conversion rate of no more than 90%, for example, no more than 80% or no more than 70%. For example, in some embodiments, the countercurrent gas shift reaction has a CO2 conversion rate of no more than 65%, for example, no more than 60%. For example, in various embodiments as described separately herein, the CO2 conversion rate is in the range of 10-90%, such as 10-80%, 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, those skilled in the art will operate with the conversion level that provides the desired product. Of course, in other embodiments, such as when in a stacked bed or mixed bed system, the CO2 conversion rate can be even higher than that described herein.

[0065] 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, various methods of this disclosure can be carried out in a temperature range of 250-900°C. For example, in some embodiments, the method for carrying out the reverse water-gas shift reaction is carried out in a temperature range of 250-850°C, such as 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C. In some embodiments of this disclosure as described herein, the method for carrying out the reverse water-gas shift reaction is carried out in a temperature range of 300-900°C, such as 350-850°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 this disclosure as described herein, the method for carrying out the reverse water-gas shift reaction is performed in the temperature 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 carrying out the reverse water-gas shift reaction is performed in the temperature range of 400-900°C, for example, in the temperature 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 carrying out the reverse water-gas shift reaction is performed in the temperature 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 carrying out the reverse water-gas shift reaction is performed in the temperature range of 500-900°C, for example, in the temperature 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 carrying out the reverse water-gas shift reaction is performed at a temperature in the range of 550-900°C, for example, 550-850°C, or 550-800°C, or 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a temperature in the range of 600-900°C, for example, 600-850°C, or 600-800°C, or 600-750°C, or 600-700°C, or 600-650°C.In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a temperature in the range of 650-900°C, for example, 650-850°C, or 650-800°C, or 650-750°C, or 650-700°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a temperature in the range of 700-900°C, for example, 700-850°C, or 700-800°C, or 700-750°C.

[0066] In some embodiments, the reverse water-gas shift reaction is carried out at temperatures ranging from 200-500°C, for example, 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 and easier integration with subsequent Fischer-Tropsch processes.

[0067] As described above, the feed stream comprises CO2 and H2. Advantageously, the inventors have recognized that both can originate from renewable or otherwise environmentally responsible sources. For example, at least a portion of the H2 can be so-called "green" hydrogen, such as that produced by water electrolysis operated using renewable electricity (e.g., wind, solar, or hydropower). In other embodiments, at least a portion of the H2 can originate from so-called "blue" sources, such as natural gas reforming processes with carbon capture. Of course, other hydrogen sources can be used in whole or in part. For example, in some embodiments, at least a portion of the H2 in the feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen. CO2 can generally be captured from the environment, or more directly from the processes that form CO2 (especially in areas where emissions reduction is difficult), so that the products subsequently made from CO are at least carbon neutral. For example, in some embodiments, at least a portion of the CO2 comes from direct air capture, or from manufacturing plants such as bioethanol plants (e.g., CO2 produced by fermentation), steel mills, or cement plants. Therefore, 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 decarbonized transport fuels (used in the automotive and aviation sectors), as the carbon monoxide produced in the reaction can be readily used to synthesize liquid hydrocarbon fuels using recognized technologies.

[0068] The feed stream contains H2 and CO2 (e.g., provided to the reaction zone in a single physical stream or multiple physical streams). As used herein, the feed stream includes all feeds of the method, whether provided as a gas mixture or as a separate gas provided to the reaction zone. In various embodiments as further described herein, the molar ratio of H2 to CO2 in the feed stream is at least 0.1:1, for example, at least 0.5:1. In some embodiments, the molar ratio of H2 to CO2 in the feed stream is at least 0.9:1, for example, at least 1:1 or at least 1.5:1. In some embodiments, the molar ratio of H2 to CO2 in the feed stream is at least 2:1, for example, at least 2.5:1. In some embodiments, the molar ratio of H2 to CO2 in the feed stream is no more than 100:1, for example, no more than 75:1 or 50:1. In some embodiments, the molar ratio of H2 to CO2 in the feed stream is no more than 20:1, for example, no more than 15:1 or 10:1. For example, in some embodiments, the molar ratio of H2 to CO2 in the feed stream is in the range of 0.5:1 to 10:1. Based on the disclosure herein, those skilled in the art will provide the desired H2:CO2 ratio in the feed stream, which provides desirable conversion and selectivity; if consistent with desirable conversion and selectivity, excess H2 can be provided to flow through the system and provide a product stream with a desirable H2:CO ratio for downstream processes.

[0069] Other gases may also be included in the feed stream. For example, in some embodiments, the feed stream further includes CO. In some embodiments of this disclosure as described separately herein, the feed stream further includes one or more inert gases. For example, in some embodiments, the feed stream further includes nitrogen and / or methane.

[0070] As will be understood by those skilled in the art, the methods described herein can be carried out under a variety of pressures. In various embodiments of this disclosure, the methods for carrying out the reverse water-gas shift reaction are carried out at pressures ranging from 1 to 100 bar (gauge pressure). For example, the method is carried out at pressures ranging from 1 to 70 bar (gauge pressure), or 1 to 50 bar (gauge pressure), or 1 to 40 bar (gauge pressure), or 1 to 35 bar (gauge pressure), or 5 to 70 bar (gauge pressure), or 5 to 50 bar (gauge pressure), or 5 to 40 bar (gauge pressure), or 5 to 35 bar (gauge pressure), or 10 to 70 bar (gauge pressure), or 10 to 50 bar (gauge pressure), or 10 to 40 bar (gauge pressure), or 10 to 35 bar (gauge pressure), or 20 to 70 bar (gauge pressure), or 20 to 50 bar (gauge pressure), or 20 to 40 bar (gauge pressure), or 20 to 35 bar (gauge pressure), or 25 to 70 bar (gauge pressure), or 25 to 50 bar (gauge pressure), or 25 to 40 bar (gauge pressure), or 25 to 35 bar (gauge pressure).

[0071] As will be understood by those skilled in the art, the methods described herein can be carried out at various GHSVs (gas hourly space velocities). Therefore, there is no particular limitation on the GHSV used for carrying out the reverse water-gas shift reaction. For example, in some embodiments of this disclosure, the method for carrying out the reverse water-gas shift reaction is performed at 1,000 to 2,000,000 h⁻¹. -1 The reaction is carried out under GHSV conditions ranging from 1,000 to 1,200,000 h⁻¹. In various embodiments, the method for performing the reverse water-gas shift reaction is carried out at GHSV conditions ranging from 1,000 to 1,200,000 h⁻¹. -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000h -1 Or 5,000 to 100,000 h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The process is carried out under GHSV conditions ranging from 1,000 to 50,000 h⁻¹. In various embodiments of this disclosure, the method for carrying out the reverse water-gas shift reaction is performed under GHSV conditions ranging from 1,000 to 50,000 h⁻¹. -1 Or 2,000 to 50,000 h -1 Or 5,000 to 50,000 h -1 Or 10,000 to 50,000 h -1 Or 1,000 to 40,000 h -1 Or 2,000 to 40,000 h -1 Or 5,000 to 40,000 h -1 Or 10,000 to 40,000 h -1 Or 1,000 to 30,000 h -1 Or 2,000 to 30,000 h -1 Or 5,000 to 30,000 h -1 Or 10,000 to 30,000 h -1 Performed within the range of GHSV.

[0072] The rWGS catalysts described herein are partially based on platinum, palladium, and / or gold. It will generally be desirable to activate the rWGS catalyst, for example, before contacting it with the feed stream. Thus, in some embodiments of this disclosure as described herein, the method includes activating the rWGS catalyst before contacting it with the feed stream. For example, in some embodiments, activating the catalyst includes contacting the catalyst with a reducing feed stream containing a reducing gas (e.g., hydrogen). In various embodiments of this disclosure, the reducing feed stream contains hydrogen in an amount of at least 25 mol%, for example, at least 50 mol%, or 75 mol%, or 90 mol%. Those skilled in the art will determine the conditions suitable for activating the rWGS catalyst. Therefore, those skilled in the art will be able to select appropriate temperature, pressure, and time to activate the rWGS catalyst. For example, in various embodiments, activation of the catalyst is carried out at temperatures ranging from 200°C to 800°C. In some embodiments, the activation of the catalyst is carried out at temperatures ranging from 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 this disclosure as described herein, the activation of the catalyst provides at least 10% of the catalyst to be reduced (e.g., at least 25%, or at least 50% reduced).

[0073] The inventors have discovered that contacting the rWGS catalyst, as described herein, with the feed stream can provide a product stream with advantageously high CO selectivity and low methane selectivity. As mentioned above, the amount of CO in the product stream can be further controlled by the rWGS reaction conditions. However, typically, the methods for carrying out the rWGS reaction as described herein provide a product stream comprising H2 and CO, wherein the product stream has a lower concentration of CO2 and a higher concentration of CO than the feed stream, consistent with the degree of conversion described herein. For example, in various embodiments, the product stream contains no more than 95 mol% CO2 or no more than 90 mol% CO2. In some embodiments, the product stream contains no more than 85 mol% CO2 or no more than 80 mol% CO2. In other examples, the product stream contains no more than 75 mol% or no more than 70 mol% CO2. However, as mentioned above, the inventors have determined that carrying out the method at an intermediate degree of conversion to provide desirable high CO selectivity and desirable low methane selectivity may be desirable. Therefore, in various embodiments as described elsewhere herein, the product stream contains a certain amount of CO2 and CO.

[0074] The product stream may also contain other gases. In some embodiments of this disclosure, as described separately herein, the product stream further contains one or more inert gases. These inert gases may be included in the feed stream or provided from sources other than the feed stream. For example, in some embodiments, the product stream further contains nitrogen and / or methane.

[0075] Depending on the degree of conversion, CO selectivity, the relative amounts of H2 and CO2 in the feed stream, and the reaction conditions, the product stream may contain H2 in various ratios combined with CO. For example, in some embodiments, the H2:CO ratio in the product stream is in the range of 0.1:1 to 100:1 (e.g., in the ranges 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).

[0076] Those skilled in the art will understand that, based on the methods described herein, the product stream can contain various amounts of H2, CO, and CO2, as well as other components. The components of the product stream can be separated and used for various purposes in the rWGS method.

[0077] For example, in various embodiments of this disclosure as described herein, the method further includes separating the product stream 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 back to the feed stream. For example, when the product stream contains CO2, the method may include recycling 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 CO2 in the product stream back to the feed stream. The product stream may also contain H2; in some embodiments, the method further includes recycling 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 H2 in the product stream back to the feed stream.

[0078] Such recycles are displayed Figure 1 (and Figure 2In method 100, at least a portion of CO2 (stream 114) is separated from product stream 112 for recycling back to feed stream 111. Similarly, method 100 includes separating at least a portion of H2 (stream 115) from product stream 112 for recycling back to product stream 111. Although stream 115 is depicted as entering reactor 110 through an inlet different from 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.

[0079] As described above, a competing reaction in the countercurrent water-gas shift reaction is the Sabatier reaction, which produces methane. While the countercurrent water-gas shift method described herein can be carried out without the formation of large amounts of methane in various embodiments, some methane may be formed in some embodiments. Therefore, in various embodiments of the method described herein, the product stream contains one or more light hydrocarbons. For example, in some embodiments, the product stream may contain one or more of methane, ethane, propane, or combinations thereof. As those skilled in the art will understand, it may be desirable to operate the countercurrent water-gas shift reaction to provide a higher amount of light hydrocarbons in the product feed. For example, such light hydrocarbons may be inert in further processing of the product stream and are therefore acceptable at higher amounts. Those skilled in the art will be able to select appropriate reaction conditions (e.g., temperature, pressure, feed stream composition) to provide a product stream containing methane in the desired amount. For example, in various embodiments further described herein, the product stream contains no more than 20 mol% methane or no more than 15 mol%. As described above, the catalyst of this disclosure can provide very low methane selectivity when a low amount of methane is desired in the product stream. Therefore, in various embodiments as further described herein, the product stream contains no more than 10 mol% methane. For example, in various embodiments, the product stream contains no more than 5 mol%, or 1 mol%, or 0.5 mol%, or no more than 0.1 mol% methane. Typically, light hydrocarbons (e.g., C1-C5 hydrocarbons) may be present in the product stream. For example, in various embodiments as further described herein, the product stream contains 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).

[0080] These light hydrocarbons (e.g., C1-C5 hydrocarbons) in the product stream 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. For example, in Figure 1In method 100, at least a portion of one or more light hydrocarbons is separated from product stream 112 to provide light hydrocarbon stream 116. The light hydrocarbon stream may, for example, be used to provide other products, may be partially oxidized to form CO, may be steam-reformed to provide hydrogen, and / or may be burned to provide heat or other energy (e.g., electricity for electrolysis) for the rWGS method or other methods.

[0081] Of course, as those skilled in the art will understand, light hydrocarbon feed streams can also be used in other processes. For example, as those skilled in the art will understand, some rWGS catalysts can have reforming capabilities. Without being bound by theory, the inventors hypothesize that one explanation for the low methane yield observed using rWGS catalysts as described herein is the formation of methane, but which is then immediately reformed into CO and H2. Therefore, in some embodiments as described herein, light hydrocarbons from the process feed stream are recycled to the feed stream used 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 feed stream. For example, in Figure 2 In method 100, at least a portion of one or more light hydrocarbons is separated from a first product stream 112 to provide a light hydrocarbon stream 118. This light hydrocarbon stream can, for example, 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 integrated methods or other methods. Of course, as those skilled in the art will understand, the light hydrocarbon stream can also be used in other methods.

[0082] Integrated Fischer-Tropsch In some embodiments as described herein, loaded countercurrent gas can be used in an rWGS method integrated with an FT method. Embodiments related to the countercurrent gas conversion portion of the integrated FT method are as described above in the previous section. For example, the feed stream of the rWGS method corresponds to the first feed stream in the integrated FT method, and the product stream of the rWGS method corresponds to the first product stream in the integrated FT method.

[0083] Another aspect of this disclosure provides a method for integrating the Fischer-Tropsch process (i.e., integrating it with the rWGS method). The method includes providing a first feed stream comprising H2 and CO2; contacting a reverse water-gas shift catalyst, as described herein, with the first feed stream at a first temperature in the range of 250-900°C and a first pressure to perform a reverse water-gas shift reaction to provide a first product stream comprising CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream. Figure 2The diagram illustrates an instance of such a method. Figure 2 In this method 100, a reverse water-gas shift reaction is performed by supplying a first feed stream 111 containing H2 and CO2 to a first reaction zone, such as reactor 110. As described herein, a reverse water-gas shift catalyst 113 is contacted with the feed stream 111 at a first temperature in the range of 250-900°C and at a first pressure to provide a first product stream 112 containing CO and H2. The first product stream has a lower concentration of CO2 and a higher concentration of CO than the first feed stream. The method of this aspect of the present disclosure further includes contacting a Fischer-Tropsch catalyst with a second feed stream containing H2 and at least a portion of the CO from the first product stream at a second temperature and a second pressure to provide a product stream containing CO. 5+ The second product stream of hydrocarbons. Figure 2 In method 100, at least a portion of the CO in the first product stream 112 is contained in a second feed stream 121, which is contacted in a second reaction zone (e.g., reactor 120) with the Fischer-Tropsch catalyst 123 therein. This provides CO-containing... 5+ The second product of hydrocarbons, stream 122.

[0084] The inventors have discovered that contacting the rWGS catalyst as described herein with the first feed stream can provide a first product stream with advantageous high CO selectivity and low methane selectivity. As mentioned above, the amount of CO in the first product stream can be further controlled by the rWGS reaction conditions. However, as mentioned above, the inventors have determined that carrying out the method at an intermediate degree of conversion to provide desirable high CO selectivity and desirable low methane selectivity may be desirable. Furthermore, the inventors have noted that downstream Fischer-Tropsch processes with relatively high inert levels may be advantageous, and thus envision that feeding a significant amount of CO2 into the Fischer-Tropsch step may be beneficial. Therefore, in the various embodiments described separately herein, the first product stream contains a certain amount of CO2 as well as CO. In various embodiments, the first product stream contains 5-95 mol% CO2, 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 10-85 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% CO2.

