Nickel catalyst for reverse water gas shift catalyst 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; nickel present in an amount ranging from 0.05 to 10 wt% of the catalyst, based on the total weight of the catalyst; and manganese present in an amount ranging from 0.5 to 20 wt% of the catalyst, based on the total weight of the catalyst.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to International Patent Application No. PCT / CN2022 / 102630 filed on June 30, 2022 and International Patent Application No. PCT / CN2022 / 102799 filed on June 30, 2022, each of which is hereby incorporated by reference in its entirety.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] 1. Field

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

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

[0007]

[0008] This can be used, for example, to change the CO:H2 ratio of the gas mixture for further processing. The carbon monoxide and hydrogen thus formed are valuable raw materials for many chemical processes, for example, the well-known Fischer-Tropsch (FT) process as shown in reaction equation (2).

[0009]

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

[0011]

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

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

[0014]

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

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

[0017]

[0018] Therefore, because the carbon-producing side reactions (Equations (5)-(7)) are also endothermic and are favored at higher temperatures, operating at higher temperatures to favor the desired carbon monoxide product may severely affect catalyst life through carbon deposition.

[0019] Given the multiple reactions at play and the competing thermodynamics, there remains a need in the art for new rWGS catalysts and methods, especially rWGS catalysts and methods that are integrated with the Fischer-Tropsch process. SUMMARY OF THE INVENTION

[0021] In one aspect, the present disclosure provides a supported reverse water gas shift catalyst comprising:

[0022] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0023] Nickel, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0024] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0025] In another aspect, the present disclosure provides a method of making a catalyst as described herein, the method comprising:

[0026] Providing a carrier, the carrier being a cerium oxide carrier, a titanium oxide carrier, an aluminum oxide carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;

[0027] contacting the support with a liquid comprising one or more nickel-containing compounds and one or more manganese-containing compounds dispersed in a solvent;

[0028] allowing the solvent to evaporate to provide a catalyst precursor; and

[0029] The catalyst precursor is calcined.

[0030] In another aspect, the present disclosure provides a catalyst as described herein, made by a method as described herein.

[0031] On the other hand, the present disclosure provides a method for performing a reverse water gas shift reaction, the method comprising contacting a catalyst as described herein with a feed stream comprising CO2 and H2 at a temperature in the range of 500-900°C to provide a product stream comprising CO and H2, wherein the product stream has a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0032] In one aspect, the present disclosure provides a method of performing an integrated Fischer-Tropsch process, the method comprising:

[0033] Providing a first feed stream comprising H2 and CO2;

[0034] contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 500-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream;

[0035] contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream of CO comprising H2 and at least a portion of the first product stream to provide a catalyst comprising C 5+ a second product stream of hydrocarbons,

[0036] The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising:

[0037] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0038] Nickel, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0039] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0040] BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The accompanying drawings are included to provide a further understanding of the method of the present disclosure, and are incorporated into and constitute a part of this specification. The drawings are not necessarily drawn to scale, and the dimensions of various elements may be distorted for clarity. The accompanying drawings illustrate one or more embodiments of the present disclosure and, together with the description, serve to explain the principles and operations of the present disclosure.

[0042] Figure 1 is a schematic diagram of the reverse water gas shift reaction as described herein.

[0043] Figure 2 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0044] Figure 3 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0045] Figure 4 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0046] Figure 5 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0047] Figure 6 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0048] Figure 7 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0050] As described above, the reverse water gas shift reaction reacts carbon dioxide with hydrogen to form carbon monoxide and water, and can be used to provide a feedstock containing carbon monoxide and hydrogen, commonly referred to as "syngas", for use in processes such as the Fischer-Tropsch process. However, the Sabatier reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction. The Sabatier reaction and CO methanation are exothermic and are dominant at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and are dominant at higher temperatures. Therefore, despite these complications, there is still a need for rWGS catalysts that can provide good performance. Here, the inventors have provided a supported reverse water gas shift catalyst comprising a metal oxide support, nickel and manganese, which can meet the requirements required for a commercially available rWGS method. In addition, the inventors have found that the rWGS method is particularly advantageous for integration with the Fischer-Tropsch process by using a supported reverse water gas shift catalyst comprising a metal oxide support, nickel and manganese.

[0051] Reverse Water Gas Shift Catalyst

[0052] In one aspect, the present disclosure provides a supported reverse water gas shift catalyst. The supported reverse water gas shift catalyst comprises a carrier, which is a cerium oxide carrier, a titanium oxide carrier, an aluminum oxide carrier, a zirconium oxide carrier, or a mixed oxide carrier comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; at least one nickel, which is present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and manganese, which is present in an amount ranging from 0.5 to 20 weight percent of the catalyst based on the total weight of the catalyst.

[0053] As described above, the reverse water gas shift catalyst of the present disclosure is a supported catalyst. In various embodiments described elsewhere herein, the support constitutes at least 70 wt %, such as at least 75 wt %, or 80 wt %, or 85 wt %, or 90 wt % of the catalyst, based on oxide.

[0054] In various embodiments as described separately herein, the carrier is a cerium oxide carrier. As used herein, a "cerium oxide" carrier is a carrier presenting at least a surface layer (e.g., a thickness of 50 microns) of cerium oxide calculated as at least 50% by weight based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the cerium oxide carrier comprises at least 60% by weight of cerium oxide, such as at least 70% by weight of cerium oxide or at least 80% by weight of cerium oxide. In some such embodiments, at least the surface layer of the cerium oxide carrier comprises at least 90% by weight of cerium oxide. For example, in some embodiments, at least the surface layer of the cerium oxide carrier comprises at least 95% by weight of cerium oxide or at least 98% by weight of cerium oxide. In various examples, the cerium oxide carrier contains substantially distributed cerium oxide, such as based on oxide, at least 50% by weight of the cerium oxide carrier is cerium oxide. For example, in various embodiments, the cerium oxide carrier comprises at least 60% by weight of cerium oxide, such as at least 70% by weight of cerium oxide or at least 80% by weight of cerium oxide. In various embodiments, the ceria support comprises at least 90 wt% ceria, such as at least 95 wt% ceria, or at least 98 wt% ceria. In some embodiments, the ceria support may further comprise additional metals or metal oxides.

[0055] In various embodiments as described elsewhere herein, the carrier is a titanium oxide carrier. As used herein, a "titania" carrier is a carrier that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% titanium oxide based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the titanium oxide carrier comprises at least 60% titanium oxide, such as at least 70% titanium oxide, or at least 80% titanium oxide. In some such embodiments, at least the surface layer of the titanium oxide carrier comprises at least 90% titanium oxide. For example, in some embodiments, at least the surface layer of the titanium oxide carrier comprises at least 95% titanium oxide or at least 98% titanium oxide. In various examples, the titanium oxide carrier contains substantially distributed titanium oxide, such as based on oxide, at least 50% by weight of the titanium oxide carrier is titanium oxide. For example, in various embodiments, the titanium oxide carrier comprises at least 60% titanium oxide, such as at least 70% titanium oxide, or at least 80% titanium oxide. In various embodiments, the titania support comprises at least 90 wt% titania, such as at least 95 wt% titania, or at least 98 wt% titania. In some embodiments, the titania support may further comprise additional metals or metal oxides.