[0085] Furthermore, as described below, Fischer-Tropsch catalysts typically require activation with a reducing gas. As those skilled in the art will understand, different Fischer-Tropsch catalysts require different activation conditions (e.g., gas composition, temperature, pressure, time). For example, iron-based Fischer-Tropsch catalysts require activation with H2 and CO, while cobalt-based Fischer-Tropsch catalysts require activation with only H2. Therefore, H2 and CO, or only H2, from the first product stream can be used for the activation. Thus, in various embodiments as separately described herein, the method includes separating at least a portion of H2 and CO (desirably in a ratio of at least 1:1 or at least 3:1) from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. In various other embodiments as separately described herein, the method includes separating at least a portion of H2 from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. For example, in… Figure 2 In this method, feed stream 125 separates H2 or H2 and CO and directs it to reactor 120. This separation does not need to be continuous; instead, it only requires a period of time to supply reducing gas to the Fischer-Tropsch catalyst for activation. Of course, as those skilled in the art will understand, other sources of H2 or CO can be used to supply reducing gas to the Fischer-Tropsch catalyst for activation.

[0086] As shown above, water is a product of the reverse water-gas shift reaction. Therefore, the first product stream will typically contain water. In many cases, it may be desirable to reduce the amount of water supplied to the Fischer-Tropsch process. Therefore, in various embodiments as described separately herein, the method further includes 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 this embodiment, dewatering zone 116 is used to remove water and provide a water-containing feed stream 117. Those skilled in the art will understand 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 dewatering 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 sieve in the guard bed, for example, by heating and vacuum. In other embodiments, a knockout vessel can be used. However, using a knockout vessel in some cases allows for sufficient cooling of the first product stream, making it desirable for reheating to be introduced into the Fischer-Tropsch process. The water removed from the first product stream can be used as feed water for, for example, the electrolysis process described herein.

[0087] As described above, the reverse-flow gas shift method can be provided at a variety of temperatures. In some cases, these temperatures can be relatively close to the temperatures of subsequent Fischer-Tropsch steps (typically 150-400°C, e.g., 200-350°C, or other temperatures as described below). In other cases, the reverse-flow gas shift method can be carried out at temperatures significantly higher than the Fischer-Tropsch step temperatures. The inventors have noted that it may be desirable to provide heat exchange with a relatively hot first product stream to cool the first product stream to a temperature more suitable for the Fischer-Tropsch step and otherwise provide heat to the integrated method. For example, in various embodiments of the method as separately 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. Figure 3 The diagram illustrates an instance of such a method. Figure 3 In this embodiment, method 200, first reactor 210, first feed stream 211, first product stream 212, reverse water-gas shift catalyst 213, second reactor 220, second feed stream 221, second product stream 222, and Fischer-Tropsch catalyst 223 are generally as described above. Here, method 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 a 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. Those skilled in the art will understand that various heat exchangers can be used for this purpose.

[0088] Of course, any excess heat in the first product stream can be used additionally or alternatively 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 generation zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generation zone. This shows Figure 3 In this context, after heat exchange with the first feed stream 211, the first product stream 212 is guided to the steam generation zone 232 to cool the first product stream 212 and provide heat to the steam generation zone 232. Steam can be generated from the provided heat, and electricity can be generated from the steam. For example, in... Figure 3 In one embodiment, current 264 is provided by generating electricity using steam produced in steam generation zone 232. Of course, as those skilled in the art will understand, the steam produced in the steam generation zone 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 one implementation, the steam stream 266 generated in the steam generation zone 232 is guided to the heat exchange zone 290 to heat the first feed stream 211.

[0089] As described above, at least a portion of the CO in the first product stream is included in the second feed stream for the reaction in the Fischer-Tropsch process. For example, in various embodiments as further described herein, at least 25% of the CO in the first product stream, such as at least 50%, at least 75%, or at least 90% of the CO in the first product stream, is included in the second feed stream. Of course, as described above, a portion of the CO in the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0090] In some embodiments, substantially all CO in the second feed stream originates from the first product stream. However, in other embodiments, CO may be supplied to the second feed stream from other sources (fossil-derived or otherwise). For example, in various embodiments, CO is supplied to the second feed stream from a CO source other than the first product stream. Figure 3 In this process, CO feed stream 226a from several other sources is included in the second feed stream 221. Those skilled in the art will understand that CO can be provided from various sources, such as gasification, reforming, or electrochemical CO2 reduction. Furthermore, 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 through the reaction of light hydrocarbon feed streams, for example, by partial oxidation or reforming (e.g., steam reforming and / or autothermal reforming).

[0091] As described above, the second feed stream comprises H2. It is noteworthy that the first product stream will typically contain H2, such as unreacted H2 from the first feed stream. In various embodiments, the first product stream contains H2, wherein the second feed stream contains at least a portion of the H2 from the first product stream. For example, in various embodiments as further described herein, at least 25%, such as at least 50%, at least 75%, or at least 90%, of the H2 from the first product stream is contained in the second feed stream. Of course, as described above, a portion of the H2 from the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0092] In some embodiments, substantially all the H2 in the second feed stream originates from the first product stream. In fact, those skilled in the art can provide more H2 in the first feed stream than is required for the reverse water-gas shift reaction, thus providing an excess of H2 in the first product stream, which can then be supplied to the second feed stream in the required amount for the Fischer-Tropsch step. However, in other embodiments, H2 can be supplied to the second feed stream from other sources. For example, in various embodiments, H2 is supplied to the second feed stream from sources other than the first product stream. Figure 3In this process, H2 stream 226b from several other sources is included in the second feed stream 221. Those skilled in the art will understand that H2 can be supplied from various sources, such as gasification, reforming, or H2O electrolysis (including the electrolysis described herein). Furthermore, as described in more detail below, H2 can be recycled from the second product stream to the second feed stream.

[0093] Based on the disclosure herein, those skilled in the art can adjust the relative amounts of H2 and CO in the second feed stream to provide the desired ratio. For example, the second feed stream may contain more or less H2 from the first feed stream and / or more or less H2 from electrolysis. Similarly, the second feed stream may contain more or less CO from the first feed stream and more or less CO from other sources (e.g., partial oxidation and reforming as described below).

[0094] As described above, it may be desirable to perform the Fischer-Tropsch process in the presence of a significant level of inert material. One such inert material—CO2—can be derived from the reverse water-gas shift reaction, for example via the first product stream. Therefore, in various embodiments as described separately herein, the second feed stream contains at least a portion of the CO2 from the first product stream. For example, in various embodiments, at least 10%, such as at least 25%, at least 50%, at least 75%, or at least 90% of the CO2 from the first product stream, is contained in the second feed stream. Of course, in other embodiments, the second feed stream may not contain any significant amount of CO2 from the first product stream. Therefore, in various embodiments, the second feed stream does not contain a significant amount of CO2 from the first product stream. While it may generally be desirable to recycle CO2 to the first feed stream for use in the reverse water-gas shift reaction, unreacted CO2 can be recycled from the second product stream to the first feed stream, as described in more detail below.

[0095] However, additionally or alternatively, it may be desirable to include an additional inert content in the second feed stream, whether it be CO2 or other inert substances such as nitrogen and methane. For example, in various embodiments, one or more inert substances (e.g., CO2, nitrogen, and / or methane) are supplied to the second feed stream from a source other than the first product stream. Figure 3 In the second feed stream 221, there is an inert material stream 226c from several other sources. Those skilled in the art will understand that inert materials can be provided from various sources. Furthermore, as described in more detail below, the inert material can be recycled from the second product stream to the second feed stream.

[0096] As described above, it may be desirable to carry out the Fischer-Tropsch process in the presence of an inert substance. Therefore, in various embodiments as described separately herein, the portion of the first product stream contained in the second feed stream has a CO2 content in the range of 10-95 mol%, 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%.

[0097] As described above, other gases may also be included in the second feed stream. For example, as mentioned above, it may be desirable to carry out the Fischer-Tropsch process in the presence of a significant amount of inert material (i.e., a component that is not H2 or CO). For example, in various embodiments, the second feed stream contains up to 80 mol% of one or more inert materials, such as 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 contains up to 70 mol% inert material, up to 60 mol% inert material, or up to 50 mol% inert material, for example, 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% inert material. In various embodiments, the second feed stream contains up to 80% of one or more inert materials selected from CO2, 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 contains up to 80 mol% CO2, 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%.

[0098] Those skilled in the art can adjust the portion of the first product stream contained in the second feed stream to provide a desirable H2:CO ratio. For example, in various embodiments, the portion of the first product stream contained in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 10:1, such as in the range of 1:1 to 2.5:1. Of course, regardless of the H2:CO ratio of the portion of the first product stream contained in the second feed stream, those skilled in the art can add H2 or CO as needed as described above to provide the desired overall ratio in the second feed stream.

[0099] As described above, the second feed stream contains H2 and CO, and the second feed stream comprises all the feed to the Fischer-Tropsch reactor, whether provided as a mixture of feeds or as a separate feed to the reaction zone. In various embodiments of this disclosure as described herein, the second feed stream has an H2:CO ratio in the range of 0.5:1 to 6:1. In some embodiments, the second feed stream has an H2:CO ratio in the range of 1:1 to 3:1, or 1:1 to 2.5:1. In some embodiments, the second feed stream has an H2:CO ratio of at least 1.4:1. For example, in some embodiments, the second feed stream has an H2:CO ratio in the range of 1.4:1 to 3:1, or 1.4:1 to 2:1. Based on the disclosure herein, those skilled in the art will provide the desired H2:CO ratio in the second feed stream, which provides desirable conversion and selectivity in the Fischer-Tropsch process.

[0100] As mentioned above, it may be desirable to reduce the amount of water introduced into the Fischer-Tropsch process step. Therefore, in various embodiments as described separately herein, 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, no more than 2 mol%, or no more than 0.5 mol%.

[0101] As mentioned above, it may be desirable to carry out the Fischer-Tropsch process in the presence of a relatively small amount of water. Therefore, in various embodiments, the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 0.5 mol%.

[0102] The method described herein involves contacting a Fischer-Tropsch catalyst with a second feed stream as described herein. There are no particular limitations on the Fischer-Tropsch catalyst used in the method described herein, and those skilled 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 combinations thereof.

[0103] For example, in some embodiments of this disclosure as described herein, the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount ranging from 5 to 25 wt% as Co(O). The terms “as Co(O)” and similar terms refer to the weight of the cobalt atoms / ions themselves used 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 ranging from 7 to 25 wt%, or 10 to 25 wt%, or 5 to 20 wt%, or 7 to 20 wt%, or 10 to 20 wt% as Co(O). As will be understood by those skilled in the art, cobalt-based catalysts are typically provided to the reaction zone in the form of cobalt oxide on a support; cobalt can be in-situ reduced and activated (e.g., with H2) to provide an active catalyst class with a significant concentration of Co(O).

[0104] In some embodiments, the Fischer-Tropsch catalyst comprises iron, for example, in an amount ranging from 5 to 95 wt% as Fe(O). For example, in various embodiments, the Fischer-Tropsch catalyst comprises iron in an amount ranging from 10 to 95 wt%, or 25 to 95 wt%, or 50 to 95 wt%, or 5 to 85 wt%, or 10 to 85 wt%, or 25 to 85 wt%, or 50 to 85 wt%, or 5 to 75 wt%, or 10 to 75 wt%, or 25 to 75 wt%. As will be understood by those skilled 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 can be activated (e.g., by reaction with H2 and CO) to provide an active catalyst class with significant concentrations of iron carbide.

[0105] In various embodiments of this disclosure as described herein, particularly when the catalyst is a cobalt-based catalyst, the Fischer-Tropsch catalyst further comprises manganese. For example, in various embodiments, the Fischer-Tropsch catalyst contains manganese in an amount of up to 15% by weight, such as up to 12% by weight, or up to 10% by weight, or up to 7% by weight, calculated as Mn(0). In some such embodiments, the catalyst material contains manganese in an amount ranging from 0.1 to 15% by weight, such as 0.1 to 10% by weight, or 0.1 to 5% by weight, 0.5 to 15% by weight, or 0.5 to 10% by weight, or 0.5 to 5% by weight, calculated as Mn(0). Of course, in other embodiments, manganese is substantially absent (e.g., less than 0.1% by weight or less than 0.5% by weight).

[0106] Fischer-Tropsch catalysts suitable for the methods described herein can be of various forms and are not particularly limited. For example, the Fischer-Tropsch catalyst can be a supported or unsupported catalyst. While 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, alumina, silica, and zinc oxide. For example, in various embodiments, the support comprises at least one of titanium oxide, alumina, and silica. In some embodiments of this disclosure as described herein, the support is a titanium dioxide support.

[0107] Those skilled in the art will understand that the Fischer-Tropsch catalysts of this disclosure can be provided in many forms, particularly depending on the specific form of the reactor system in which they are to be used, such as in a fixed bed or as a fluidized bed. The support for the Fischer-Tropsch catalyst itself can be provided as a discrete body of material, for example as porous microparticles, pellets, or shaped extrusions, with a metal provided thereon to provide the Fischer-Tropsch catalyst. However, in other embodiments, the Fischer-Tropsch catalyst of this disclosure can itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It can be formed of, for example, a metal or metal oxide, and can itself be provided in various forms, such as microparticles, pellets, shaped extrusions, or bulk materials. Those skilled in the art will select a suitable Fischer-Tropsch catalyst for a particular reactor system.

[0108] Similar to rWGS catalysts, Fischer-Tropsch catalysts are typically activated before use to, for example, provide cobalt(O) compounds on cobalt-based catalysts or iron carbide compounds on iron-based catalysts. Such activation can take place before the Fischer-Tropsch catalyst comes into contact with the second feed stream.

[0109] For example, in some embodiments, the Fischer-Tropsch catalyst is activated by contacting it with a reducing gas. Hydrogen, for example, can be a gas particularly suitable for activating Fischer-Tropsch catalysts, such as when activation is a reduction to a metal (O) compound, as is the case for many cobalt-based catalysts. In various embodiments of this disclosure as described separately herein, the reducing gas comprises at least a portion of H2 from the first product stream. For example, in some embodiments, the method further comprises separating at least a portion of the H2 from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. Figure 2In the schematically illustrated method 100, 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, H2 present in the second feed stream can be used to activate the catalyst. As those skilled in the art will understand, the activation temperature can 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.

[0110] In various embodiments, the Fischer-Tropsch catalyst is activated by contacting it with H2 and CO. This may be particularly suitable when activation provides a conversion to carbides, for example, for many iron-based catalysts. In various embodiments of this disclosure, as described separately herein, the reducing gas comprises at least a portion of H2 and CO from the first product stream. For example, in some embodiments, the method further includes separating at least a portion of the H2 and at least a portion of the CO from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. Figure 3 In the schematically illustrated method 200, at least a portion of the H2 and CO stream 227 is separated from the first product stream 212 and contacted with the Fischer-Tropsch catalyst 223 to activate it. In other embodiments, H2 and CO present in the second feed stream can be used to activate the catalyst. The activation temperature can vary, for example, in the range of 200-400°C.

[0111] As described above, the method involves contacting a Fischer-Tropsch catalyst with a second feed stream at a second temperature and a second pressure. Those skilled in the art will select appropriate reaction conditions by combining the specific feed and catalyst used to provide the desired Fischer-Tropsch process. In some embodiments of this 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 200-250°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.

[0112] It is worth noting 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 desirablely 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.

[0113] However, in other embodiments, the first and second temperatures are not very close to each other. The inventors have noted that in many cases, the desirable reverse-flow gas shift process temperature will be significantly higher than the desirable Fischer-Tropsch process 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 or at least 200°C higher. The excess heat in the first product stream can be used for various purposes, such as preheating at least a portion of the first feed stream or generating steam for power generation, as described above.