[0056] In various embodiments as described elsewhere herein, the support is an alumina support. As used herein, an "alumina" support is a support that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% by weight of alumina based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the alumina support comprises at least 60% by weight of alumina, such as at least 70% by weight of alumina, or at least 80% by weight of alumina. In some such embodiments, at least the surface layer of the alumina support comprises at least 90% by weight of alumina. For example, in some embodiments, at least the surface layer of the alumina support comprises at least 95% by weight of alumina or at least 98% by weight of alumina. In various examples, the alumina support contains substantially distributed alumina, such as at least 50% by weight of the alumina support is alumina based on oxide. For example, in various embodiments, the alumina support comprises at least 60% by weight of alumina, such as at least 70% by weight of alumina, or at least 80% by weight of alumina. In various embodiments, the alumina support comprises at least 90 wt% alumina, such as at least 95 wt% alumina, or at least 98 wt% alumina. In some embodiments, the alumina support may further comprise additional metals or metal oxides.

[0057] In various embodiments as described elsewhere herein, the carrier is a zirconia carrier. As used herein, a "zirconia" carrier is a carrier that presents at least a surface layer (e.g., a thickness of 50 microns) of at least 50% zirconia based on oxide. In various embodiments of the present disclosure as described herein, at least the surface layer of the zirconia carrier comprises at least 60% zirconia, such as at least 70% zirconia, or at least 80% zirconia. In some such embodiments, at least the surface layer of the zirconia carrier comprises at least 90% zirconia. For example, in some embodiments, at least the surface layer of the zirconia carrier comprises at least 95% zirconia or at least 98% zirconia. In various examples, the zirconia carrier contains substantially distributed zirconia, such as at least 50% zirconia based on oxide. For example, in various embodiments, the zirconia carrier comprises at least 60% zirconia, such as at least 70% zirconia, or at least 80% zirconia. In various embodiments, the zirconia support comprises at least 90 wt% zirconia, such as at least 95 wt% zirconia, or at least 98 wt% zirconia. In some embodiments, the zirconia support may further comprise additional metals or metal oxides.

[0058] In various embodiments as described separately herein, the carrier is a mixed oxide carrier. These can be provided, for example, by admixing a variety of the above-mentioned oxides and being formed into a carrier comprising both. For example, in some embodiments, the mixed oxide carrier is a mixture of two or more metal oxides such as cerium oxide, titanium oxide, aluminum oxide and zirconium oxide. In some embodiments, based on oxide, at least the surface layer of the carrier comprises two or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide totaling at least 50 weight %. In some embodiments, at least the surface layer of the mixed oxide carrier comprises at least 60 weight %, for example, at least 70 weight % or at least 80 weight % of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide two or more. In some embodiments, at least the surface layer of the mixed oxide carrier comprises at least 90 weight %, for example, at least 95 weight % or at least 98 weight % of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide two or more. In various examples, the mixed oxide carrier contains oxides that are substantially distributed, for example, at least 50 weight % of the mixed oxide carrier 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 wt%, such as at least 70 wt%, or at least 80 wt% of 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 wt%, such as at least 95 wt%, or at least 98 wt% of 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.

[0059] The inventors have discovered that cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide can provide good performance in the absence of significant amounts of other metals in the support. For example, in various embodiments of the present disclosure as described elsewhere herein, the support does not contain more than 2 wt. %, such as more than 1 wt. %, or more than 0.5 wt. % of the total amount of the additional metal, based on the oxide.

[0060] However, the inventors have noted that in many cases, performance can be desirably affected by including other metals in the support. Therefore, in other embodiments as described elsewhere herein, the support includes at least one additional metal. In various embodiments, the total amount of at least one additional metal is in the range of 0.5-20 wt %, such as 1-20 wt %, or 2-20 wt %, or 0.5-15 wt %, or 1-15 wt %, or 2-15 wt %, or 0.5-10 wt %, or 1-10 wt %, or 2-10 wt %, or 0.5-5 wt %, or 1-5 wt %, based on the oxide.

[0061] The carrier suitable for use herein can be provided with a certain range of pore volume. One of ordinary skill in the art will select a pore volume suitable for the desired catalytic method. For example, in various embodiments as described separately herein, the pore volume is at least 0.05 mL / g, for example at least 0.1 mL / g. In various embodiments as described separately herein, the pore volume is at most 1.5 mL / g, for example at most 1 mL / g. In various embodiments of the disclosure as described herein, the pore volume is in the range of 0.05-1.5 mL / g, for example 0.1 mL / g to 1 mL / g. The pore volume is measured by mercury porosimetry, for example as measured according to ASTM D4284-12.

[0062] As described above, the supported reverse water gas shift catalyst of the present disclosure comprises nickel. For example, in various embodiments as described elsewhere herein, nickel is present in the catalyst. For the present disclosure, the amount of nickel present is calculated as the weight percentage of nickel atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which the nickel may exist. Nickel can be present in the catalyst in various forms; most commonly, nickel is present primarily as a metal, a metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, nickel is present in the catalyst in an amount ranging from 0.05 to 10% by weight, such as from 0.1 to 10% by weight, or from 0.5 to 10% by weight, 1 to 10% by weight, or from 2 to 10% by weight, or from 5 to 10% by weight, based on the total weight of the catalyst. For example, in some embodiments, nickel is present in the catalyst in an amount ranging from 0.05 to 7% by weight, such as from 0.1 to 7% by weight, or from 0.5 to 7% by weight, or from 1 to 7% by weight, or from 2 to 7% by weight, based on the total weight of the catalyst. In some embodiments, nickel is present in the catalyst in an amount ranging from 0.05 to 5 wt %, for example, from 0.1 to 5 wt %, or from 0.5 to 5 wt %, or from 1 to 5 wt %, or from 2 to 5 wt %, based on the total weight of the catalyst. For example, in some embodiments of the disclosure as described herein, nickel is present in the catalyst in an amount ranging from 0.05 to 2 wt %, for example, from 0.1 to 2 wt %, or from 0.3 to 2 wt %, or from 0.5 to 2 wt %, based on the total weight of the catalyst. In some embodiments, nickel is present in the catalyst in an amount ranging from 0.05 to 1.5 wt %, for example, from 0.1 to 1.5 wt %, or from 0.3 to 1.5 wt %, or from 0.5 to 1.5 wt %, based on the total weight of the catalyst. In some embodiments, nickel is present in an amount ranging from 0.05 to 1 wt %, such as 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst. In some embodiments, nickel is present in an amount ranging from 0.05 to 0.8 wt %, such as 0.1 to 0.8 wt %, or 0.3 to 0.8 wt %, or 0.5 to 0.8 wt %, based on the total weight of the catalyst.

[0063] As described above, the supported reverse water gas shift catalyst of the present disclosure also includes manganese. The inventors have determined that including manganese in the catalyst can provide improved performance, as described in the following examples. For the purposes of the present disclosure, the amount of manganese present is calculated as the weight percentage of manganese atoms in the catalyst based on the total weight of the catalyst, regardless of the form in which manganese may be present. Manganese can be present in the catalyst in various forms; most commonly, manganese is present primarily as a metal oxide, a metal, or a combination thereof. In various embodiments of the present disclosure as described elsewhere herein, manganese is present in the catalyst in an amount ranging from 0.5 to 20 weight %, based on the total weight of the catalyst. For example, in various embodiments, manganese is present in the catalyst in an amount ranging from 0.5 to 15 weight %, or 0.5 to 12 weight %, or 0.5 to 10 weight %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in the catalyst in an amount ranging from 1 to 20 wt %, for example, 1 to 15 wt %, or 1 to 12 wt %, or 1 to 10 wt %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in an amount ranging from 2 to 20 wt %, for example, 2 to 15 wt %, or 2 to 12 wt %, or 2 to 10 wt %, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in an amount ranging from 4 to 20 wt %, for example, 4 to 15 wt %, or 4 to 12 wt %, or 4 to 10 wt %, based on the total weight of the catalyst.

[0064] Nickel and manganese can be provided in various weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of nickel to manganese present in the catalyst is at least 0.05: 1. For example, in various embodiments, the weight ratio of nickel to manganese is at least 0.1: 1. In various embodiments of the present disclosure as described herein, the weight ratio of nickel to manganese present in the catalyst is at most 5: 1. For example, the weight ratio of nickel to manganese is at most 2: 1, or 1: 1, or 0.5: 1. For example, in various embodiments, the weight ratio of nickel to manganese present in the catalyst is in the range of 0.05: 1 to 5: 1. For example, the weight ratio of nickel to manganese ranges from 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.

[0065] The inventors have determined that suitable reverse water gas shift catalysts can be formed by one or more of cerium oxide, titanium oxide, aluminum oxide and zirconium oxide as carriers and nickel combined with manganese contained in / on the catalyst. As will be understood by those of ordinary skill in the art, the amount of cerium, titanium, aluminum, zirconium, nickel and manganese can be quantified based on metals, regardless of the form in which these metals may exist. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of the metal in the catalyst (i.e., based on metal), i.e., oxygen or non-metallic counterions are not included in the calculation. Therefore, in various embodiments of the present disclosure as described herein, based on metal, the total amount of cerium, titanium, aluminum, zirconium, manganese and nickel in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight or at least 98% by weight. For example, in some specific embodiments, based on metal, the total amount of cerium, manganese and nickel in the catalyst is at least 90% by weight of the catalyst, such as at least 95% by weight or at least 98% by weight. In other embodiments, the total amount of titanium, manganese and nickel in the catalyst is at least 90% by weight of the catalyst, e.g., at least 95% by weight, or at least 98% by weight, based on the metal. In other embodiments, the total amount of aluminum, manganese and nickel in the catalyst is at least 90% by weight of the catalyst, e.g., at least 95% by weight, or at least 98% by weight, based on the metal. In other embodiments, the total amount of zirconium, manganese and nickel in the catalyst is at least 90% by weight of the catalyst, e.g., at least 95% by weight, or at least 98% by weight, based on the metal.

[0066] As described above, the catalyst as described herein is mainly composed of cerium, titanium, aluminum, zirconium, manganese and nickel. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has an additional metal content of no more than 10% by weight. The additional metal can be any metal other than nickel, manganese, cerium, titanium, aluminum or zirconium. For example, the additional metal can be selected from alkali metals, alkaline earth metals, rare earth metals, other coin metals, precious metals or other transition metals. For example, in various embodiments, based on the total weight of the catalyst, the catalyst has an additional metal content of no more than 5% by weight, or no more than 2% by weight, or no more than 2% by weight. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has a copper content of no more than 10% by weight. For example, in various embodiments, based on the total weight of the catalyst, the catalyst has a copper content of no more than 5% by weight, or no more than 2% by weight, or no more than 1% by weight. In some embodiments as described herein, based on the total weight of the catalyst, the catalyst has an alkali metal content of no more than 10% by weight. For example, in various embodiments, the catalyst has an alkali metal content of no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has an alkaline earth metal content of no more than 10 wt %, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has an alkaline earth metal content of no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, based on the total weight of the catalyst.

[0067] As mentioned above, the supported catalyst comprises manganese and nickel. Depending on the synthesis method, these species, which are usually present mainly in metallic form and / or oxide form, can be arranged at various different positions on the support. For example, they can be found in the pores of the support and on the outer surface of the support. They can be found substantially throughout the support, such as when a large amount of impregnation liquid is used, or only in the surface layer of the support, such as when the impregnation liquid does not penetrate into the entire support, such as when using the incipient wetness impregnation technique.

[0068] Without intending to be bound by theory, it is believed that the active form of nickel is generally in a substantially metallic form. As described below, since nickel may exist substantially in an oxide form after catalyst preparation and during transportation and storage, it is generally desirable to activate the catalyst by contacting the catalyst with a reducing agent (e.g., hydrogen gas) so as to convert a majority of such oxides into a metallic form. However, one of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a variety of nickel forms in its catalysts, as these forms may be active or may be readily converted into an active form.

[0069] After catalyst preparation and during transportation and storage, manganese will generally be provided in the form of oxides. Without intending to be bound by theory, the inventors believe that manganese improves the catalytic activity of supported nickel catalysts by reducing CO methanation (which affects CO selectivity) that may occur within a typical reverse water gas shift reaction temperature range. The inventors believe that the improved activity is attributable to the interfacing of manganese and nickel and carriers (e.g., cerium oxide, titanium oxide, aluminum oxide, zirconium oxide or mixed oxides). The inventors envision that in the activation process of nickel species, some manganese oxides can be converted into metallic forms. However, it will be appreciated by those of ordinary skill in the art that the present disclosure contemplates the usefulness of a variety of manganese forms in its catalyst, because these manganese forms can provide promotion or can be easily converted into forms that will have promotion.

[0070] It will be appreciated by those skilled in the art that catalysts of the present disclosure can be provided in many forms, particularly depending on the particular form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The carrier itself can be provided as a discrete body of material, for example as a porous particle, a pellet or a shaped extrudate, wherein nickel and manganese are arranged thereon to provide the catalyst. However, in other embodiments, the catalyst of the present disclosure itself can be formed as a layer on the substrate below. The substrate below is not particularly limited. It can be formed by, for example, a metal or a metal oxide, and itself can be provided in various forms, such as a particle, a pellet, a shaped extrudate or a monolith. Of course, as will be appreciated by those skilled in the art, other embodiments may be possible.

[0071] Another aspect of the present disclosure provides a method for making a catalyst as described herein. As described above, the method includes providing a support, the support being a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; contacting the support with one or more liquids, each of the one or more liquids comprising one or more nickel-containing compounds and / or one or more manganese-containing compounds dispersed in a solvent; allowing the solvent to evaporate to provide a catalyst precursor; and calcining the catalyst precursor. Of course, one of ordinary skill in the art will appreciate that other methods may be used to make the catalyst as described herein.

[0072] In some embodiments of the disclosure as described herein, contacting the carrier with the liquid comprises adding the liquid in an amount approximately equal to the pore volume of the carrier (i.e., within 25% thereof, or within 10% thereof). In other embodiments, contacting the carrier with the liquid comprises adding the liquid in an amount greater than the pore volume of the carrier. For example, in some embodiments, the ratio of the amount of liquid to the amount of carrier on a mass basis is in the range of 0.75:1 to 5:1, such as in the range of 0.9:1 to 3:1. In some embodiments, contacting the carrier with the liquid provides a slurry.

[0073] In various embodiments of the present disclosure as described herein, solvent evaporation is allowed to proceed at ambient temperature. In various embodiments, solvent evaporation is allowed to proceed for a drying time at an elevated temperature. One of ordinary skill in the art will be able to select appropriate equipment or instruments to allow solvent evaporation, and such equipment or instruments are not particularly limited. In addition, one of ordinary skill in the art will appreciate that the elevated temperature at which solvent evaporation is allowed depends on the boiling point of the solvent. Therefore, one of ordinary skill in the art will be able to select an appropriate elevated temperature. For example, in some embodiments, the elevated temperature is in the range of 50-150° C., for example, in the range of 50-120° C., or 50-100° C., or 100-150° C., or 100-120° C. In some embodiments, the drying time is in the range of 1 to 48 hours, for example, in the range of 10 to 36 hours, or 12 to 24 hours. For example, in a particular embodiment, the drying time is about 24 hours. In some embodiments, solvent evaporation is allowed to proceed for a drying time at a vacuum and elevated temperature, as described herein. In some embodiments, the solvent is allowed to evaporate at elevated temperature, for example in the range of 30-100°C in a stirred dry bath.