[0114] In some embodiments of this disclosure as described herein, the second pressure is in the range of 10-50 bar (gauge pressure). For example, in various embodiments, the second pressure is in the range of 20-50 bar (gauge pressure), or 25-50 bar (gauge pressure), or 10-40 bar (gauge pressure), or 20-40 bar (gauge pressure), or 25-40 bar (gauge pressure), or 10-35 bar (gauge pressure), or 20-35 bar (gauge pressure), or 25-35 bar (gauge pressure). In some embodiments, the second pressure is in the range of 20-50 bar (gauge pressure).

[0115] As will be understood by those skilled in the art, the Fischer-Tropsch process described herein can be carried out at a variety of GHSV (gas hourly space velocity) values. Therefore, there is no particular limitation on the GHSV at which the Fischer-Tropsch reaction is carried out. For example, in some embodiments of this disclosure, the Fischer-Tropsch reaction is carried out at 1,000 to 2,000,000 h⁻¹. -1 The process is carried out under GHSV within a certain range. In various implementation schemes, the reverse water-gas shift reaction is carried out over a period of 1,000 to 1,200,000 h. -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000h -1 Or 10,000 to 1,200,000 h-1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The process is carried out under GHSV conditions ranging from 1,000 to 50,000 h. In various embodiments of this disclosure, the Fischer-Tropsch reaction is performed over a period of 1,000 to 50,000 h. -1 Or 2,000 to 50,000 h -1 Or 5,000 to 50,000 h -1 Or 10,000 to 50,000 h -1 Or 1,000 to 40,000 h -1 Or 2,000 to 40,000 h -1 Or 5,000 to 40,000 h -1 Or 10,000 to 40,000 h -1 Or 1,000 to 30,000 h -1 Or 2,000 to 30,000 h -1 Or 5,000 to 30,000 h -1 Or 10,000 to 30,000 h -1 Performed under the range of GHSV.

[0116] 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 (e.g., C) 5+ (Alcohols, aldehydes, ketones, carboxylic acids). In various embodiments of this disclosure as described herein, the Fischer-Tropsch catalyst is contacted with a second feed stream to provide a second product stream with at least 30%, for example at least 50%, or at least 70% C. 5+ Selectivity (i.e., for all C) 5+ (Class of objects). For example, in some implementations, C is... 5+ The selectivity for alkanes is at least 30%, for example at least 50%, or at least 70%. In some embodiments, the selectivity for C... 5+ Alkanes and C 5+ The selectivity of the alcohol is at least 30%, for example at least 50%, or at least 70%.

[0117] Additional components may be present in the second product stream. For example, in some embodiments, the second product stream contains water, which is another product of the Fischer-Tropsch reaction. One or more light hydrocarbons (i.e., C1-C4) may also be present as byproducts. CO and / or H2 may be present, such as unreacted CO and / or H2 from the second feed stream. CO2 or other inert substances described herein may also be present. Such components of the second product stream can be separated and / or recycled in various ways.

[0118] For example, in various embodiments, the method further includes separating at least a portion of water from the second product stream. This is illustratively shown Figure 4 In. Figure 4 In one embodiment, the reverse water-gas shift catalyst 313 and the Fischer-Tropsch catalyst 323 are provided in separate beds within the same reactor. Thus, the first reaction zone 310 is the volume of reactor 305 comprising a bed 314 containing the reverse water-gas shift catalyst 313, and the second reaction zone 320 is the volume of reactor 305 comprising a bed 324 containing the Fischer-Tropsch catalyst 323. A first feed stream 311 contacts the reverse water-gas shift catalyst 313 to provide a first product stream 312, which is then fed directly to the Fischer-Tropsch catalyst 323 as a second feed stream 321 to provide a second product stream 322. Optionally, the method further 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.

[0119] Light hydrocarbons, while not typically the desired component of Fischer-Tropsch products intended for use as fuel or lubricant, can be used for many purposes. Therefore, in various embodiments, the method further includes separating at least a portion of C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. This light hydrocarbon stream can, for example, be recycled to either the first or second feed stream. Figure 3 In method 200, light hydrocarbons may be provided as part of a recycle stream 236, which becomes part of a second feed stream 221. Figure 4 In method 300, light hydrocarbons may be provided as part of a recycle stream 336, which becomes part of a first feed stream 311. Figure 5 In method 400, light hydrocarbons are recycled to the first feed stream 411 via recirculation stream 442.

[0120] Light hydrocarbon feed streams also have other uses. For example, in some embodiments, the method further includes oxidizing at least a portion of the light hydrocarbon feed stream to provide a partially oxidized (pOX) feed stream containing CO and / or CO2, and including at least a portion of the pOX feed stream in a first feed stream and / or a second feed stream. Figure 5 The diagram schematically illustrates an example of such a method, wherein method 400, a first feed stream 411, a first product stream 412, a reverse water-gas shift catalyst 413, a second feed stream 421, a second product stream 422, and a Fischer-Tropsch catalyst 423 may be described separately herein. Here, the method comprises oxidizing at least a portion of the light hydrocarbon stream 450 in a partial oxidation reaction zone 452 to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream 454 in the first feed stream 411 and / or the second feed stream 421.

[0121] Other methods can be used to provide CO and / or CO2 from light hydrocarbon feed streams. For example, reforming technologies such as steam reforming and autothermal reforming can be used to provide CO through the reaction of hydrocarbons with water. Therefore, in various embodiments, the method further includes reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon feed stream to provide a reformate stream containing CO and / or CO2, and including at least a portion of the reformate stream in a first feed stream and / or a second feed stream. Water separated from the first and / or second product streams can be provided as part of the feed to the reforming process described herein.

[0122] Furthermore, light hydrocarbon streams can be burned to provide thermal energy, which can be used to heat various process streams or for power generation. Therefore, in various embodiments, the method includes burning at least a portion of the light hydrocarbon stream to provide energy, such as thermal or electrical energy. For example, in… Figure 5 In method 400, a portion of the light hydrocarbon feedstock 450 is burned in the power generation zone (here, in generator 470) to generate current 472. In various embodiments, thermal energy can be used to provide the required heat load for the reverse water-gas shift process. For example, in... Figure 5 In method 400, a portion of the light hydrocarbon feed stream 450 is combusted in a power generation zone (here, in a heat generator 480) to generate a heat stream 482. The heat stream 482 is directed to a heat exchange zone 490 to heat the first feed stream 411. Thermal energy can be similarly provided to the Fischer-Tropsch reaction. And as those skilled in the art will understand, other treatments of the light hydrocarbon feed stream (e.g., partial oxidation) can also provide energy, which can be used, for example, as described herein.

[0123] Similar to the first product stream, heat can be exchanged from the second product stream to provide heat to, for example, the feed stream or a steam generation 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 method 300, heat is exchanged between at least a portion of the second product stream 322 and the first feed stream 311 in the second heat exchange zone 330, 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 method 400, heat is exchanged between at least a portion of the second product stream 422 and the second feed stream 421 in a second heat exchange zone 430, thereby cooling the second product stream 422 and heating the second feed stream 421. Those skilled in the art will understand that various heat exchangers can be used for this purpose.

[0124] Of course, any excess heat in the second product stream can be used additionally or alternatively 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 generation zone, thereby cooling at least a portion of the second product stream and providing heat to the steam generation zone. This shows Figure 4 In this process, after heat exchange with the first feed stream 311, the second product stream 322 is directed to the steam generation zone 332 to cool the second product stream 322 and provide heat to the steam generation zone 332. Steam can be generated from the provided heat, and electricity can be generated from the steam (not shown here).

[0125] 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 at least a portion of the H2 from 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 H2 of the second product stream can be recycled to the second feed stream 221 via the recycling stream 236. In various embodiments, the method includes recycling at least a portion of the H2 of the second product stream to the first feed stream. For example, in Figure 4In this method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the second product stream can be recycled back to the first feed stream 311 via the recycling stream 336. In various embodiments, at least 25%, for example, at least 50%, of the H2 of the second product stream is recycled back to the first feed stream or the second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the H2 of the second product stream is recycled back to the first feed stream or the second feed stream.

[0126] In some cases, for example, when H2 is supplied to the second feed stream from a source other than the first product stream, the H2 from the second product stream can constitute a large portion of the H2 in the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the H2 in the first feed stream. This is shown, for example, in... Figure 5 In this context, the primary H2 input of the method is through feed stream 440, which becomes part of the second feed stream 421. The H2 of the second product stream is included in the recirculation stream 442, which becomes part of the first feed stream 411.

[0127] Similarly, it may be desirable to recycle the CO 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 at least a portion of the CO from 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 in 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 in the second product stream to the first feed stream. For example, in... Figure 4 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO in the second product stream can be recycled back to the first feed stream 311 via the recycling stream 336. In various embodiments, at least 25%, for example, at least 50%, of the CO in the second product stream is recycled back to the first feed stream or the second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the CO in the second product stream is recycled back to the first feed stream or the second feed stream.

[0128] In many cases, the CO and H2 from the second product stream will be recycled.

[0129] Furthermore, when one or more inert materials are used in the Fischer-Tropsch process, it may be desirable to recycle these inert materials. For example, in various embodiments, the method includes recycling at least a portion of the inert materials from the second product stream to the second feed stream. For example, in Figure 3In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inert material in the second product stream can be recycled to the second feed stream 221 via the recycling stream 236. In various embodiments, the method includes recycling at least a portion of the inert material in the second product stream to the first feed stream. For example, in... Figure 4 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inert material in the second product stream can be recycled back to the first feed stream 311 via recirculation stream 336. In various embodiments, at least 25%, for example, at least 50%, of the inert material in the second product stream is recycled back to the first or second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the inert material in the second product stream is recycled back to the first or second feed stream. In various embodiments, the purge stream can be combined with the recirculation stream to prevent uncontrolled accumulation of inert material in the recirculation stream (not shown here).

[0130] Specifically, since CO2 is the carbon source for the reverse water-gas shift process steps, it may be particularly desirable to recycle the CO2 back to the first feed stream. Therefore, in various embodiments, the method includes recycling at least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the CO2 from the second product stream back to the first feed stream. For example, in… Figure 4 In the method, at least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the CO2 in the second product stream can be recycled to the first feed stream 311 via the recycle stream 336.

[0131] In some cases, such as when CO2 is supplied to the second feed stream from a source other than the first product stream, the CO2 from the second product stream can constitute a large portion of the CO2 in the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 in the first feed stream. This is illustrated, for example, in... Figure 5 In this method, the primary CO2 input is through stream 440, which becomes part of the second feed stream 421. The CO2 of the second product stream is contained in the recycle stream 442, which becomes part of the first feed stream 411.

[0132] As described above, the Fischer-Tropsch process provides a method that includes C 5+ A second product stream of hydrocarbons (e.g., unsubstituted hydrocarbons such as alkanes and alkenes, and / or oxygen-containing hydrocarbons such as alcohols). Therefore, in various embodiments, the C2 of the second product stream... 5+ At least a portion of the hydrocarbon provides one or more products. The C 5+Hydrocarbons can be used as a base for various fuels, such as gasoline, diesel, and aviation fuel. They can also be used to produce other products, such as waxes and lubricants. Furthermore, olefins and oxygenated compounds can be used as raw materials in a variety of other processes.

[0133] Those skilled in the art will use conventional post-processing techniques to process C 5+ The hydrocarbon products are converted into desirable products such as desirable fuels. For example, in various embodiments, the method further includes hydrotreating the second product stream with C... 5+ At least a portion of the hydrocarbons. As those skilled in the art will understand, hydrotreating is the treatment of a hydrocarbon feed stream with hydrogen in the presence of a suitable catalyst. Various hydrotreating technologies are known, and those skilled in the art will apply them herein. For example, in Figure 4 In method 300, the second product stream 322 is hydrogenated in a hydrotreating reactor 350 to provide a hydrotreated product stream 352.

[0134] As stated above, CO2 and H2 are essential inputs to the claimed method. Advantageously, the inventors have recognized that each of these inputs can come from renewable or otherwise environmentally responsible sources.

[0135] CO2 can typically be captured from the environment, or more directly from the processes that generate CO2 (especially in areas where emissions reduction is difficult). This can result in the final hydrocarbon products being substantially carbon neutral or having a low carbon intensity. Therefore, in some embodiments of this disclosure as described herein, at least a portion of the CO2 in the first feed stream and / or the second feed stream originates from a renewable source. In some embodiments, 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 originates from direct air capture. In some embodiments, 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 originates from manufacturing plants such as bioethanol plants (e.g., CO2 generated from fermentation), steel mills, or cement plants. Therefore, the rWGS-Fischer-Tropsch integrated method of this 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 approach particularly attractive for decarbonized transport fuels (for automotive and aviation applications), as the carbon monoxide produced in the rWGS reaction can be readily used with recognized techniques to synthesize liquid hydrocarbon fuels via the Fischer-Tropsch process.

[0136] Similarly, H2 can be provided from environmentally responsible sources. In some embodiments, at least a portion of the H2 in the first feed stream and / or the second feed stream comes from a renewable source. For example, in various embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream can be so-called "green" hydrogen, such as that produced by water electrolysis operated using renewable electricity (such as wind, solar, or hydropower). In some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream can come from so-called "blue" sources, such as those from natural gas reforming processes with carbon capture. Of course, other hydrogen sources can be used in part or in whole. For example, in some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0137] The inventors have noted that water electrolysis is a desirable method for providing hydrogen to the claimed method. Therefore, in some embodiments, the method includes providing at least a portion of H2 to a first feed stream and / or a second feed stream via water electrolysis. In some embodiments, water electrolysis is performed at least partially 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 a first or second product stream, or by burning light hydrocarbons as described above. In some embodiments, water electrolysis is performed at least partially using electricity generated according to the methods described herein. For example, in Figure 3 In method 200, electricity 264 generated from steam produced by heat exchange from a first product stream in steam generation zone 232 is used to electrolyze water 262 separated from the first product stream in electrolyzer 260. H2 generated in the electrolysis is provided to the first feed stream via feed stream 265. In some embodiments, at least a portion of the O2 generated in the electrolysis is provided to the feed stream as described herein and as... Figure 7 The embodiment illustrates the partial oxidation reaction zone. Hydrogen from the electrolysis can also be burned to provide thermal energy, for example, it can be used to heat the first feed stream.

[0138] The methods described herein can be operated in a variety of reactor systems. In some embodiments, a first reaction zone (i.e., in which the reverse water-gas shift process steps are performed) includes a first reactor in which a reverse water-gas shift catalyst is disposed, and a second reaction zone (i.e., in which the Fischer-Tropsch process steps are performed) includes a second reactor in which a Fischer-Tropsch catalyst is disposed. Illustrative examples of such methods are shown in [illustrative examples]. Figure 1 ,2 In examples 100, 200, and 400, the methods (100, 200, 400) are carried out in a reactor system comprising a first reactor (110, 210, 410) in which a counter-current 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. There are no particular limitations on the reactors used for the integrated methods of this disclosure as described herein, and those skilled in the art will be able to select appropriate reactors.

[0139] However, other implementations are also possible. For example, in some implementations, the method is carried out in a reactor system comprising a first catalyst bed in which a counter-current gas shift catalyst is disposed, and wherein a second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed. In some implementations, the first and second reactor beds are disposed within the same reactor. Figure 4 This configuration is illustrated in the image, where a reverse water-gas shift catalyst 313 is disposed in a first catalyst bed 314, and a Fischer-Tropsch catalyst 323 is disposed in a second catalyst bed 324. Here, catalyst beds 314 and 324 are in the same reactor 305, and the process gas flows between them. This configuration may be particularly desirable when the first and second temperatures are relatively close to each other.

[0140] In various embodiments, the method is carried out in a reactor system comprising a first catalyst vessel in which one or more counter-current water-gas shift catalysts are disposed, and a second reaction zone comprising a second catalyst vessel in which one or more Fischer-Tropsch catalysts are disposed. These can be provided in the same reactor, as described above regarding catalyst beds.