[0074] In some embodiments of the present disclosure as described herein, the calcined catalyst precursor is subjected to a calcination time in a furnace at a calcination temperature. For example, in some embodiments, the calcination time is in the range of 0.5 to 24 hours, or 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours. In some embodiments, the calcination temperature is in the range of 100-600° C., such as in the range of 120-500° C.

[0075] As described above, the method for manufacturing a catalyst as described herein includes contacting a carrier with one or more liquids, each of which includes one or more compounds containing nickel and / or one or more compounds containing manganese dispersed in a solvent. The compound containing nickel and manganese is not particularly limited, and one of ordinary skill in the art will be able to select a suitable compound soluble in a solvent. For example, in some embodiments of the disclosure as described herein, the compound containing nickel and manganese can be selected from metal salts (such as nitrates and acetates). The solvent is also not particularly limited, and one of ordinary skill in the art will be able to select a suitable solvent that can be absorbed by the carrier. For example, in some embodiments of the disclosure as described herein, the solvent is water. As will be appreciated by one of ordinary skill in the art, these metal species are conveniently provided in the same liquid, so that only a step of contacting the carrier with the liquid is required. However, other schemes are also possible.

[0076] In another aspect, the present disclosure provides a catalyst as described herein prepared by a method as described herein.

[0077] Reverse Water Gas Shift Reaction

[0078] 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 comprising CO2 and H2 at a temperature in the range of 500-900°C to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream. Figure 1 An example of such a method is shown schematically in Figure 1 In the process 100 herein, a reverse water gas shift reaction is performed by providing a feed stream 111 comprising H2 and CO2 to a reaction zone, such as a 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 500-900° C. to provide a product stream 112 comprising CO and H2. The product stream has a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0079] As used herein, "feed stream" is used to refer to the total material input to a process step, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single inlet or through multiple inlets. For example, the H2 and CO of the feed stream can be provided to the reverse water gas shift catalyst in a single physical stream (e.g., in a single conduit to the reactor 110) or in multiple physical streams (e.g., separate inlets for CO and H2, or one inlet for fresh CO and H2 and another inlet for recycled CO and / or H2). Similarly, "product stream" is used to refer to the total material output from a process step, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single outlet or through multiple outlets.

[0080] In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO selectivity of at least 50%, e.g., at least 60%, or 70%, or 80%, or 90%. "Selectivity" for a given reaction product as used herein is the mole fraction of the feed (here CO2) that is converted to the product (CO for "CO selectivity"). The inventors have determined that the catalysts of the present invention can provide excellent CO selectivity even when operated at lower temperatures than many conventional reverse water gas shift catalysts, despite the competing potential of the Sabatier reaction and CO methanation. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO selectivity in the range of 50-99 weight %. For example, in various embodiments, the reverse water gas shift reaction has a CO selectivity in the range of 50-90 wt%, or 50-80 wt%, or 50-70 wt%, or 50-60 wt%, or 60-99 wt%, or 60-90 wt%, or 60-80 wt%, or 60-70 wt%, or 70-99 wt%, or 70-90 wt%, or 70-80 wt%.

[0081] It is noteworthy that the catalysts described herein can be operated to provide carbon monoxide with only a minimal degree of methane formation. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a methane selectivity of no more than 40%, such as no more than 35%, or 30%, or 25%, or 20%. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a methane selectivity of no more than 10%, such as no more than 8%. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a methane selectivity of no more than 5%, such as no more than 4%. For example, in some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 2%, such as no more than 1%. In some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, such as no more than 0.4%.

[0082] 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. "Conversion" as used herein is the mole fraction of the feed to the reaction (whether the reaction is a desirable product or an undesirable species). In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO2 conversion of at least 5%, such as at least 10%, or 20%. For example, in some embodiments, the reverse water gas shift reaction has a CO2 conversion of at least 30%, such as at least 40%, or 50%, or 60%. In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO2 conversion of no more than 90%, such as no more than 80% or no more than 70%. For example, in some embodiments, the reverse water gas shift reaction has a CO2 conversion of no more than 65%, such as no more than 60%. For example, in various embodiments as described separately herein, CO conversion rate is 10-90%, for example 10-80%, or 10-70%, or 10-60%, or 10-65%, or 20-90%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30-90%, or 30-80%, or 30-70%, or 30-60%, or 30-65%, or 40-90%, or 40-80%, or 40-70%, or 40-60%, or 40-65% scope. Based on the disclosure herein, those of ordinary skill in the art will operate under the degree of conversion that provides the desired product. Of course, in other embodiments, for example when in a stacked bed or mixed bed system, the CO conversion rate can be even higher than the conversion rate described herein.

[0083] Advantageously, the methods described herein can be carried out at temperatures lower than those used in many conventional reverse water gas shift methods. As described above, the various methods of the present disclosure can be carried out at temperatures in the range of 500-900°C. For example, in various embodiments of the present disclosure as described herein, the method for carrying out the reverse water gas shift reaction is carried out at a temperature in the range of 500-850°C, for example, in the range of 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 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. In some embodiments, the method for performing the reverse water gas shift reaction 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. In some embodiments, the method for performing the reverse water gas shift reaction 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. In some embodiments, the method for performing the reverse water gas shift reaction 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.

[0084] In some embodiments, the reverse water gas shift reaction is carried out at a temperature in the range of 200-500° C., e.g., 200-450° C., or 200-400° C., or 200-350° C., or 250-500° C., or 250-450° C., or 250-400° C., or 250-350° C. The inventors have noted that operation at these temperatures can provide lower energy requirements.

[0085] As described above, the feed stream comprises CO2 and H2. Advantageously, the inventors have recognized that both can come from renewable or otherwise environmentally responsible sources. For example, at least part of H2 can be so-called "green" hydrogen, such as produced by water electrolysis using renewable electricity (such as wind power, solar energy or hydroelectric power). In other embodiments, at least part of H2 can come from so-called "blue" sources, such as from a natural gas reforming process 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 of the H2 of the feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen. CO2 can be captured generally from the environment, or more directly from the process of forming CO2 (especially in areas where it is difficult to reduce emissions), so that the product subsequently made from CO is at least carbon neutral. For example, in some embodiments, at least part of CO2 comes from direct air capture, or from a manufacturing plant such as a bioethanol plant (such as CO2 produced by fermentation), a steel plant or a cement plant. 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 decarbonizing transportation fuels (for the automotive and aviation sectors), because the carbon monoxide produced in the reaction can be easily used to synthesize liquid hydrocarbon fuels through recognized technologies.

[0086] 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 gas provided separately to the reaction zone. In various embodiments as described elsewhere 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, one of ordinary skill in the art will provide a desired ratio of H2:CO2 in the feed stream that provides a desired conversion and selectivity; if consistent with the desired conversion and selectivity, an excess of H2 can be provided to flow through the system and provide a product stream having a desired H2 to CO ratio for downstream processes.

[0087] Other gases may also be included in the feed stream. For example, in some embodiments, the feed stream further comprises CO. In some embodiments of the present disclosure as otherwise described herein, the feed stream further comprises one or more inert gases. For example, in some embodiments, the feed stream further comprises nitrogen and / or methane.

[0088] As will be appreciated by those of ordinary skill in the art, the methods described herein can be carried out at various pressures. In various embodiments of the present disclosure, the method for carrying out reverse water-gas shift reaction is carried out at a pressure of 1 to 100 bar. For example, the method is carried out at a pressure of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 70 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar.

[0089] As will be appreciated by one of ordinary skill in the art, the methods described herein can be performed at various GHSVs (gas hourly space velocities). Thus, the GHSV for performing the reverse water gas shift reaction is not particularly limited. For example, in some embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is performed at 1,000 to 2,000,000 h 2 . -1 In various embodiments, the method for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is carried out at a GHSV of 1,000 to 50,000 h -1 , or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1, or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h -1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

[0090] The rWGS catalyst described herein is based in part on nickel. It will generally be desirable, for example, to activate the rWGS catalyst before contacting the feed stream. Thus, in some embodiments of the present disclosure as described herein, the method includes activating the rWGS catalyst before contacting the catalyst with the feed stream. For example, in some embodiments, activating the catalyst includes contacting the catalyst with a reducing stream containing a reducing gas (e.g., hydrogen). In various embodiments of the present disclosure, the reducing stream contains hydrogen in an amount of at least 25 mol%, such as at least 50 mol%, or 75 mol%, or 90 mol%. One of ordinary skill in the art will determine conditions suitable for reducing and activating the rWGS catalyst. Therefore, one of ordinary skill in the art will be able to select appropriate temperature, pressure, and time to activate the rWGS catalyst. For example, in various embodiments, the activated catalyst is carried out at a temperature in the range of 200° C. to 800° C. In some embodiments, activating the catalyst is carried out at a temperature in the range of 250° C. to 800° C., or 300° C. to 800° C., or 200° C. to 700° C., or 250° C. to 800° C., or 300° C. to 700° C. In some embodiments of the disclosure as described herein, activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or at least 50% reduced).

[0091] The inventors have found that contacting the rWGS catalyst as described herein with a feed stream can provide a product stream having advantageously high CO selectivity and low methane selectivity. As described above, the amount of CO in the product stream can be further controlled by the rWGS reaction conditions. However, in general, the method for performing the rWGS reaction as described herein provides 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, which is consistent with the degree of conversion described herein. For example, in various embodiments, the product stream comprises no more than 95 mol % of CO2, or no more than 90 mol % of CO2. In some embodiments, the product stream comprises no more than 85 mol % of CO2, or no more than 80 mol % of CO2. In other examples, the product stream comprises no more than 75 mol % or no more than 70 mol % of CO2. However, as described above, the inventors have determined that it may be desirable to carry out the method at an intermediate degree of conversion to provide a desirable high CO selectivity and a desirable low methane selectivity. Thus, in various embodiments as otherwise described herein, the product stream comprises an amount of CO 2 as well as CO.

[0092] Other gases may also be included in the product stream. In some embodiments of the present disclosure as described elsewhere herein, the product stream further comprises one or more inert gases. These inert gases may be included in the feed stream or provided from a source other than the feed stream. For example, in some embodiments, the product stream further comprises nitrogen and / or methane.

[0093] The product stream may include H2 in various ratios combined with CO, depending on, among other things, the degree of conversion, CO selectivity, the relative amounts of H2 and CO2 in the feed stream, and the reaction conditions. For example, in some embodiments, the ratio of H2:CO 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).

[0094] One of ordinary skill in the art will appreciate that based on the process as described herein, the product stream may contain H2, CO, and CO2 as well as various amounts of other components. The components of the product stream may be separated and used for various purposes in the rWGS process.

[0095] For example, in various embodiments of the present disclosure as described herein, the method further includes separating the product stream so that at least a portion of one or more components of the product stream (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%) is recycled to the feed stream. For example, when the product stream comprises CO2, the method may include recycling at least a portion of the CO2 of the product stream (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%) to the feed stream. The product stream may also include H2; in some embodiments, the method further includes recycling at least a portion of the H2 of the product stream (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%) to the feed stream.

[0096] This type of recirculation is shown in Figure 1 (and Figure 2 ). Here, method 100 includes separating at least a portion of CO2 (stream 114) from product stream 112 for recycling to feed stream 111. Similarly, method 100 includes separating at least a portion of H2 (stream 115) from product stream 112 for recycling to product stream 111. Although stream 115 is depicted as entering reactor 110 through a different inlet than the rest of feed stream 111, it is considered part of the feed stream because it is part of the material input to the process step.

[0097] As mentioned above, one of the competing reactions in the reverse water gas shift reaction is the Sabatier reaction, which manufactures methane. Although in various embodiments, the reverse water gas shift method described herein can be carried out without forming a large amount of methane, in some embodiments, some methane may be formed. Therefore, in various embodiments of the method as described herein, the product stream comprises one or more light hydrocarbons. For example, in some embodiments, the product stream may comprise one or more of methane, ethane, propane, or a combination thereof. As will be appreciated by those of ordinary skill in the art, it may be desirable to operate the reverse water gas shift reaction so as to provide a higher amount of light hydrocarbons in the product feed. For example, such light hydrocarbons may be inert in the further processing of the product stream, and therefore may be acceptable at higher amounts. Those of ordinary skill in the art will be able to select appropriate reaction conditions (e.g., temperature, pressure, feed stream composition) to provide a product stream comprising methane in a desired amount. Therefore, in various embodiments as described separately herein, the product stream comprises no more than 40 moles, or 35 moles, or 30 moles, or 25 moles, or 20 moles, or 15 moles, or 10 moles of methane. As described above, when a lower amount of methane is desired in the product stream, the catalyst of the present disclosure can provide very low methane selectivity. For example, in various embodiments, the product stream comprises no more than 5 moles, or 1 mole, or no more than 0.5 mole of methane. Typically, light hydrocarbons (e.g., C1-C5 hydrocarbons) may be present in the product stream. For example, in various embodiments as described separately herein, the product stream comprises no more than 20 moles of light hydrocarbons (e.g., no more than 15 moles, no more than 10 moles, no more than 5 moles, no more than 1 mole, no more than 0.5 moles, or no more than 0.1 mole of light hydrocarbons).

[0098] The light hydrocarbons (e.g., C1-C5 hydrocarbons) of 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. Figure 1 In the method 100, at least a portion of one or more light hydrocarbons is separated from the product stream 112 to provide a light hydrocarbon stream 116. The light hydrocarbon stream can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be combusted to provide heat or other energy (e.g., electricity for electrolysis) for use in the rWGS process or other processes.

[0099] Of course, as will be appreciated by one of ordinary skill in the art, the light hydrocarbon stream may also be used in other processes. For example, as will be appreciated by one of ordinary skill in the art, some rWGS catalysts may have reforming capabilities. Without being bound by theory, the inventors hypothesize that one explanation for the low methane yields observed using rWGS catalysts as described herein is that methane is formed but then immediately reformed to CO and H2. Therefore, in some embodiments as described herein, the light hydrocarbons of the process stream are recycled to the feed stream for the rWGS reaction. These light hydrocarbons may be separated and used for other purposes. For example, in various embodiments, the method further comprises separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream. For example, in Figure 2 In the method 100, at least a portion of one or more light hydrocarbons is separated from the first product stream 112 to provide a light hydrocarbon stream 118. The light hydrocarbon stream can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be burned to provide heat or other energy (e.g., electricity for electrolysis) for an integrated process or other processes. Of course, as will be appreciated by those of ordinary skill in the art, the light hydrocarbon stream can also be used in other processes.

[0100] Integrated Fischer-Tropsch process

[0101] In some embodiments as described herein, the supported reverse water gas can be used in a rWGS process integrated with a FT process. Embodiments related to the reverse water gas shift portion of the integrated FT process are as described above in the previous section. For example, the feed stream of the rWGS process corresponds to the first feed stream in the integrated FT process, and the product stream of the rWGS process corresponds to the first product stream in the integrated FT process.