[0141] As described above, the reverse water-gas shift process steps and the Fischer-Tropsch process steps using the palladium and platinum catalysts described herein can be carried out under similar conditions. Therefore, 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... Figure 6 In this context, method 500 is carried out in a reactor system including reactor 505, in which the reverse water-gas shift catalyst 513 and the 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 as mixtures of process gases within the mixed catalyst.

[0142] In the embodiments specifically described above, individual rWGS and Fischer-Tropsch catalysts are used, for example, in separate reactors, in separate areas of the same reactor, or even mixed in the same area of ​​the reactor.

[0143] However, the inventors also note that the rWGS catalyst described herein shares certain commonalities with some Fischer-Tropsch catalysts. For example, as those skilled in the art will understand, manganese is a common modifier used in Fischer-Tropsch catalysts, especially those based on cobalt. The inventors also note that similar supports can be used for each catalyst.

[0144] Therefore, in addition to the above-described structure, the inventors envision providing a single bifunctional catalyst possessing both reverse water-gas shift activity and Fischer-Tropsch activity. This bifunctional catalyst comprises both an rWGS active catalyst metal and a Fischer-Tropsch active catalyst metal within the same bulk. Those skilled in the art will understand that both the rWGS catalyst and the Fischer-Tropsch catalyst are supported catalysts, such as metal oxide supported catalysts. Therefore, in various embodiments of this disclosure, the rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal can be disposed together on the same support to provide a bifunctional catalyst. For example, in some embodiments, the support for the bifunctional catalyst is itself provided as a discrete body of material, such as porous microparticles, pellets, or shaped extrusions, wherein the rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal are provided thereon to provide the bifunctional catalyst. The rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal can be uniformly distributed throughout the support, or they can be distributed in discrete regions throughout the support. However, in other embodiments, the bifunctional catalyst of this disclosure can itself be formed as a layer on an underlying substrate. For example, in some embodiments, the bifunctional catalyst is formed of an rWGS active catalyst metal layer and an FT active catalyst metal layer on an underlying substrate. The rWGS active catalyst metal and the FT active catalyst metal can be uniformly distributed on the underlying substrate. In other embodiments, the rWGS active catalyst metal and the FT active catalyst metal can be in discrete regions on the underlying substrate. The underlying substrate is not particularly limited. It can be formed of, for example, a metal or a metal oxide, and can be provided in various forms, such as microparticles, pellets, shaped extrusions, or monolithic materials.

[0145] 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, and a co-catalyst metal as described herein, and at least one of cobalt, iron, rhodium, and ruthenium. In some embodiments of this disclosure, the bifunctional catalyst comprises a support as a metal oxide support as described herein, at least one of platinum, palladium, and gold, a co-catalyst metal as described herein, and cobalt. In some embodiments of this 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, a co-catalyst metal as described herein, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, at least one of platinum, palladium, and gold, a co-catalyst metal as described herein, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, platinum, a co-catalyst metal as described herein, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, palladium, a co-catalyst metal as described herein, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, gold, a co-catalyst metal as described herein, 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 wt%, a co-catalyst metal as described herein present in an amount ranging from 0.5 to 20 wt%, and cobalt present in an amount ranging from 7 to 25 wt%. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, platinum present in an amount ranging from 0.05 to 10 wt%, a co-catalyst metal as described herein present in an amount ranging from 0.5 to 20 wt%, and cobalt present in an amount ranging from 7 to 25 wt%. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, palladium present in an amount ranging from 0.05 to 10 wt%, a co-catalyst metal as described herein present in an amount ranging from 0.5 to 20 wt%, and cobalt present in an amount ranging from 7 to 25 wt%. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, gold in an amount ranging from 0.05 to 10 wt%, a co-catalyst metal as described herein in an amount ranging from 0.5 to 20 wt%, and cobalt in an amount ranging from 7 to 25 wt%.

[0146] There is no particular limitation on the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst, and those skilled 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.

[0147] Such catalysts can be used in implementation schemes such as those described above. Figure 6 Of those described, those skilled in the art will select reaction conditions that provide a suitable balance between the reverse water-gas shift activity and the Fischer-Tropsch activity.

[0148] Figure 7 This is a schematic depiction of another integrated method according to this disclosure. Here, the reverse-flow gas shift and Fischer-Tropsch process steps are integrated with the following processes: partial oxidation of light hydrocarbons to provide CO and H2 to the Fischer-Tropsch process steps; electrolysis to provide H2 for the reverse-flow gas shift process steps and O2 for partial oxidation; and various recycling and optional feeds, as described throughout this specification.

[0149] Those skilled in the art will provide the materials described herein and perform the methods described herein based on the above general disclosure and with reference to the following embodiments. Example

[0150] The following examples illustrate specific embodiments of the catalysts and methods of this disclosure and their various uses. They are set forth for illustrative purposes only and should not be construed as limiting the scope of this disclosure.

[0151] Example 1. Modeling The inventors have modeled various equilibrium conditions for the reverse water-gas shift reaction. The predicted carbon dioxide conversion and product composition of the rWGS reaction (reaction 1), competing with the Sabatier reaction (reaction 3) and the CO methanation reaction (reaction 4), are calculated based on thermodynamic equilibrium in a temperature range of 400-800°C. From this modeling, carbon monoxide selectivity increases at temperatures above 600°C, while methane selectivity decreases at even higher temperatures.

[0152] These results clearly show that the Sabatil reaction (reaction (3)) and CO methanation (reaction (4)) side reactions are exothermic and predominant at lower temperatures, while the rWGS reaction (reaction (1)) is endothermic and predominant at higher temperatures. However, other carbon-producing side reactions not considered in the examples may occur at higher temperatures. Therefore, the inventors have investigated catalysts that operate at moderate temperatures. These catalysts are discussed in more detail below.

[0153] Example 2. Catalyst Preparation Before testing its feasibility for the reverse water-gas shift reaction, the catalyst was prepared using a conventional impregnation method. The supports used are described in Table 1.

[0154] Table 1. chemicals supplier Pore ​​volume Cerium oxide (IV) Sigma-Aldrich 0.1 mL / g To prepare the catalyst, solutions of active metal salts (e.g., Pd or Pt) and / or co-catalysts (e.g., Nb, V, Zr, Ga, or In) were prepared in deionized water. For platinum-containing solutions, a platinum(II) nitrate solution from Umicore with 17.5 wt% Pt and 99.95% metal purity was used. For palladium-containing solutions, a palladium(II) nitrate solution from Umicore with 23.9 wt% Pd and 99.95% metal purity was used. The following compounds were used as co-catalysts: ammonium niobium(V) oxalate hydrate (99.99% purity, Sigma-Aldrich), ammonium metavanadate (99% purity, Sigma-Aldrich), zirconium(IV) oxynitrate hydrate (99.5% purity, Acros Organics BVBA), gallium(III) nitrate hydrate (99.9% purity, Sigma-Aldrich), and indium(III) nitrate hydrate (99.9% purity, Sigma-Aldrich). A solution of the active metal salt and co-catalyst was added to the support powder. The amount of support added was based on the amount of water by mass, resulting in a water:support ratio of 3:1. The slurry was then stirred at room temperature for 4 hours. Excess water was then evaporated using a stirred drying bath at 60°C. The resulting catalyst precursor powder was then dried in a drying oven at 90°C for 24 hours.

[0155] The catalyst precursor powder was then calcined by uniformly spreading it in a crucible. The crucible was placed in a calcination furnace, and the temperature was increased from ambient temperature to 120°C at a rate of 10°C / min. The temperature was then maintained at 120°C for 1 hour, followed by an increase from 120°C to 500°C at a rate of 2°C / min. The temperature was then maintained at 500°C for 4 hours, followed by cooling to ambient temperature. The feasibility of using the obtained catalyst for a reverse water-gas shift reaction was then tested.

[0156] Example 3. Performance of catalysts without platinum, palladium, or gold The catalysts described herein were prepared using the methods described herein, and their catalytic performance for the reverse water-gas shift reaction was tested. The tested catalysts were cerium dioxide supported catalysts containing 5% by weight of a co-catalyst selected from Nb, V, Zr, Ga, or In. To test the catalytic performance of these catalysts, a Meryer quartz reactor and 0.1 g of catalyst were used, with a catalyst density of approximately 2 g / mL. The total flow rate was 37.7 mL / min (9.6 mol% CO2 partial pressure, with H2 partial pressure variations equilibrated with Ar for different H2:CO2 ratios). The catalysts were then contacted with a feed stream comprising H2 and CO2 in a 3:1 ratio at four different temperatures to carry out the rWGS reaction. The total pressure was maintained at 1 bar, and the GHSV was maintained for 17,280 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 2. In Table 2 and Tables 3-6 below, the amount of co-catalyst present in the catalyst is shown in parentheses. These figures are in weight percentage and are based on the total weight of the catalyst. For example, CeO2Nb(5) corresponds to a catalyst with 5 wt% Nb and 95 wt% CeO2.

[0157] Table 2. As can be seen from Table 2, the addition of zirconium and gallium improved activity without sacrificing CO selectivity. The addition of niobium decreased activity but did not sacrifice CO selectivity. The activity of vanadium depended on the operating temperature, with better activity observed at higher temperatures.

[0158] Example 4. Performance of platinum catalysts with co-catalyst metals The reverse water-gas shift (rWGS) activity of cerium dioxide-supported platinum catalysts with various co-catalysts was evaluated. Platinum was present in the catalyst at 0.5 wt%, and co-catalysts (e.g., Ga, In, La, Ti, Nb, V, or Zr) were present at 5 wt%. These catalysts were prepared as described herein. To test the catalytic performance of these catalysts, 20 μL of catalyst diluted with SiC F100 to provide a 1:10 ratio 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. The catalyst was activated at 590 °C in an atmosphere of 97% hydrogen and 3% argon for 5 h prior to the rWGS reaction. Subsequently, the catalysts were subjected to 600 °C at 30 or 40 bar (gauge pressure) for 1,200,000 h. -1The reactor was contacted with feed streams of H2 and CO2 in two different ratios under GHSV conditions to carry out the rWGS reaction. 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 3.

[0159] Table 3. As can be seen from Table 3, the 0.5 wt% Pt catalyst supported on cerium dioxide exhibits extremely high CO selectivity at 600 °C. Adding 5 wt% Ga, In, La, Ti, Nb, V, or Zr to the formulation results in CO selectivity exceeding 97%. CO selectivity appears to be minimally affected by increasing the reaction pressure and the H2:CO ratio, which generally enhances method formation and the formation of other carbon-containing products.

[0160] These same catalysts were subjected to temperatures of 500°C, pressures of 30 or 40 bar (gauge pressure), and 1,200,000 h⁻¹. -1 The rWGS reaction was evaluated under GHSV with two different feed streams of H2 and CO2 in ratios. The results are shown in Table 4.

[0161] Table 4. As can be seen from Table 4, the catalyst exhibits high selectivity for rWGS, with CO selectivity exceeding 98% except for gallium-containing catalysts. CO selectivity appears to be minimally affected by increasing reaction pressure and the H2:CO ratio, which generally enhances methane formation and the formation of other carbon-containing products.

[0162] These same catalysts were subjected to temperatures of 400°C, pressures of 30 or 40 bar (gauge pressure), and 1,200,000 h⁻¹. -1 The rWGS reaction was evaluated under GHSV with two different feed streams of H2 and CO2 in ratios. The results are shown in Table 5.

[0163] Table 5. As can be seen in Table 5, at lower temperatures, dopants containing La, Ti, and Zr are more effective in terms of both selectivity and conversion. Compared to 500 °C and 600 °C as shown in Tables 3 and 4, Ga and In are less effective in reducing methane formation at 400 °C.

[0164] Example 5. Environmental stress test The reverse water-gas shift (rWGS) activity of cerium dioxide-supported platinum catalysts with various co-catalysts was evaluated. Platinum was present in the catalyst at 0.5 wt%, and co-catalysts (e.g., Ga, In, Nb, V, or Zr) at 5 wt%. Platinum catalysts without co-catalysts were also tested. These catalysts were prepared as described herein. The reactor setup described in Example 3 was also used. Subsequently, these catalysts were contacted with feed streams of H2 and CO2 at 600 °C, ambient pressure, and three different GHSVs to carry out the rWGS reaction. 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.

[0165] Table 6. The inclusion of co-catalyst metals improved the CO selectivity of the catalysts under all conditions tested in Table 6. In and Ga exhibited the best selectivity, independent of the H2:CO2 ratio. The selectivity of Zr and Nb decreased with increasing H2:CO2 ratio. Overall, the activity of each catalyst increased with increasing H2:CO2 ratio and GHSV.

[0166] Additional aspects of this disclosure are provided by the following enumerated embodiments, which can be combined in any number and in any combination that is not logically or technically inconsistent.

[0167] Implementation Scheme 1. A supported reverse water gas shift catalyst, comprising: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst.

[0168] Implementation Scheme 2. The catalyst of Implementation Scheme 1, wherein the support constitutes at least 70% by weight (e.g., at least 75% by weight, or 80% by weight, or 85% by weight, or 90% by weight) of the catalyst based on oxides.

[0169] Implementation Scheme 3. The catalyst described in Implementation Scheme 1 or Implementation Scheme 2, wherein the support is a cerium oxide support.

[0170] Implementation Scheme 4. The catalyst of Implementation Scheme 3, wherein, based on oxides, at least the surface layer of the cerium oxide support contains at least 60 wt% cerium oxide, for example at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide.

[0171] Implementation Scheme 5. The catalyst of Implementation Scheme 3, wherein, based on oxides, at least the surface layer of the cerium oxide support comprises at least 90% by weight cerium oxide, such as at least 95% by weight cerium oxide, or at least 98% by weight cerium oxide.

[0172] Implementation Scheme 6. The catalyst described in any one of Implementation Schemes 3-5, wherein the cerium oxide support comprises at least 50% by weight cerium oxide, for example at least 60% by weight cerium oxide, or at least 70% by weight cerium oxide, or at least 80% by weight cerium oxide, based on oxide content.

[0173] Implementation Scheme 7. The catalyst described in any one of Implementation Schemes 3-5, wherein the cerium oxide support comprises at least 90% by weight cerium oxide, for example at least 95% by weight cerium oxide, or at least 98% by weight cerium oxide, based on oxide content.

[0174] Implementation Scheme 8. The catalyst described in Implementation Scheme 1 or Implementation Scheme 2, wherein the support is a titanium oxide support.

[0175] Implementation Scheme 9. The catalyst of Implementation Scheme 8, wherein, based on oxides, at least the surface layer of the titanium oxide support comprises at least 60 wt% titanium oxide, such as at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide.

[0176] Implementation Scheme 10. The catalyst of Implementation Scheme 8, wherein, based on oxides, 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.

[0177] Implementation Scheme 11. The catalyst described in any one of Implementation Schemes 8-10, wherein the titanium oxide support comprises at least 50% by weight of titanium oxide, for example at least 60% by weight of titanium oxide, or at least 70% by weight of titanium oxide, or at least 80% by weight of titanium oxide, based on oxide content.

[0178] Implementation Scheme 12. The catalyst described in any one of Implementation Schemes 8-10, wherein the titanium oxide support comprises at least 90% by weight titanium oxide, such as at least 95% by weight titanium oxide or at least 98% by weight titanium oxide, based on oxide content.

[0179] Implementation Scheme 14. The catalyst described in Implementation Scheme 1 or Implementation Scheme 2, wherein the support is an alumina support.

[0180] Implementation Scheme 15. The catalyst of Implementation Scheme 14, wherein, based on oxides, at least the surface layer of the alumina support comprises at least 60% by weight alumina, for example at least 70% by weight alumina, or at least 80% by weight alumina.

[0181] Implementation Scheme 16. The catalyst of Implementation Scheme 14, wherein, based on oxides, at least the surface layer of the alumina support comprises at least 90% by weight alumina, for example at least 95% by weight alumina, or at least 98% by weight alumina.