[0102] Another aspect of the present disclosure provides a method for performing an integrated Fischer-Tropsch process (i.e., integrated with an rWGS process). The method 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 500-900°C and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H2, wherein the first product stream has a lower concentration of CO2 and a higher concentration of CO than the first feed stream. Figure 2 An example of such a method is shown schematically in Figure 2In the method 100, a reverse water gas shift reaction is performed by providing a first feed stream 111 comprising H2 and CO2 to a first reaction zone, such as a 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 500-900°C and at a first pressure to provide a first product stream 112 comprising 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 also includes contacting the Fischer-Tropsch catalyst with a second feed stream comprising H2 and at least a portion of the CO of the first product stream at a second temperature and a second pressure to provide a first product stream 112 comprising CO and H2. 5+ A second product stream of hydrocarbons. Figure 2 In the process 100, at least a portion of the CO of the first product stream 112 is contained in the second feed stream 121, which is contacted with the Fischer-Tropsch catalyst 123 in the second reaction zone (e.g., reactor 120). This provides a catalyst containing C 5+ A second product stream 122 of hydrocarbons.

[0103] The inventors have discovered that contacting a rWGS catalyst as described herein with a first feed stream can provide a first product stream having advantageously high CO selectivity and low methane selectivity. As described above, the amount of CO in the first product stream can be further controlled by the rWGS reaction conditions.

[0104] However, as described above, the inventors have determined that it may be desirable to conduct the process at an intermediate degree of conversion to provide a desirably high CO selectivity and a desirably low methane selectivity. In addition, the inventors have noted that it may be advantageous to conduct the downstream Fischer-Tropsch process at relatively high inert levels, and thus contemplate that it may be beneficial to feed a significant amount of CO2 to the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the first product stream comprises an amount of CO2 as well as CO. In various embodiments, 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% CO2.

[0105] In addition, as described below, the Fischer-Tropsch catalyst generally requires activation by a reducing gas. As will be appreciated by those skilled in the art, different Fischer-Tropsch catalysts require different activation conditions (e.g., gas composition, temperature, pressure, time). For example, an iron-based Fischer-Tropsch catalyst requires activation with H2 and CO, while a cobalt-based Fischer-Tropsch catalyst requires only H2 activation. Therefore, H2 and CO or only H2 from the first product stream can be used to perform the activation. Therefore, in various embodiments as described elsewhere herein, the method includes separating at least a portion of the H2 and CO from the first product stream (desirably in a ratio of at least 1:1 or at least 3:1) and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. In various other embodiments as described elsewhere herein, the method includes separating at least a portion of the H2 from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. For example, in Figure 2 In the process, stream 125 separates H2 or H2 from CO and directs it to reactor 120. This separation need not be continuous; rather, it only needs to be performed for a period of time required to provide a reducing gas to the Fischer-Tropsch catalyst for activation. Of course, as will be appreciated by those skilled in the art, other sources of H2 or CO may be used to provide a reducing gas to the Fischer-Tropsch catalyst for activation.

[0106] As indicated above, water is a product of the reverse water gas shift reaction. Thus, the first product stream will typically contain water. In many cases, it may be desirable to reduce the amount of water provided to the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream. Figure 2 In the embodiment of the present invention, the water removal zone 116 is used to remove water and provide an aqueous stream 117. It will be understood by those of ordinary skill in the art that various methods can be used to remove water from the first product stream. For example, the first product stream can be contacted with a water removal agent to remove water therefrom. For example, a molecular sieve guard bed can be used to remove water from the first product stream; water can be recovered from the molecular sieves of the guard bed, for example, by heating and vacuum. In other embodiments, a separator (knockout vessel) can be used. However, the use of a separator can in some cases sufficiently cool the first product stream so that it is desirable to reheat it for introduction into the Fischer-Tropsch process step. The water removed from the first product stream can be used as, for example, feed water for the electrolysis process described herein.

[0107] As described above, the reverse water gas shift process can be provided at a variety of temperatures. In some cases, these temperatures can be relatively close to the temperature of the subsequent Fischer-Tropsch step (typically 150-400°C, such as 200-350°C, or other temperatures as described below). In other cases, the reverse water gas shift process can be carried out at a temperature significantly higher than the temperature of the Fischer-Tropsch step. The inventors have noted that it may be desirable to provide heat exchange with a relatively hot first product stream in order to cool the first product stream to a temperature more suitable for the Fischer-Tropsch step and to provide heat to the integrated process elsewhere. For example, in various embodiments of the method as otherwise described herein, the method further includes exchanging heat between at least a portion of the first product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the first product stream and heating at least a portion of the first feed stream. In Figure 3 An example of such a method is shown schematically in Figure 3 In the process 200, the first reactor 210, the first feed stream 211, the first product stream 212, the reverse water gas shift catalyst 213, the second reactor 220, the second feed stream 221, the second product stream 222 and the Fischer-Tropsch catalyst 223 are generally as described above. Here, the process 200 includes exchanging heat between at least a portion of the first product stream 212 and at least a portion of the first feed stream 211 in the first heat exchange zone 230, thereby cooling at least a portion of the first product stream 212 and heating at least a portion of the first feed stream 211. It will be appreciated by those of ordinary skill in the art that a variety of heat exchangers may be used for this purpose.

[0108] Of course, any excess heat in the first product stream can additionally or alternatively be used for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the first product stream and the steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone. This is shown in FIG. Figure 3 Here, after heat exchange with the first feed stream 211, the first product stream 212 is directed to the steam generating zone 232 to cool the first product stream 212 and provide heat to the steam generating zone 232. Steam can be generated from the provided heat, and electricity can be generated from the steam. For example, in Figure 3 In the embodiment of the present invention, the electric current 264 is provided by generating electricity using the steam generated in the steam generating area 232. Of course, as will be appreciated by one of ordinary skill in the art, the steam generated in the steam generating area can be used for other processes. In various embodiments, the steam can be used to heat the first feed stream. For example, in Figure 3 In the embodiment of the present invention, the steam stream 266 generated in the steam generating zone 232 is directed to the heat exchange zone 290 to heat the first feed stream 211.

[0109] As described above, at least a portion of the CO of the first product stream is included in the second feed stream for reaction in the Fischer-Tropsch process. For example, in various embodiments as described elsewhere herein, at least 25% of the CO of the first product stream, for example, at least 50% of the CO of the first product stream, at least 75% of the CO, or at least 90% of the CO is included in the second feed stream. Of course, as described above, a portion of the CO of the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0110] In some embodiments, substantially all of the CO in the second feed stream is from the first product stream. However, in other embodiments, the CO can be provided to the second feed stream from other sources (fossil-derived or other). For example, in various embodiments, CO is provided to the second feed stream from a CO source other than the first product stream. Figure 3 In the embodiment of the present invention, a CO stream 226a from some other source is included in the second feed stream 221. It will be appreciated by those skilled in the art that CO can be provided from a variety of sources, such as gasification, reforming, or electrochemical CO2 reduction. In addition, as described in more detail below, CO can be recycled from the second product stream to the second feed stream; and / or can be provided by reaction of a light hydrocarbon stream, such as by partial oxidation or reforming (e.g., steam reforming and / or autothermal reforming).