[0182] Implementation Scheme 17. The catalyst described in any one of Implementation Schemes 14-16, wherein the alumina support comprises at least 50% by weight alumina, for example at least 60% by weight alumina, or at least 70% by weight alumina, or at least 80% by weight alumina, based on oxides.

[0183] Implementation Scheme 18. The catalyst described in any one of Implementation Schemes 14-16, wherein the alumina support comprises at least 90% by weight alumina, for example at least 95% by weight alumina, or at least 98% by weight alumina, based on oxides.

[0184] Implementation Scheme 19. The catalyst described in Implementation Scheme 1 or Implementation Scheme 2, wherein the support is a zirconium oxide support.

[0185] Implementation Scheme 20. The catalyst of Implementation Scheme 19, wherein, based on oxides, at least the surface layer of the zirconium support comprises at least 60 wt% zirconium oxide, for example at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide.

[0186] Implementation Scheme 21. The catalyst of Implementation Scheme 19, wherein, based on oxides, at least the surface layer of the zirconium support comprises at least 90% by weight zirconium oxide, for example at least 95% by weight zirconium oxide, or at least 98% by weight zirconium oxide.

[0187] Implementation Scheme 22. The catalyst of any one of Implementation Schemes 19-21, wherein the zirconia support comprises at least 50% by weight of zirconia, for example at least 60% by weight of zirconia, or at least 70% by weight of zirconia, or at least 80% by weight of zirconia, based on oxides.

[0188] Implementation Scheme 23. The catalyst described in any one of Implementation Schemes 19-22, wherein the zirconium support comprises at least 90% by weight zirconium oxide, for example at least 95% by weight zirconium oxide, or at least 98% by weight zirconium oxide, based on oxide content.

[0189] Implementation Scheme 24. The catalyst described in Implementation Scheme 1 or Implementation Scheme 2, wherein, based on oxides, the support is a mixed oxide support having at least a surface layer comprising at least 50% by weight of two or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide.

[0190] Implementation Scheme 25. The catalyst described in any one of Implementation Schemes 1-24, wherein, based on oxides, the support does not contain more than 2% by weight of additional metals, for example, more than 1% by weight or more than 0.5% by weight of additional metals.

[0191] Implementation Scheme 26. The catalyst of any one of Implementation Schemes 1-24, wherein the support comprises at least one additional metal.

[0192] Implementation Scheme 27. The catalyst of Implementation Scheme 26, wherein the total amount of the at least one additional metal, based on oxides, is 0.5-20% by weight, for example 1-20% by weight, or 2-20% by weight, or 0.5-15% by weight, or 1-15% by weight, or 2-15% by weight, or 0.5-10% by weight, or 1-10% by weight, or 2-10% by weight, or 0.5-5% by weight, or 1-5% by weight.

[0193] Implementation Scheme 28. The catalyst of any one of Implementation Schemes 1-27, wherein the support has a pore volume of at least 0.05 mL / g.

[0194] Implementation Scheme 29. The catalyst of any one of Implementation Schemes 1-28, wherein the support has a pore volume of up to 1.5 mL / g.

[0195] Implementation Scheme 30. The catalyst of any one of Implementation Schemes 1-29, wherein the support has a pore volume in the range of 0.05-1.5 mL / g.

[0196] Implementation Scheme 31. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is gallium.

[0197] Implementation Scheme 32. The catalyst of Implementation Scheme 31, wherein gallium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0198] Implementation Scheme 33. The catalyst of Implementation Scheme 31, wherein gallium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0199] Implementation Scheme 34. The catalyst of Implementation Scheme 31, wherein gallium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0200] Implementation Scheme 35. The catalyst of Implementation Scheme 31, wherein gallium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example, from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0201] Implementation Scheme 36. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst is indium.

[0202] Implementation Scheme 37. The catalyst of Implementation Scheme 36, wherein indium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0203] Implementation Scheme 38. The catalyst of Implementation Scheme 36, wherein indium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0204] Implementation Scheme 39. The catalyst of Implementation Scheme 36, wherein indium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0205] Implementation Scheme 40. The catalyst of Implementation Scheme 36, wherein indium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example, from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0206] Implementation Scheme 41. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is lanthanum.

[0207] Implementation Scheme 42. The catalyst of Implementation Scheme 41, wherein lanthanum is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0208] Implementation Scheme 43. The catalyst of Implementation Scheme 41, wherein lanthanum is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0209] Implementation Scheme 44. The catalyst of Implementation Scheme 41, wherein lanthanum is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0210] Implementation Scheme 45. The catalyst of Implementation Scheme 41, wherein lanthanum is present in the catalyst in an amount ranging from 4 to 20% by weight, for example, from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0211] Implementation Scheme 46. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is titanium.

[0212] Implementation Scheme 47. The catalyst of Implementation Scheme 46, wherein titanium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0213] Implementation Scheme 48. The catalyst of Implementation Scheme 46, wherein titanium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0214] Implementation Scheme 49. The catalyst of Implementation Scheme 46, wherein titanium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0215] Implementation Scheme 50. The catalyst of Implementation Scheme 46, wherein titanium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0216] Implementation Scheme 51. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is niobium.

[0217] Implementation Scheme 52. The catalyst of Implementation Scheme 51, wherein niobium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0218] Implementation Scheme 53. The catalyst of Implementation Scheme 51, wherein niobium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0219] Implementation Scheme 54. The catalyst of Implementation Scheme 51, wherein niobium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0220] Implementation Scheme 55. The catalyst of Implementation Scheme 51, wherein niobium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example, from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0221] Implementation Scheme 56. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is vanadium.

[0222] Implementation Scheme 57. The catalyst of Implementation Scheme 56, wherein vanadium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0223] Implementation Scheme 58. The catalyst of Implementation Scheme 56, wherein vanadium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0224] Implementation Scheme 59. The catalyst of Implementation Scheme 56, wherein vanadium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0225] Implementation Scheme 60. The catalyst of Implementation Scheme 56, wherein vanadium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0226] Implementation Scheme 61. The catalyst described in any one of Implementation Schemes 1-30, wherein the co-catalyst metal is zirconium.

[0227] Implementation Scheme 62. The catalyst of Implementation Scheme 61, wherein zirconium is present in the catalyst in an amount ranging from 0.5% to 15% by weight, for example from 0.5% to 12% by weight or from 0.5% to 10% by weight, based on the total weight of the catalyst.

[0228] Implementation Scheme 63. The catalyst of Implementation Scheme 61, wherein zirconium is present in the catalyst in an amount ranging from 1 to 20% by weight, for example from 1 to 15% by weight, or from 1 to 12% by weight, or from 1 to 10% by weight, based on the total weight of the catalyst.

[0229] Implementation Scheme 64. The catalyst of Implementation Scheme 61, wherein zirconium is present in the catalyst in an amount ranging from 2 to 20% by weight, for example, from 2 to 15% by weight, or from 2 to 12% by weight, or from 2 to 10% by weight, based on the total weight of the catalyst.

[0230] Implementation Scheme 65. The catalyst of Implementation Scheme 61, wherein zirconium is present in the catalyst in an amount ranging from 4 to 20% by weight, for example from 4 to 15% by weight, or from 4 to 12% by weight, or from 4 to 10% by weight, based on the total weight of the catalyst.

[0231] Implementation Scheme 66. The catalyst of any one of Implementation Schemes 1-65, wherein, based on metals, the total amount of cerium, titanium, aluminum, zirconium, and co-catalyst metals (e.g., gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium) in the catalyst is at least 90% by weight, for example at least 95% by weight or at least 98% by weight.

[0232] Implementation Scheme 67. The catalyst described in any one of Implementation Schemes 1-66, wherein platinum, palladium or gold is present in the catalyst.

[0233] Implementation Scheme 68. A supported reverse water gas shift catalyst, comprising: The carrier is a cerium oxide carrier, a titanium oxide carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium, or gold, present in an amount ranging from 0.05 to 10% by weight of the catalyst based on the total weight of the catalyst. Implementation Scheme 69. The catalyst of Implementation Scheme 68, wherein the support is as described in any one of Implementation Schemes 2-30.

[0234] Implementation Scheme 70. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is gallium and is present in the amount described in Implementation Schemes 31-35.

[0235] Implementation Scheme 71. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is indium and is present in the amount described in Implementation Schemes 36-40.

[0236] Implementation Scheme 72. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is lanthanum and is present in the amount described in Implementation Schemes 41-45.

[0237] Implementation Scheme 73. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is titanium and is present in the amount described in Implementation Schemes 46-50.

[0238] Implementation Scheme 74. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is niobium and is present in the amount described in Implementation Schemes 51-55.

[0239] Implementation Scheme 75. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is vanadium and is present in the amount described in Implementation Schemes 56-60.

[0240] Implementation Scheme 76. The catalyst described in Implementation Scheme 68 or Implementation Scheme 69, wherein the co-catalyst metal is zirconium and is present in the amount described in Implementation Schemes 61-65.

[0241] Implementation Scheme 77. The catalyst described in any one of Implementation Schemes 68-76, wherein platinum is present in the catalyst.

[0242] Implementation Scheme 78. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.1% to 10% by weight, for example, from 0.5% to 10% by weight, or from 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.

[0243] Implementation Scheme 79. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05% to 7% by weight, for example, 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.

[0244] Implementation Scheme 80. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05% to 5% by weight, for example, from 0.1% to 5% by weight, or from 0.5% to 5% by weight, or from 1% to 5% by weight, or from 2% to 5% by weight, based on the total weight of the catalyst.

[0245] Implementation Scheme 81. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05% to 2% by weight, for example, from 0.1% to 2% by weight, or from 0.3% to 2% by weight, or from 0.5% to 2% by weight, or from 1% to 2% by weight, based on the total weight of the catalyst.

[0246] Implementation Scheme 82. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 1.5% by weight, for example, from 0.1 to 1.5% by weight, or from 0.3 to 1.5% by weight, or from 0.5 to 1.5% by weight, based on the total weight of the catalyst.

[0247] Implementation Scheme 83. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05% to 1% by weight, for example, from 0.1% to 1% by weight, or from 0.3% to 1% by weight, or from 0.5% to 1% by weight, based on the total weight of the catalyst.

[0248] Implementation Scheme 84. The catalyst of Implementation Scheme 77, wherein platinum is present in the catalyst in an amount ranging from 0.05 to 0.8% by weight, for example, from 0.1 to 0.8% by weight, or from 0.3 to 0.8% by weight, or from 0.5 to 0.8% by weight, based on the total weight of the catalyst.

[0249] Implementation Scheme 85. The catalyst described in any one of Implementation Schemes 68-76, wherein palladium is present in the catalyst.

[0250] Implementation Scheme 86. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.1% to 10% by weight, for example, from 0.5% to 10% by weight, or from 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.

[0251] Implementation Scheme 87. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05% to 7% by weight, for example, 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.

[0252] Implementation Scheme 88. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05% to 5% by weight, for example, from 0.1% to 5% by weight, or from 0.5% to 5% by weight, or from 1% to 5% by weight, or from 2% to 5% by weight, based on the total weight of the catalyst.

[0253] Implementation Scheme 89. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05% to 2% by weight, for example, from 0.1% to 2% by weight, or from 0.3% to 2% by weight, or from 0.5% to 2% by weight, based on the total weight of the catalyst.

[0254] Implementation Scheme 90. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 1.5% by weight, for example, from 0.1 to 1.5% by weight, or from 0.3 to 1.5% by weight, or from 0.5 to 1.5% by weight, based on the total weight of the catalyst.

[0255] Implementation Scheme 91. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05% to 1% by weight, for example, from 0.1% to 1% by weight, or from 0.3% to 1% by weight, or from 0.5% to 1% by weight, based on the total weight of the catalyst.

[0256] Implementation Scheme 92. The catalyst of Implementation Scheme 85, wherein palladium is present in the catalyst in an amount ranging from 0.05 to 0.8% by weight, for example, from 0.1 to 0.8% by weight, or from 0.3 to 0.8% by weight, or from 0.5 to 0.8% by weight, based on the total weight of the catalyst.

[0257] Implementation Scheme 93. The catalyst described in any one of Implementation Schemes 68-76, wherein gold is present in the catalyst.

[0258] Implementation Scheme 94. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.1% to 10% by weight, for example, from 0.5% to 10% by weight, or from 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.

[0259] Implementation Scheme 95. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05% to 7% by weight, for example, 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.

[0260] Implementation Scheme 96. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05% to 5% by weight, for example, from 0.1% to 5% by weight, or from 0.5% to 5% by weight, or from 1% to 5% by weight, or from 2% to 5% by weight, based on the total weight of the catalyst.

[0261] Implementation Scheme 97. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05% to 2% by weight, for example, from 0.1% to 2% by weight, or from 0.3% to 2% by weight, or from 0.5% to 2% by weight, based on the total weight of the catalyst.

[0262] Implementation Scheme 98. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05 to 1.5% by weight, for example, from 0.1 to 1.5% by weight, or from 0.3 to 1.5% by weight, or from 0.5 to 1.5% by weight, based on the total weight of the catalyst.

[0263] Implementation Scheme 99. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05% to 1% by weight, for example, from 0.1% to 1% by weight, or from 0.3% to 1% by weight, or from 0.5% to 1% by weight, based on the total weight of the catalyst.

[0264] Implementation Scheme 100. The catalyst of Implementation Scheme 93, wherein gold is present in the catalyst in an amount ranging from 0.05 to 0.8% by weight, for example, from 0.1 to 0.8% by weight, or from 0.3 to 0.8% by weight, or from 0.5 to 0.8% by weight, based on the total weight of the catalyst.

[0265] Implementation Scheme 101. The catalyst described in any one of Implementation Schemes 68-100, wherein the weight ratio of platinum, palladium and / or gold to the co-catalyst metal (e.g., gallium, indium, lanthanum, titanium, niobium, vanadium and zirconium) is at least 0.05:1, for example at least 0.1:1.

[0266] Implementation Scheme 102. The catalyst described in any one of Implementation Schemes 68-101, wherein the weight ratio of platinum, palladium and / or gold to the co-catalyst metal (e.g., gallium, indium, lanthanum, titanium, niobium, vanadium and zirconium) is at most 5:1, for example at most 2:1, or 1:1, or 0.5:1.

[0267] Implementation Scheme 103. The catalyst described in any one of Implementation Schemes 68-102, wherein the ratio of platinum, palladium and / or gold to the co-catalyst metal (e.g., gallium, indium, lanthanum, titanium, niobium, vanadium and zirconium) 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).

[0268] Implementation Scheme 104. The catalyst of any one of Implementation Schemes 68-103, wherein, based on metals, the total amount of cerium, titanium, zirconium, co-catalyst metals (e.g., gallium, indium, lanthanum, titanium, niobium, vanadium and zirconium), platinum, palladium and gold in the catalyst is at least 90% by weight, for example at least 95% by weight, or at least 98% by weight.

[0269] Implementation Scheme 105. A method for preparing the catalyst according to any one of Implementation Schemes 1-104, the method comprising: Provide a carrier, which is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide; The carrier is brought into contact with one or more liquids, each of which contains one or more compounds containing a co-catalyst metal dispersed in a solvent, and optionally one or more compounds containing platinum, palladium, or gold, wherein the co-catalyst metal is selected from gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium. Allowing the solvent to evaporate to provide a catalyst precursor; and The catalyst precursor is calcined.

[0270] Implementation Scheme 106. The method of Implementation Scheme 105, wherein contacting the carrier with the liquid comprises adding the liquid in an amount equal to the pore volume of the carrier.

[0271] Implementation Scheme 107. The method of Implementation Scheme 105, wherein contacting the carrier with the liquid comprises adding the liquid in an amount greater than the pore volume of the carrier.

[0272] Implementation Scheme 108. The method of any one of Implementation Schemes 105-107, wherein, based on a mass meter, the ratio of liquid volume to carrier volume is in the range of 1:1 to 5:1 (e.g., in the range of 1:1 to 3:1).