[0111] As described above, the second feed stream includes H2. It is worth noting that the first product stream will generally include H2, such as unreacted H2 from the first feed stream. In various embodiments, the first product stream includes H2, wherein the second feed stream includes at least a portion of the H2 of the first product stream. For example, in various embodiments as described elsewhere herein, at least 25% of the H2 of the first product stream, such as at least 50% of the H2 of the first product stream, at least 75% of the H2, or at least 90% of the H2 is included in the second feed stream. Of course, as described above, a portion of the H2 of the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0112] In some embodiments, substantially all of the H2 in the second feed stream comes from the first product stream. In fact, one of ordinary skill in the art can provide more H2 in the first feed stream than is required for the reverse water gas shift reaction so as to provide excess H2 in the first product stream, which can then provide the required amount of H2 to the second feed stream for the Fischer-Tropsch step. However, in other embodiments, H2 can be provided to the second feed stream from other sources. For example, in various embodiments, H2 is provided to the second feed stream from a source of H2 other than the first product stream. Figure 3In the embodiment of the present invention, H2 stream 226b from some other source is included in the second feed stream 221. It will be appreciated by one of ordinary skill in the art that H2 can be provided from a variety of sources, such as gasification, reforming, or H2O electrolysis (including the electrolysis described herein). In addition, as described in more detail below, H2 can be recycled from the second product stream to the second feed stream.

[0113] Based on the disclosure herein, one of ordinary skill in the art can adjust the relative amounts of H2 and CO in the second feed stream to provide a desired ratio. For example, more or less of the H2 of the first feed stream and / or more or less of the H2 from electrolysis may be included in the second feed stream. Similarly, more or less of the CO of the first feed stream and more or less of the CO from other sources (e.g., partial oxidation and reforming as described below) may be included in the second feed stream.

[0114] As described above, it may be desirable to carry out the Fischer-Tropsch process step in the presence of significant levels of inerts. One such inert, CO2, may come from the reverse water-gas shift, for example via the first product stream. Therefore, in various embodiments as described elsewhere herein, the second feed stream comprises at least a portion of the CO2 of the first product stream. For example, in various embodiments, at least 10% of the CO2 of the first product stream, such as at least 25% of the CO2 of the first product stream, at least 50% of the CO2, at least 75% of the CO2, or at least 90% of the CO2 is contained in the second feed stream. Of course, in other embodiments, the second feed stream may not contain any significant amount of CO2 of the first product stream. Therefore, in various embodiments, the second feed stream does not contain a significant amount of CO2 of the first product stream. Although it may generally be desirable to recycle CO2 to the first feed stream for use in the reverse water-gas shift reaction, as described in more detail below, unreacted CO2 may be recycled from the second product stream to the first feed stream.

[0115] Additionally or alternatively, however, it may be desirable to include additional inert content in the second feed stream, whether CO2 or other inerts such as nitrogen and methane. For example, in various embodiments, one or more inerts (e.g., CO2, nitrogen, and / or methane) are provided to the second feed stream from a source other than the first product stream. Figure 3 In the second feed stream 221, an inert material stream 226c from some other source is included. It will be appreciated by those skilled in the art that inerts can be provided from a variety of sources. In addition, as described in more detail below, inerts can be recycled from the second product stream to the second feed stream.

[0116] As described above, it may be desirable to carry out the Fischer-Tropsch process step in the presence of an inert. Thus, in various embodiments as described elsewhere herein, the portion of the first product stream contained in the second feed stream has a CO content in the range of 10-95 mol % CO, e.g., 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 % CO.

[0117] As described above, other gases may also be included in the second feed stream. For example, as described above, it may be desirable to conduct the Fischer-Tropsch process step in the presence of a significant amount of inerts (i.e., components other than H2 or CO). For example, in various embodiments, the second feed stream comprises up to 80 mol% of one or more inerts, 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 comprises up to 70 mol% inerts, up to 60 mol% inerts, or up to 50 mol% inerts, 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% inerts. In various embodiments, the second feed stream comprises up to 80% of one or more inerts selected from CO2, methane and nitrogen, 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%. In various embodiments, the second feed stream comprises up to 80 mol% CO2, 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%.

[0118] One of ordinary skill in the art can adjust the portion of the first product stream included in the second feed stream to provide a desired H2: CO ratio. For example, in various embodiments, the portion of the first product stream included 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 included in the second feed stream, one of ordinary skill in the art can add H2 or CO as needed to provide the desired overall ratio in the second feed stream as described above.

[0119] As described above, the second feed stream contains H2 and CO, and the second feed stream comprises all feeds to the Fischer-Tropsch reactor, whether the second feed stream is provided as a mixture of feeds or as a separate feed provided to the reaction zone. In various embodiments of the present disclosure as described herein, the second feed stream has a H2:CO ratio in the range of 0.5:1 to 6:1. In some embodiments, the second feed stream has a 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 a H2:CO ratio of at least 1.4:1. For example, in some embodiments, the second feed stream has a 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, one of ordinary skill in the art will provide a desired ratio of H2:CO in the second feed stream that provides a desirable conversion and selectivity in the Fischer-Tropsch process.

[0120] As described above, it may be desirable to reduce the amount of water introduced into the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, e.g., or no more than 2 mol%, or no more than 0.5 mol%.

[0121] As noted above, it may be desirable to conduct the Fischer-Tropsch process in the presence of relatively small amounts of water. Thus, in various embodiments, the second feed stream has a water content of no more than 10 mol%, for example, or no more than 2 mol%, or no more than 0.5 mol%.

[0122] The method described herein comprises contacting a Fischer-Tropsch catalyst with a second feed stream as described herein. There is no particular limitation on the Fischer-Tropsch catalyst used in the method as described herein, and one of ordinary skill in the art will be able to select a catalyst suitable for their desired Fischer-Tropsch product. In some embodiments, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0123] For example, in some embodiments of the present disclosure as described herein, the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount in the range of 5-25 wt % calculated as Co(0). "Calculated as Co(0)" and similar terms refer to the use of the weight of the cobalt atoms / ions themselves in the calculation, rather than the total amount of any compounds or polynuclear ions in which those cobalt atoms / ions may be combined. For example, in various embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 7-25 wt %, or 10-25 wt %, or 5-20 wt %, or 7-20 wt %, or 10-20 wt %, calculated as Co(0). As will be understood by those of ordinary skill in the art, cobalt-based catalysts are typically provided to the reaction zone in the form of cobalt oxide on a support; the cobalt can be reduced and activated in situ (e.g., with H2) to provide an active catalyst species having a significant concentration of Co(0).

[0124] In some embodiments, the Fischer-Tropsch catalyst comprises iron, for example, in an amount in the range of 5-95 wt % calculated as Fe(0). For example, in various embodiments, the Fischer-Tropsch catalyst comprises iron in an amount in the range of 10-95 wt %, or 25-95 wt %, or 50-95 wt %, or 5-85 wt %, or 10-85 wt %, or 25-85 wt %, or 50-85 wt %, or 5-75 wt %, or 10-75 wt %, or 25-75 wt % calculated as Fe(0). As will be appreciated by those of ordinary skill in the art, iron-based catalysts are typically provided to the reaction zone in the form of metallic iron or iron oxide optionally on a carrier; iron can be activated (e.g., by reaction with H2 and CO) to provide an active catalyst species having a significant concentration of iron carbide.

[0125] In various embodiments of the present disclosure as described herein, especially when the catalyst is a cobalt-based catalyst, the Fischer-Tropsch catalyst further comprises manganese. For example, in various embodiments, the Fischer-Tropsch catalyst comprises manganese in an amount of up to 15 wt %, such as up to 12 wt %, or up to 10 wt %, or up to 7 wt %, calculated as Mn(0). In certain such embodiments, the catalyst material comprises manganese in an amount of 0.1-15 wt %, such as 0.1-10 wt %, or 0.1-5 wt %, 0.5-15 wt %, or 0.5-10 wt %, or 0.5-5 wt %, calculated as Mn(0). Of course, in other embodiments, manganese is substantially absent (e.g., there is less than 0.1 wt % or less than 0.5 wt % manganese).