[0273] Implementation Scheme 109. The method of any one of Implementation Schemes 105-108, wherein contacting the carrier with the liquid provides a slurry.

[0274] Implementation Scheme 110. The method of any one of Implementation Schemes 105-109, wherein solvent evaporation is permitted to take place at ambient temperature.

[0275] Implementation Scheme 111. The method described in Implementation Schemes 105-110, wherein the solvent is allowed to evaporate at an elevated temperature (e.g., in the range of 50-150°C) for a drying time (e.g., 24 hours).

[0276] Implementation Scheme 112. The method described in Implementation Schemes 105-110, wherein the solvent is allowed to evaporate under vacuum and at elevated temperatures (e.g., in the range of 50-150°C) for a drying time (e.g., 24 hours).

[0277] Implementation Scheme 113. The method of any one of Implementation Schemes 105-110, wherein solvent evaporation is permitted to be carried out in a stirred drying bath at elevated temperatures (e.g., in the range of 30-100°C).

[0278] Implementation Scheme 114. The method of any one of Implementation Schemes 105-113, 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).

[0279] Implementation Scheme 115. The method of any one of Implementation Schemes 105-114, wherein the calcination of the catalyst precursor is carried out at a temperature in the range of 100-600°C (e.g., the range of 120-500°C).

[0280] Implementation Scheme 116. The catalyst described in any one of Implementation Schemes 1-104 is prepared by the method according to Implementation Schemes 105-115.

[0281] Implementation Scheme 117. A method for performing a reverse water-gas shift reaction, the method comprising: The catalyst according to any one of embodiments 1-104 and 116 is contacted with a feed stream containing CO2 and H2 at a temperature in the range of 250-900°C to provide a product stream containing CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0282] Implementation Scheme 118. The method of Implementation Scheme 117, wherein the reverse water gas shift reaction has a CO selectivity of at least 50%, for example, at least 60%.

[0283] Implementation Scheme 119. The method of Implementation Scheme 117, wherein the reverse water gas shift reaction has a CO selectivity of at least 70%, for example, at least 80%.

[0284] Implementation Scheme 119a. The method of Implementation Scheme 117, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, for example, at least 95%.

[0285] Implementation scheme 119b. The method of implementation scheme 117, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, for example, at least 96%.

[0286] Implementation Scheme 119c. The method of Implementation Scheme 117, wherein the reverse water-gas shift reaction has a CO selectivity of 50-99% by weight, for example 60-99%, or 70-99%, or 80-99%, or 90-99%, or 95-99%.

[0287] Implementation Scheme 119d. The method of Implementation Scheme 117, wherein the reverse water-gas shift reaction has a CO selectivity of 50-90%, for example 60-90%, or 70-90%, or 50-80%, or 60-80%, or 50-70%.

[0288] Implementation scheme 119e. The method of any one of implementation schemes 117-119d, wherein the reverse water gas shift reaction has a methane selectivity of no more than 40%, for example no more than 35%, or 30%, or 25%, or 20%.

[0289] Scheme 119f. The method of any one of Schemes 117-119d, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 15%, for example, no more than 12%, or 10%, or 8%.

[0290] Implementation Scheme 120. The method of any one of Implementation Schemes 117-119d, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example, no more than 4%.

[0291] Implementation Scheme 121. The method described in any one of Implementation Schemes 117-119d, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, for example, no more than 1%.

[0292] Implementation Scheme 122. The method of any one of Implementation Schemes 117-119d, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0293] Implementation Scheme 123. The method described in any one of Implementation Schemes 117-122 has a CO2 conversion rate of at least 5%, for example at least 10% or 20%.

[0294] Implementation Scheme 124. The method described in any one of Implementation Schemes 117-122 has a CO2 conversion rate of at least 30%, for example, at least 40%.

[0295] Implementation Scheme 125. The method described in any one of Implementation Schemes 117-124 has a CO2 conversion rate of no more than 90%, for example, no more than 80% or no more than 70%.

[0296] Implementation Scheme 126. The method described in any one of Implementation Schemes 117-124 has a CO2 conversion rate of no more than 65%, for example, no more than 60%.

[0297] Implementation Scheme 127. The method described in any one of Implementation Schemes 117-126 is carried out at a temperature in the range of 250-850°C, for example, in the range of 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C.

[0298] Implementation Scheme 128. The method described in any one of Implementation Schemes 117-126 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.

[0299] Implementation Scheme 129. The method described in any one of Implementation Schemes 117-126 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.

[0300] Implementation Scheme 130. The method described in any one of Implementation Schemes 117-126 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.

[0301] Implementation Scheme 131. The method described in any one of Implementation Schemes 117-126 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.

[0302] Implementation Scheme 132. The method described in any one of Implementation Schemes 117-126 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.

[0303] Implementation Scheme 133. The method described in any one of Implementation Schemes 117-126 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.

[0304] Implementation Scheme 134. The method described in any one of Implementation Schemes 117-126 is carried out at a temperature in the range of 600-900°C, for example, in the range of 600-850°C, or 600-800°C, or 600-750°C, or 600-700°C, or 600-650°C.

[0305] Implementation Scheme 135. The method described in any one of Implementation Schemes 117-126 is carried out at a temperature in the range of 650-900°C, for example, in the range of 650-850°C, or 650-800°C, or 650-750°C, or 650-700°C.

[0306] Implementation Scheme 136. The method described in any one of Implementation Schemes 117-126 is carried out at a temperature in the range of 700-900°C, for example, in the range of 700-850°C, or 700-800°C, or 700-750°C.

[0307] Implementation Scheme 137. The method of any one of Implementation Schemes 117-136, wherein at least a portion of the H2 of the feed stream comes from a renewable source.

[0308] Implementation Scheme 138. The method of any one of Implementation Schemes 117-137, wherein at least a portion of the H2 in the feed stream is green hydrogen.

[0309] Implementation Scheme 139. The method of any one of Implementation Schemes 117-138, wherein at least a portion of the H2 in the feed stream is blue hydrogen.

[0310] Implementation Scheme 140. The method of any one of Implementation Schemes 117-139, wherein at least a portion of the H2 in the feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0311] Implementation Scheme 141. The method of any one of Implementation Schemes 117-140, wherein at least a portion of the CO2 in the feed stream comes from a renewable source.

[0312] Implementation Scheme 142. The method of any one of Implementation Schemes 117-141, wherein at least a portion of the CO2 in the feed stream is derived from direct air capture.

[0313] Implementation Scheme 143. The method of any one of Implementation Schemes 117-142, wherein at least a portion of the CO2 in the feed stream is captured from a manufacturing plant, such as a bioethanol plant, a steel plant, or a cement plant.

[0314] Implementation Scheme 144. The method of any one of Implementation Schemes 117-143, wherein the molar ratio of H2 to CO2 in the feed stream is at least 0.1:1, for example at least 0.5:1.

[0315] Implementation Scheme 145. The method of any one of Implementation Schemes 117-143, wherein the molar ratio of H2 to CO2 in the feed stream is at least 0.9:1, for example at least 1:1 or at least 1.5:1.

[0316] Implementation Scheme 146. The method of any one of Implementation Schemes 117-143, wherein the molar ratio of H2 to CO2 in the feed stream is at least 2:1, for example at least 2.5:1.

[0317] Implementation Scheme 147. The method described in any one of Implementation Schemes 117-146, wherein the molar ratio of H2 to CO2 in the feed stream is not more than 100:1, for example, not more than 75:1 or 50:1.

[0318] Implementation Scheme 148. The method described in any one of Implementation Schemes 117-146, wherein the molar ratio of H2 to CO2 in the feed stream is not more than 20:1, for example, not more than 15:1 or 10:1.

[0319] Implementation Scheme 149. The method of any one of Implementation Schemes 117-146, wherein the molar ratio of H2 to CO2 in the feed stream is in the range of 0.5:1 to 10:1.

[0320] Implementation Plan 150. The method described in any of embodiments 117-149 is carried out at a pressure ranging from 1 to 100 bar (gauge pressure) (e.g., from 1 to 70 bar (gauge pressure), or 1 to 50 bar (gauge pressure), or 1 to 40 bar (gauge pressure), or 1 to 35 bar (gauge pressure), or 5 to 80 bar (gauge pressure), or 5 to 50 bar (gauge pressure), or 5 to 40 bar (gauge pressure), or 5 to 35 bar (gauge pressure), or 10 to 70 bar (gauge pressure), or 10 to 50 bar (gauge pressure), or 10 to 40 bar (gauge pressure), or 10 to 35 bar (gauge pressure), or 20 to 70 bar (gauge pressure), or 20 to 50 bar (gauge pressure), or 20 to 40 bar (gauge pressure), or 20 to 35 bar (gauge pressure), or 25 to 70 bar (gauge pressure), or 25 to 50 bar (gauge pressure), or 25 to 40 bar (gauge pressure), or 25 to 35 bar (gauge pressure).

[0321] Implementation Scheme 151. The method described in any one of Implementation Schemes 117-150, for 1,000 to 2,000,000 h -1 The range (e.g., from 1,000 to 1,200,000 h) -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000 h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The range is GHSV.

[0322] Implementation Scheme 152. The method of any one of Implementation Schemes 117-151, wherein the product stream contains no more than 95 mol% CO2 (e.g., no more than 90 mol% CO2).

[0323] Implementation Scheme 153. The method of any one of Implementation Schemes 117-151, wherein the product stream contains no more than 85 mol% CO2 (e.g., no more than 80 mol% CO2).

[0324] Implementation Scheme 154. The method of any one of Implementation Schemes 117-151, wherein the product stream contains no more than 75 mol% CO2 (e.g., no more than 70 mol% CO2).

[0325] Implementation Scheme 155. The method of any one of Implementation Schemes 117-154, wherein the product stream further comprises CO2, and wherein the method further comprises recycling at least a portion of the CO2 in the product stream to the feed stream.

[0326] Implementation Scheme 156. The method of any one of Implementation Schemes 117-155, wherein the product stream further comprises hydrogen, and wherein the method further comprises recycling at least a portion of the hydrogen in the product stream to the feed stream.

[0327] Implementation Scheme 157. The method of any one of Implementation Schemes 117-156, wherein the H2:CO ratio in the product stream 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).

[0328] Implementation Scheme 158. The method of any one of Implementation Schemes 117-157, wherein the product stream contains no more than 20 mol% methane, for example no more than 15 mol% methane.

[0329] Implementation Scheme 159. The method of any one of Implementation Schemes 117-157, wherein the product stream comprises 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.

[0330] Implementation Scheme 160. The method of any one of Implementation Schemes 117-159, wherein the method includes activating the catalyst before contacting the catalyst with the feed stream.

[0331] Implementation Scheme 161. The method of Implementation Scheme 160, wherein activating the catalyst includes contacting the catalyst with a reducing feed stream containing a reducing gas (e.g., hydrogen).

[0332] Implementation Scheme 162. The method of Implementation Scheme 160 or Implementation Scheme 161, wherein the reducing agent stream contains hydrogen in an amount of at least 25 mol% (e.g., at least 50 mol%, or 75 mol%, or 90 mol%).

[0333] Implementation Scheme 163. The method of any one of Implementation Schemes 160-162, wherein the activation of the catalyst is carried out at a temperature in the range of 200 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).

[0334] Implementation Scheme 164. The method of any one of Implementation Schemes 160-163, wherein activating the catalyst provides at least 10% of the catalyst to be reduced (e.g., at least 25% or 50% reduced).

[0335] Implementation Scheme 165. A method for performing integrated Fehling-Tropsch method, the method comprising: Provide a first feed stream containing H2 and CO2; The reverse water gas shift catalyst is contacted with the first feed stream at a first temperature in the range of 250-900°C and a first pressure to carry out the reverse water gas shift reaction, so as to provide a first product stream containing CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream containing at least a portion of H2 and CO from the first product stream at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons, The aforementioned countercurrent gas shift catalyst is a supported countercurrent gas shift catalyst, which comprises: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst.

[0336] Implementation Scheme 166. The method of Implementation Scheme 165, wherein the reverse water gas shift catalyst is as described in any one of Implementation Schemes 1 to 104.

[0337] Implementation Scheme 167. The method of any implementation scheme 165, wherein the reverse water gas shift catalyst is prepared by any one of the methods of implementation schemes 105 to 115.

[0338] Implementation Scheme 168. The method of any one of Implementation Schemes 165-167, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 0.1:1, for example at least 0.5:1.

[0339] Implementation Scheme 169. The method of any one of Implementation Schemes 165-167, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 0.9:1, for example at least 1:1 or at least 1.5:1.

[0340] Implementation Scheme 170. The method of any one of Implementation Schemes 165-167, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 2:1, for example at least 2.5:1.

[0341] Implementation Scheme 171. The method described in any one of Implementation Schemes 165-170, wherein the molar ratio of H2 to CO2 in the first feed stream is not more than 100:1, for example, not more than 75:1 or 50:1.

[0342] Implementation Scheme 172. The method described in any one of Implementation Schemes 165-170, wherein the molar ratio of H2 to CO2 in the first feed stream is not more than 20:1, for example, not more than 15:1 or 10:1.

[0343] Implementation Scheme 173. The method of any one of Implementation Schemes 165-172, wherein the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:1.

[0344] Implementation Scheme 174. The method according to any one of Implementation Schemes 165-173, wherein the first feed stream further comprises CO.

[0345] Implementation Scheme 175. The method according to any one of Implementation Schemes 165-174, wherein the first feed stream further comprises one or more inert gases (e.g., nitrogen and / or methane).

[0346] Implementation Scheme 176. The method of Implementation Scheme 175, wherein the reverse water gas shift reaction has a CO selectivity of at least 50%, for example, at least 60%.

[0347] Implementation Scheme 177. The method of Implementation Scheme 175, wherein the reverse water gas shift reaction has a CO selectivity of at least 70%, for example, at least 80%.

[0348] Implementation Scheme 178. The method of Implementation Scheme 175, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, for example, at least 95%.

[0349] Implementation Scheme 179. The method of Implementation Scheme 175, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, for example, at least 96%.

[0350] Implementation Scheme 179a. The method of Implementation Scheme 175, wherein the reverse water-gas shift reaction has a CO selectivity of 50-99% by weight, for example 60-99%, or 70-99%, or 80-99%, or 90-99%, or 95-99%.

[0351] Implementation Scheme 179b. The method of Implementation Scheme 175, wherein the reverse water-gas shift reaction has a CO selectivity of 50-90%, for example 60-90%, or 70-90%, or 50-80%, or 60-80%, or 50-70%.

[0352] Implementation scheme 179c. The method of any one of implementation schemes 165-179b, wherein the reverse water gas shift reaction has a methane selectivity of no more than 40%, for example no more than 35%, or 30%, or 25%, or 20%.

[0353] Implementation scheme 179d. The method of any one of implementation schemes 165-179b, wherein the reverse water gas shift reaction has a methane selectivity of no more than 15%, for example no more than 12%, or 10%, or 8%.

[0354] Implementation Scheme 180. The method of any one of Implementation Schemes 165-179b, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example, no more than 4%.

[0355] Implementation Scheme 181. The method of any one of Implementation Schemes 165-179b, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, for example, no more than 1%.

[0356] Implementation Scheme 182. The method of any one of Implementation Schemes 165-179b, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0357] Implementation Scheme 183. The method of any one of Implementation Schemes 165-182, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 5%, for example at least 10%, or 20%.

[0358] Implementation Scheme 184. The method of any one of Implementation Schemes 165-182, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 30%, for example, at least 40%.

[0359] Implementation Scheme 185. The method of any one of Implementation Schemes 165-184, wherein the reverse water gas shift reaction has a CO2 conversion rate of not more than 90%, for example not more than 80%, or not more than 70%.

[0360] Implementation Scheme 186. The method of any one of Implementation Schemes 165-184, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 65%, for example, no more than 60%.

[0361] Implementation Scheme 187. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out in the range of 250-850°C, for example, in the range of 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C.

[0362] Implementation Scheme 188. The method described in any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0363] Implementation Scheme 189. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0364] Implementation Scheme 190. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0365] Implementation Scheme 191. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0366] Implementation Scheme 192. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0367] Implementation Scheme 193. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out 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.

[0368] Implementation Scheme 194. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out in the range of 600-900°C, for example in the range of 600-850°C, or 600-800°C, or 600-750°C, or 600-700°C, or 600-650°C.

[0369] Implementation Scheme 195. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out in the range of 650-900°C, for example, in the range of 650-850°C, or 650-800°C, or 650-750°C, or 650-700°C.

[0370] Implementation Scheme 196. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out in the range of 700-900°C, for example, in the range of 700-850°C, or 700-800°C, or 700-750°C.

[0371] Implementation Scheme 197. The method of any one of Implementation Schemes 165-186, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 200-500°C, for example, in the range of 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, for example, in the range of 250-450°C, or 250-400°C, or 250-350°C.

[0372] Implementation Scheme 198. The method of any one of Implementation Schemes 165-197, wherein the reverse water-gas shift reaction is in the range of 1 to 100 bar (gauge pressure) (e.g., 1 to 70 bar (gauge pressure), or 1 to 50 bar (gauge pressure), or 1 to 40 bar (gauge pressure), or 1 to 35 bar (gauge pressure), or 5 to 80 bar (gauge pressure), or 5 to 50 bar (gauge pressure), or 5 to 40 bar (gauge pressure), or 5 to 35 bar (gauge pressure), or 10 to 70 bar (gauge pressure). The pressure ranges from 10 to 50 bar (gauge pressure), or 10 to 40 bar (gauge pressure), or 10 to 35 bar (gauge pressure), or 20 to 70 bar (gauge pressure), or 20 to 50 bar (gauge pressure), or 20 to 40 bar (gauge pressure), or 20 to 35 bar (gauge pressure), or 25 to 70 bar (gauge pressure), or 25 to 50 bar (gauge pressure), or 25 to 40 bar (gauge pressure), or 25 to 35 bar (gauge pressure).

[0373] Implementation Scheme 199. The method described in any one of Implementation Schemes 165-198, wherein the reverse water-gas shift reaction is carried out at a time of 1,000 to 2,000,000 h. -1 The range (e.g., from 1,000 to 1,200,000 h) -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000 h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The range is GHSV.

[0374] Implementation Scheme 200. The method of any one of Implementation Schemes 165-199, wherein the method includes activating the reverse water gas shift catalyst, for example before contacting the reverse water gas shift catalyst with the first feed stream.

[0375] Implementation Scheme 201. The method of Implementation Scheme 200, wherein activating the rWGS catalyst includes contacting the rWGS catalyst with a reducing feed stream containing a reducing gas (e.g., hydrogen).

[0376] Implementation Scheme 202. The method of Implementation Scheme 200 or Implementation Scheme 201, wherein the reducing agent stream contains hydrogen in an amount of at least 25 mol% (e.g., at least 50 mol%, or 75 mol%, or 90 mol%).

[0377] Implementation Scheme 203. The method of any one of Implementation Schemes 200-202, wherein the activation of the rWGS 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 700°C, or 300°C to 700°C).

[0378] Implementation Scheme 204. The method of any one of Implementation Schemes 200-203, wherein the activated rWGS catalyst provides at least 10% of the catalyst that is reduced (e.g., at least 25% or 50% reduced).

[0379] Implementation Scheme 205. The method of any one of Implementation Schemes 165-204, wherein the first product stream contains no more than 95 mol% CO2 (e.g., no more than 90 mol% CO2).

[0380] Implementation Scheme 206. The method of any one of Implementation Schemes 165-204, wherein the first product stream contains no more than 85 mol% CO2 (e.g., no more than 80 mol% CO2).

[0381] Implementation Scheme 207. The method of any one of Implementation Schemes 165-204, wherein the first product stream contains no more than 75 mol% CO2 (e.g., no more than 70 mol% CO2).

[0382] Implementation Scheme 208. The method of any one of Implementation Schemes 165-204, wherein the first product stream contains CO2 in the range of 5-95 mol%, 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%.

[0383] Implementation Scheme 209. The method of any one of Implementation Schemes 165-208, wherein the first product stream contains no more than 20 mol% methane, for example no more than 15 mol% methane.

[0384] Implementation Scheme 210. The method of any one of Implementation Schemes 165-208, wherein the first product stream comprises 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.

[0385] Implementation Scheme 211. The method of any one of Implementation Schemes 165-210, wherein the H2:CO ratio in the first product stream is at most 100:1, for example at most 50:1, or at most 25:1, or at most 10:1.

[0386] Implementation Scheme 212. The method of any one of Implementation Schemes 165-210, wherein the H2:CO ratio in the first product stream 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).

[0387] Implementation Scheme 213. The method of any one of Implementation Schemes 165-212, wherein the method further comprises separating a first product stream to recycle at least a portion of one or more components of the first product stream to a first feed stream.

[0388] Implementation Scheme 214. The method of any one of Implementation Schemes 165-213, wherein the method further comprises separating the first product stream 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 the CO2 in the first product stream back to the first feed stream.

[0389] Implementation Scheme 215. The method of any one of Implementation Schemes 165-214, wherein the method further comprises separating the first product stream to recycle at least a portion of H2 (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%) back to the first feed stream.

[0390] Implementation Scheme 216. The method of any one of Implementation Schemes 165-215, wherein the method comprises separating at least a portion of H2 and / or CO from a first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst.

[0391] Implementation Scheme 217. The method of any one of Implementation Schemes 165-216, wherein the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of water from the first product stream.

[0392] Implementation Scheme 218. The method of any one of Implementation Schemes 165-217, wherein the first product stream comprises one or more light hydrocarbons (e.g., methane, ethane, propane).

[0393] Implementation Scheme 219. The method according to Implementation Scheme 218 further includes separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream.

[0394] Implementation Scheme 220. The method of any one of Implementation Schemes 165-219, 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.

[0395] Implementation Scheme 221. The method of any one of Implementation Schemes 165-220, wherein the method further includes exchanging heat between at least a portion of the first product stream and the steam generation zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generation zone.

[0396] Implementation Scheme 222. The method of Implementation Scheme 221 further includes generating steam from heat supplied to the steam generation zone and generating electricity from the steam.

[0397] Implementation Scheme 223. The method of Implementation Scheme 221 or 222, wherein the steam is used to heat the first feed stream and / or the second feed stream.

[0398] Implementation Scheme 224. The method of any one of Implementation Schemes 165-223, wherein at least 25% of the CO of the first product stream, for example, at least 50%, at least 75%, or at least 90% of the CO of the first product stream is contained in the second feed stream.

[0399] Implementation Scheme 225. The method of any one of Implementation Schemes 165-224, wherein CO is supplied to the second feed stream from a CO source other than the first product stream.

[0400] Implementation Scheme 226. The method of any one of Implementation Schemes 165-225, wherein the first product stream comprises H2, and wherein the second feed stream comprises at least a portion of the H2 of the first product stream.

[0401] Implementation Scheme 227. The method of any one of Implementation Schemes 165-226, wherein at least 25% of H2 of the first product stream, for example at least 50%, at least 75%, or at least 90% of H2 of the first product stream is included in the second feed stream.

[0402] Implementation Scheme 228. The method of any one of Implementation Schemes 165-227, wherein H2 is supplied to the second feed stream from a hydrogen source other than the first product stream.

[0403] Implementation Scheme 229. The method of any one of Implementation Schemes 165-228, wherein the second feed stream comprises at least a portion of CO2 from the first product stream.

[0404] Implementation Scheme 230. The method of any one of Implementation Schemes 165-229, wherein at least 10% of the CO2 in the first product stream, for example at least 25%, at least 50%, at least 75%, or at least 90% of the CO2 in the first product stream is contained in the second feed stream.

[0405] Implementation Scheme 231. The method of any one of Implementation Schemes 165-229, wherein the second feed stream does not contain a significant amount of CO2 from the first product stream.

[0406] Implementation Scheme 232. The method of any one of Implementation Schemes 165-231, wherein a portion of the first product stream in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 10:1, for example, in the range of 1:1 to 3:1.

[0407] Implementation Scheme 233. The method of any one of Implementation Schemes 165-232, 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, no more than 2 mol%, or no more than 0.5 mol%.

[0408] Implementation Scheme 234. The method of any one of Implementation Schemes 165-233, wherein a portion of the first product stream in the second feed stream has a CO2 content in the range of 10-95 mol%, 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%.

[0409] Implementation Scheme 235. The method of any one of Implementation Schemes 165-234, wherein the second feed stream has an H2:CO ratio in the range of 0.5:1 to 6:1.

[0410] Implementation Scheme 236. The method of any one of Implementation Schemes 165-234, wherein the second feed stream has an H2:CO ratio in the range of 1:1 to 3:1, for example 1:1 to 2.5:1.

[0411] Implementation Scheme 237. The method of any one of Implementation Schemes 165-234, wherein the second feed stream has an H2:CO 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.

[0412] Implementation Scheme 238. The method of any one of Implementation Schemes 165-237, wherein the second feed stream comprises up to 80%, for example 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%.

[0413] Implementation Scheme 239. The method of any one of Implementation Schemes 165-237, wherein the second feed stream comprises up to 80%, for example 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%, one or more inert substances selected from CO2, methane, and nitrogen.

[0414] Implementation Scheme 240. The method of any one of Implementation Schemes 165-239, wherein the second feed stream comprises up to 80%, for example 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 CO2.

[0415] Implementation Scheme 241. The method of any one of Implementation Schemes 165-240, wherein the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 0.5 mol%.

[0416] Implementation Scheme 242. The method of any one of Implementation Schemes 165-241, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0417] Implementation Scheme 243. The method of any one of Implementation Schemes 165-241, wherein the Fischer-Tropsch catalyst contains cobalt in an amount calculated as Co(O), for example, in the range of 5-25 wt%, such as 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt%.

[0418] Implementation Scheme 244. The method of any one of Implementation Schemes 165-241, wherein the Fischer-Tropsch catalyst comprises iron in an amount ranging from 5-95 wt%, 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%.

[0419] Implementation Scheme 245. The method of any one of Implementation Schemes 240-244, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0420] Implementation Scheme 246. The method of Implementation Scheme 245, wherein manganese is present in an amount of up to 15% by weight, for example up to 12% by weight, or up to 10% by weight, or up to 7% by weight, calculated as Mn(0), or in the range of 0.1-15% by weight, for example 0.1-10% by weight, or 0.1-5% by weight, 0.5-15% by weight, or 0.5-10% by weight, or 0.5-5% by weight.

[0421] Implementation Scheme 247. The method of any one of Implementation Schemes 165-246, wherein 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.

[0422] Implementation Scheme 248. The method of any one of Implementation Schemes 165-246, wherein the Fischer-Tropsch catalyst is a supported catalyst, and wherein the support comprises at least one of titanium oxide, alumina and silicon oxide.

[0423] Implementation Scheme 249. The method of any one of Implementation Schemes 165-246, wherein the Fischer-Tropsch catalyst is a supported catalyst and wherein the support is a titanium dioxide support.

[0424] Implementation Scheme 250. The method of any one of Implementation Schemes 165-249, wherein the Fischer-Tropsch catalyst is activated by contacting a reducing gas, such as hydrogen.

[0425] Implementation Scheme 251. The method of Implementation Scheme 250, wherein the reducing gas comprises at least a portion of hydrogen from the first product stream.

[0426] Implementation Scheme 252. The method of any one of Implementation Schemes 165-251, wherein the Fischer-Tropsch catalyst is activated by contacting H2 and CO.

[0427] Implementation Scheme 253. The method of Implementation Scheme 252, wherein the reducing gas comprises at least a portion of H2 and CO from the first product stream.

[0428] Implementation Scheme 254. The method of any one of Implementation Schemes 251-253, wherein the activation is carried out at a temperature in the range of 200-400°C.

[0429] Implementation Scheme 255. The method of any one of Implementation Schemes 165-254, wherein the second temperature is in the range of 150-400°C (e.g., 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 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0430] Implementation Scheme 256. The method of any one of Implementation Schemes 165-255, wherein the second temperature is in the range of 200-350°C.

[0431] Implementation Scheme 257. The method of any one of Implementation Schemes 165-256, wherein the first temperature is within 100°C of the second temperature, for example within 50°C of the second temperature, or within 25°C of the second temperature.

[0432] Implementation Scheme 258. The method of any one of Implementation Schemes 165-256, wherein the first temperature is at least 100°C higher than the second temperature, for example at least 150°C higher or at least 200°C higher than the second temperature.

[0433] Implementation Scheme 259. The method of any one of Implementation Schemes 165-258, wherein the second pressure is in the range of 10-50 bar (gauge pressure) (e.g., 20-50 bar (gauge pressure), or 25-50 bar (gauge pressure), or 10-40 bar (gauge pressure), or 20-40 bar (gauge pressure), or 25-40 bar (gauge pressure), or 10-35 bar (gauge pressure), or 20-35 bar (gauge pressure), or 25-35 bar (gauge pressure)).

[0434] Implementation Scheme 260. The method of any one of Implementation Schemes 165-259, wherein the second pressure is in the range of 20-50 bar (gauge pressure).

[0435] Implementation Scheme 261. The method of any one of Implementation Schemes 165-260, wherein the Fischer-Tropsch reaction is carried out at 1,000 to 2,000,000 h. -1 The range (e.g., from 1,000 to 1,200,000 h) -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The range is GHSV.

[0436] Implementation Scheme 262. The method of any one of Implementation Schemes 165-261, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50%, or at least 70% C 5+ Selective implementation.

[0437] Implementation Scheme 263. The method of any one of Implementation Schemes 165-262, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50%, or at least 70% of the C 5+ The selective processing of alkanes is carried out.

[0438] Implementation Scheme 264. The method of any one of Implementation Schemes 165-263, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50%, or at least 70% of the C 5+ Alkanes and C 5+ The selective reaction of alcohols is carried out.

[0439] Implementation Scheme 265. The method of any one of Implementation Schemes 165-264 further includes separating at least a portion of water from the second product stream.

[0440] Implementation Scheme 266. The method of any one of Implementation Schemes 165-265 further includes separating at least a portion of C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0441] Implementation Scheme 267. The method described in Implementation Scheme 266 further includes including at least a portion of a light hydrocarbon stream in the first feed stream and / or the second feed stream.

[0442] Implementation Scheme 268. The method described in Implementation Scheme 266 or Implementation Scheme 267 further includes oxidizing at least a portion of the light hydrocarbon feed stream to provide a pOX feed stream containing CO and / or CO2, and including at least a portion of the pOX feed stream in the first feed stream and / or the second feed stream.

[0443] Implementation Scheme 269. The method of any one of Implementation Schemes 266-268 further includes reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon feed stream to provide a reformed feed stream containing CO and / or CO2, and includes at least a portion of the reformed feed stream in the first feed stream and / or the second feed stream.

[0444] Implementation scheme 270. The method described in implementation scheme 268 or implementation scheme 269, wherein the oxidation or reforming provides energy, thermal energy or electrical energy.

[0445] Implementation Scheme 271. The method of any one of Implementation Schemes 266-270 further includes burning at least a portion of the light hydrocarbon feed stream to provide energy, such as thermal or electrical energy.

[0446] Implementation Scheme 272. The method of Implementation Scheme 271, wherein thermal energy is provided and said thermal energy is used to heat the first feed stream.

[0447] Implementation Scheme 273. The method of any one of Implementation Schemes 165-272, wherein the method further includes exchanging heat between at least a portion of the second product stream and the steam generation zone, thereby cooling at least a portion of the first feed stream and providing heat to the steam generation zone.

[0448] Implementation Scheme 274. The method described in Implementation Scheme 273 further includes generating steam from heat supplied to the steam generation zone and generating electricity from the steam.

[0449] Implementation Scheme 275. The method described in Implementation Scheme 273 or 274, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0450] Implementation Scheme 276. The method of any one of Implementation Schemes 165-275, 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.

[0451] Implementation Scheme 277. The method of any one of Implementation Schemes 165-276 further includes recycling at least a portion of H2 of the second product stream to the second feed stream.

[0452] Implementation Scheme 278. The method of any one of Implementation Schemes 165-277 further includes recycling at least a portion of H2 of the second product stream to the first feed stream.

[0453] Implementation Scheme 279. The method described in Implementation Scheme 278 further includes providing H2 to the second feed stream from an H2 source other than the first product stream.

[0454] Implementation Scheme 280. The method of Implementation Scheme 279, wherein H2 from the second product stream constitutes a majority of H2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of H2 of the first feed stream.

[0455] Implementation Scheme 281. The method of any one of Implementation Schemes 165-280 further includes recycling at least a portion of the CO of the second product stream to the second feed stream.

[0456] Implementation Scheme 282. The method of any one of Implementation Schemes 165-281 further includes recycling at least a portion of the CO of the second product stream to the first feed stream.

[0457] Implementation Scheme 283. The method of any one of Implementation Schemes 165-282 further includes recycling at least a portion of the inert material of the second product stream to the second feed stream.

[0458] Implementation Scheme 284. The method of any one of Implementation Schemes 165-283 further includes recycling at least a portion of the inert material of the second product stream to the first feed stream.

[0459] Implementation Scheme 285. The method of any one of Implementation Schemes 165-284 further includes recycling at least a portion of the CO2 in the second product stream to the first feed stream.

[0460] Implementation Scheme 286. The method described in Implementation Scheme 285 further includes providing CO2 to the second feed stream from a CO2 source other than the first product stream.

[0461] Implementation Scheme 287. The method of Implementation Scheme 286, wherein the CO2 from the second product stream constitutes a majority of the CO2 in the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 in the first product stream.

[0462] Implementation Scheme 288. The method described in any one of Implementation Schemes 165-287, wherein the C of the second product stream 5+ At least a portion of the hydrocarbon provides one or more products.

[0463] Implementation Scheme 289. The method of Implementation Scheme 288, wherein one or more products include fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants, and waxes.

[0464] Implementation Scheme 290. The method of any one of Implementation Schemes 165-289 further includes hydrotreating the C of the second product stream. 5+ At least a portion of hydrocarbons.

[0465] Implementation Scheme 291. The method of any one of Implementation Schemes 165-290, wherein at least a portion of the CO2 in the first feed stream and / or the second feed stream is derived from a renewable source.

[0466] Implementation Scheme 292. The method of any one of Implementation Schemes 165-291, wherein at least a portion of the CO2 in the first feed stream and / or the second feed stream is derived from direct air capture.

[0467] Implementation Scheme 293. The method of any one of Implementation Schemes 165-292, wherein at least a portion of the CO2 in the first feed stream and / or the second feed stream is captured from a manufacturing plant such as a bioethanol plant, steel plant, or cement plant.

[0468] Implementation Scheme 294. The method of any one of Implementation Schemes 165-293, wherein at least a portion of H2 of the first feed stream or the second feed stream originates from a renewable source.

[0469] Implementation Scheme 295. The method of any one of Implementation Schemes 165-294, wherein at least a portion of the H2 in the first feed stream or the second feed stream is green hydrogen.

[0470] Implementation Scheme 296. The method of any one of Implementation Schemes 165-295, wherein at least a portion of the H2 in the first feed stream or the second feed stream is blue hydrogen.

[0471] Implementation Scheme 297. The method of any one of Implementation Schemes 165-296, wherein at least a portion of the H2 in the first feed stream or the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0472] Implementation Scheme 298. The method of any one of Implementation Schemes 165-297 further includes providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water.

[0473] Implementation Scheme 299. The method described in Implementation Scheme 298, wherein at least part of the electricity from a renewable source is used for the electrolysis of water.

[0474] Implementation Scheme 300. The method of Implementation Scheme 298 or Implementation Scheme 299, wherein at least part of the water electrolysis is performed using electricity generated by heat exchange from the first product stream and / or the second product stream or by steam produced by burning a light hydrocarbon stream.

[0475] Implementation Scheme 301. The method of any one of Implementation Schemes 298-300 further includes providing at least a portion of the O2 generated in the electrolysis to the partial oxidation.

[0476] Implementation Scheme 302. The method of any one of Implementation Schemes 165-301, 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.

[0477] Implementation Scheme 303. The method of any one of Implementation Schemes 165-301, wherein the method is carried out in a reactor system, the reactor system comprising a first catalyst bed in which a counter-current gas shift catalyst is disposed and wherein a second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0478] Implementation Scheme 304. The method described in Implementation Scheme 303, wherein the first reactor bed and the second reactor bed are disposed in the same reactor.

[0479] Implementation Scheme 305. The method of any one of Implementation Schemes 165-304, wherein the method is carried out in a reactor system comprising a first catalyst vessel in which one or more reverse water-gas shift catalysts are disposed, and wherein a second reaction zone comprises a second catalyst vessel in which one or more Fischer-Tropsch catalysts are disposed.

[0480] Implementation Scheme 306. The method of Implementation Scheme 305, wherein the one or more first catalyst containers and the one or more second catalyst containers are disposed in the same reactor.

[0481] Implementation Scheme 307. The method of any one of Implementation Schemes 165-306, wherein the method is carried out in a reactor system comprising a reactor in which a reverse water gas shift catalyst and a Fischer-Tropsch catalyst are, for example, mixed together.

[0482] The details shown herein are merely illustrative and for the purpose of discussing preferred embodiments of the invention in an illustrative manner, and are intended to provide the most useful and readily understood description of the principles and concepts considered to be among the various embodiments of the invention. In this regard, no attempt is made to show the structural details of the invention in more detail than is necessary for a basic understanding of the invention, and the description, taken in conjunction with the accompanying drawings and / or embodiments, makes it clear to those skilled in the art how several forms of the invention may be embodied in practice. Therefore, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, devices, or constructions, and thus, variations are naturally possible. It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting unless specifically defined herein.

[0483] Unless otherwise stated herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar designations used in the context of describing the invention (particularly in the context of the following claims) shall be interpreted to cover both the singular and the plural. The description of numerical ranges herein is intended only as a shorthand method of individually referring to each individual value falling within the range. Unless otherwise stated 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 and independent of the other endpoint.

[0484] Unless otherwise stated herein or otherwise clearly contradicts the context, all methods described herein may be performed in any suitable order of steps. The use of any and all embodiments or exemplary language (e.g., "as") provided herein is intended only to better illustrate the invention and not to limit the scope of the separately claimed invention. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0485] Unless the context explicitly requires otherwise, throughout the specification and claims, the terms "comprising," "containing," etc., shall be interpreted in an inclusive sense, rather than an exclusive or exhaustive sense; that is, in the sense of "including but not limited to." The use of singular or plural terms shall also include both singular and plural forms, respectively. Furthermore, when used in this application, the terms "this article," "above," and "below," and terms with similar meanings, shall refer to the entire application and not any specific part thereof.

[0486] As will be understood by those skilled in the art, each embodiment disclosed herein may include, consist of, or be substantially composed of the elements, steps, ingredients, or components specifically stated herein. As used herein, the transitional terms “comprising” or “containing” mean, but are not limited to, and allow the inclusion of unspecified elements, steps, ingredients, or components, even in substantial quantities. The transitional phrase “consisting of” excludes any unspecified elements, steps, ingredients, or components. The transitional phrase “substantially composed of” limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not substantially affect the embodiment.

[0487] Unless otherwise stated, the numerical parameters listed in the specification and appended claims are approximate values ​​and may vary depending on the desired properties sought to be obtained according to the invention. At least, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter shall be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0488] Although the wide range of numerical values ​​and parameters described in this invention are approximate, the values ​​described in the specific embodiments are reported as accurately as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in their respective test measurements.

[0489] The grouping of alternative elements or embodiments of the invention disclosed herein should not be construed as limiting. Each member of a group may be mentioned and claimed individually or in any combination with other members of that group or other elements found herein. For convenience and / or patentability reasons, it is contemplated that one or more members of a group may be included in or removed from the group. When any such inclusion or removal occurs, this specification is deemed to contain the modified group, thereby satisfying the written description of all Markush groups used in the appended claims.

[0490] This document describes some embodiments of the invention, including the best mode known to the inventors for carrying out the invention. Of course, variations of these described embodiments will become apparent to those skilled in the art after reading the foregoing specification. The inventors expect those skilled in the art to appropriately adopt these variations, and the inventors intend to practice the invention in ways other than those specifically described herein. Therefore, the invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or otherwise clearly contradicted by the context, the invention covers any combination of the foregoing elements in all possible variations.

[0491] Furthermore, it should be understood that the embodiments of the invention disclosed herein illustrate the principles of the invention. Other modifications may be employed within the scope of the invention. Therefore, alternative configurations of the invention can be utilized based on the teachings herein, by way of example and not limitation. Thus, the invention is not limited to what is precisely shown and described.

Claims

1. A supported reverse water gas shift catalyst, comprising: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst.

2. The catalyst of claim 1, wherein the support constitutes at least 70% by weight of the catalyst based on oxides.

3. The catalyst of claim 1, wherein the support is a cerium oxide support.

4. The catalyst of claim 3, wherein the cerium oxide support comprises at least 90% by weight cerium oxide based on oxide content.

5. The catalyst of claim 1, wherein the support is a titanium oxide support.

6. The catalyst of claim 5, wherein the titanium oxide support comprises at least 90% by weight titanium oxide based on oxide content.

7. The catalyst of claim 1, wherein the support is an alumina support or a zirconium oxide support.

8. The catalyst of claim 1, wherein the co-catalyst metal is gallium.

9. The catalyst of claim 8, wherein gallium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

10. The catalyst of claim 1, wherein the co-catalyst metal is indium.

11. The catalyst of claim 10, wherein indium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

12. The catalyst of claim 1, wherein the co-catalyst metal is lanthanum.

13. The catalyst of claim 12, wherein lanthanum is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

14. The catalyst of claim 1, wherein the co-catalyst metal is titanium.

15. The catalyst of claim 14, wherein titanium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

16. The catalyst of claim 1, wherein the co-catalyst metal is niobium.

17. The catalyst of claim 16, wherein niobium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

18. The catalyst of claim 1, wherein the co-catalyst metal is vanadium.

19. The catalyst of claim 18, wherein vanadium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

20. The catalyst of claim 1, wherein the co-catalyst metal is zirconium.

21. The catalyst of claim 20, wherein zirconium is present in the catalyst in an amount ranging from 2 to 20% by weight, based on the total weight of the catalyst.

22. The catalyst of claim 1, wherein platinum is present in the catalyst.

23. The catalyst of claim 22, wherein platinum is present in the catalyst in an amount ranging from 0.05% to 5% by weight, based on the total weight of the catalyst.

24. The catalyst of claim 1, wherein palladium is present in the catalyst.

25. The catalyst of claim 24, wherein palladium is present in the catalyst in an amount ranging from 0.05% to 5% by weight, based on the total weight of the catalyst.

26. The catalyst of claim 1, wherein gold is present in the catalyst.

27. The catalyst of claim 26, wherein gold is present in the catalyst in an amount ranging from 0.05% to 5% by weight, based on the total weight of the catalyst.

28. The catalyst of claim 1, wherein the weight ratio of platinum, palladium and / or gold to the co-catalyst metal is at least 0.05:

1.

29. The catalyst of claim 1, wherein the weight ratio of platinum, palladium and / or gold to the co-catalyst metal is at most 2:

1.

30. The catalyst of claim 1, wherein the weight ratio of platinum, palladium and / or gold to the co-catalyst metal is in the range of 0.05:1 to 1:

1.

31. The catalyst of claim 1, wherein the total amount of cerium, titanium, aluminum, zirconium, co-catalyst metal, platinum, palladium and gold in the catalyst is at least 90% by weight, based on metal content.

32. A method for preparing the catalyst according to any one of claims 1-31, the method comprising: Provide a carrier, which is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide; The carrier is brought into contact with one or more liquids, each of which contains one or more compounds containing a co-catalyst metal dispersed in a solvent, and optionally one or more compounds containing platinum, palladium, or gold, wherein the co-catalyst metal is selected from gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium. The solvent is allowed to evaporate to provide a catalyst precursor; and The catalyst precursor is calcined.

33. A method for performing a reverse water-gas shift reaction, the method comprising: The catalyst according to any one of claims 1-31 is contacted with a feed stream containing CO2 and H2 at a temperature in the range of 250-900°C to provide a product stream containing CO and H2, said product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream.

34. A method for performing integrated Fischer-Tropsch method, the method comprising: Provide a first feed stream containing H2 and CO2; The reverse water gas shift catalyst is contacted with the first feed stream at a first temperature in the range of 250-900°C and a first pressure to carry out the reverse water gas shift reaction, so as to provide a first product stream containing CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream. The Fischer-Tropsch catalyst is contacted with at least a portion of a second feed stream containing H2 and CO from the first product stream at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons, The aforementioned countercurrent gas shift catalyst is a supported countercurrent gas shift catalyst, which comprises: The carrier is a cerium oxide carrier, a titanium oxide carrier, an alumina carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising two or more of cerium oxide, titanium oxide, alumina and zirconium oxide. A co-catalyst metal, selected from at least one of gallium, indium, lanthanum, titanium, niobium, vanadium, and zirconium, is present in an amount ranging from 0.5% to 20% by weight of the catalyst, based on the total weight of the catalyst; and At least one of platinum, palladium or gold is optionally present in an amount ranging from 0.05% to 10% by weight of the catalyst, based on the total weight of the catalyst.

35. The method of claim 34, wherein the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:

1.

36. The method of claim 34, wherein the reverse water-gas shift reaction has at least 85% CO selectivity.

37. The method of claim 34, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 15%.

38. The method of claim 34, wherein the reverse water-gas shift reaction has a CO2 conversion rate of at least 30%.

39. The method of claim 34, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 400-800°C.

40. The method of claim 34, wherein the method comprises activating the reverse water gas shift catalyst with a reducing feed stream containing a reducing gas.

41. The method of claim 34, wherein the first product stream contains no more than 75 mol% CO2.

42. The method of claim 34, wherein the first product stream comprises no more than 15 mol% methane.

43. The method of claim 34, wherein the method further comprises separating the first product stream to recycle at least a portion of the CO2 or H2 of the first product stream back to the first feed stream.

44. The method of claim 34, wherein at least 25% of the CO of the first product stream is contained in the second feed stream.

45. The method of claim 34, wherein the first product stream comprises H2, and wherein at least 25% of the H2 in the first product stream is included in the second feed stream.

46. ​​The method of claim 34, wherein at least 10% of the CO2 in the first product stream is contained in the second feed stream.

47. The method of claim 34, wherein the second feed stream does not contain a significant amount of CO2 from the first product stream.

48. The method of claim 34, wherein the second feed stream has an H2:CO ratio in the range of 0.5:1 to 6:

1.

49. The method of claim 34, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

50. The method of claim 49, wherein the Fischer-Tropsch catalyst further comprises manganese.

51. The method of claim 34, wherein the second temperature is in the range of 200-350°C.

52. The method of claim 34, wherein the first temperature is at least 100°C higher than the second temperature.

53. The method of claim 34, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30% C 5+ The selective processing of alkanes is carried out.

54. The method of claim 34, further comprising separating at least a portion of C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

55. The method of claim 34, 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.

56. The method of claim 34, further comprising recycling at least a portion of the H2 of the second product stream to the second feed stream.

57. The method of claim 34, 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.

58. The method of claim 34, 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.

59. The method of claim 34, further comprising recycling at least a portion of the CO2 from the second product stream to the first feed stream, wherein the CO2 from the second product stream constitutes at least 90% of the CO2 from the first feed stream.

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