[0126] The Fischer-Tropsch catalyst suitable for the method as described herein can be in various forms and is not particularly limited. For example, the Fischer-Tropsch catalyst can be a supported or unsupported catalyst. Although the form of the catalyst is not particularly limited, in various desirable embodiments, the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide and zinc oxide. For example, in various embodiments, the support comprises at least one of titanium oxide, aluminum oxide and silicon oxide. In some embodiments of the present disclosure as described herein, the support is a titanium dioxide support.

[0127] Those of ordinary skill in the art will appreciate that the Fischer-Tropsch catalysts of the present disclosure may be provided in many forms, particularly depending on the particular form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The support for the Fischer-Tropsch catalyst may itself be provided as a discrete body of material, for example as a porous particle, pellet or shaped extrudate, wherein the metal is provided thereon to provide the Fischer-Tropsch catalyst. However, in other embodiments, the Fischer-Tropsch catalyst of the present disclosure may itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths. Those of ordinary skill in the art will select an appropriate Fischer-Tropsch catalyst for a particular reactor system.

[0128] As with rWGS catalysts, Fischer-Tropsch catalysts are typically activated prior to use, for example to provide cobalt(0) species on cobalt-based catalysts, or iron carbide species on iron-based catalysts. Such activation may be performed prior to contacting the Fischer-Tropsch catalyst with the second feed stream.

[0129] For example, in some embodiments, the Fischer-Tropsch catalyst is activated by contact with a reducing gas. For example, hydrogen can be a gas that is particularly suitable for activating a Fischer-Tropsch catalyst, such as when the activation is a reduction to a metal (0) species, such as for many cobalt-based catalysts. In various embodiments of the present disclosure as described elsewhere herein, the reducing gas comprises at least a portion of the H2 from the first product stream. For example, in some embodiments, the method further includes separating at least a portion of the H2 from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 2 In the method 100 schematically shown in , 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 will be understood by those of ordinary skill in the art, the activation temperature may vary depending on the Fischer-Tropsch catalyst used. Therefore, those of ordinary skill in the art will be able to select an appropriate temperature for activating the catalyst, for example in the range of 200-400°C.

[0130] In various embodiments, the Fischer-Tropsch catalyst is activated by contact with H2 and CO. This may be particularly suitable when the activation provides for conversion to carbides, such as for many iron-based catalysts. In various embodiments of the present disclosure as described elsewhere herein, the reducing gas comprises at least a portion of the H2 and CO from the first product stream. For example, in some embodiments the method further comprises separating at least a portion of the H2 and at least a portion of the CO from the first product stream and contacting them with the Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 3 In the method 200 schematically shown in FIG. 2 , 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, the 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.

[0131] As described above, the method includes contacting the Fischer-Tropsch catalyst with the second feed stream at a second temperature and a second pressure. One of ordinary skill in the art will select appropriate reaction conditions in conjunction with the specific feed and catalyst for providing the desired Fischer-Tropsch process. In some embodiments of the present disclosure as described herein, the second temperature is in the range of 150-400°C. For example, in various embodiments, the second temperature is in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C. In some specific embodiments, the second temperature is in the range of 200-350°C.

[0132] It is noteworthy that in many embodiments, the first temperature and the second temperature can be relatively close to each other. The inventors have noted that the reverse water gas shift catalyst described herein can provide suitable activity and CO selectivity even at relatively low temperatures. Therefore, the first product stream can be provided with a temperature suitable for or at least close to that suitable for the Fischer-Tropsch reaction step. This can desirably provide improved process integration. For example, in various embodiments, the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

[0133] However, in other embodiments, the first temperature and the second temperature are not too close to each other. The inventors have noted that in many cases, the desired reverse water gas shift process temperature will be significantly higher than the desired Fischer-Tropsch temperature. For example, in various embodiments, the first temperature is at least 100°C higher than the second temperature, such as at least 150°C higher than the second temperature, or at least 200°C higher than the second temperature. The excess heat in the first product stream can be used for a variety of purposes, such as for preheating at least a portion of the first feed stream or generating steam for power generation, as described above.

[0134] In some embodiments of the present disclosure as described herein, the second pressure is in the range of 10-50 bar. For example, in various embodiments, the second pressure is in the range of 20-50 bar, or 25-50 bar, or 10-40 bar, or 20-40 bar, or 25-40 bar, or 10-35 bar, or 20-35 bar, or 25-35 bar. In some embodiments, the second pressure is in the range of 20-50 bar.

[0135] As will be appreciated by those of ordinary skill in the art, the Fischer-Tropsch process described herein can be performed at various GHSV (gas hourly space velocity) values. Thus, there is no particular limitation on the GHSV at which the Fischer-Tropsch reaction is performed. For example, in some embodiments of the present disclosure, the process of performing the Fischer-Tropsch reaction is performed at 1,000 to 2,000,000 h -1 In various embodiments, the process for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the process of carrying out the Fischer-Tropsch reaction is carried out at a GHSV of 1,000 to 50,000 h. - 1 , or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1 , or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h-1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

[0136] The Fischer-Tropsch process is commonly used to prepare C 5+ Hydrocarbons, such as unsubstituted C 5+ Hydrocarbons (such as alkanes and alkenes) and oxygen-containing C 5+ Hydrocarbons (such as C 5+ alcohols, aldehydes, ketones, carboxylic acids). In various embodiments of the present disclosure as described herein, the Fischer-Tropsch catalyst is contacted with the second feed stream to provide a second product stream with at least 30%, such as at least 50%, or at least 70% C 5+ Selectivity (i.e. for all C 5+ For example, in some embodiments, C 5+ The selectivity for alkanes is at least 30%, such as at least 50%, or at least 70%. 5+ Alkanes and C 5+ The selectivity to alcohol is at least 30%, such as at least 50%, or at least 70%.

[0137] Additional components may be present in the second product stream. For example, in some embodiments, the second product stream comprises water, which is another product of the Fischer-Tropsch reaction. One or more light hydrocarbons (i.e., 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 inerts described herein may also be present. Such components of the second product stream may be separated and / or recycled in various ways.

[0138] For example, in various embodiments, the method further comprises separating at least a portion of the water from the second product stream. This is schematically shown in Figure 4 In. Figure 4In an embodiment, the reverse water gas shift catalyst 313 and the Fischer-Tropsch catalyst 323 are provided in separate beds in the same reactor. Thus, the first reaction zone 310 is the volume of the reactor 305 including the bed 314 containing the reverse water gas shift catalyst 313, and the second reaction zone 320 is the volume of the reactor 305 including the bed 324 containing the Fischer-Tropsch catalyst 323. The first feed stream 311 is contacted with the reverse water gas shift catalyst 313 to provide a first product stream 312, which is directly fed to the Fischer-Tropsch catalyst 323 as a second feed stream 321 to provide a second product stream 322. Here, the method also optionally includes separating at least a portion of the water (e.g., at least 50%, at least 75%, or at least 90%) from the second product stream 322 to provide a water-containing stream 334.

[0139] Light hydrocarbons, while generally not a desired portion of a Fischer-Tropsch product for use as a fuel or lubricant, can themselves be used for many purposes. Thus, in various embodiments, the method further comprises separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. The light hydrocarbon stream can, for example, be recycled to the first feed stream or the second feed stream. For example, in Figure 3 In the method 200, the light hydrocarbons can be provided as part of the recycle stream 236, which becomes part of the second feed stream 221. Figure 4 In the method 300, the light hydrocarbons can be provided as part of the recycle stream 336, which becomes part of the first feed stream 311. Figure 5 In the method 400 , light hydrocarbons are recycled to the first feed stream 411 via the recycle stream 442 .

[0140] Light hydrocarbon streams also have other uses. For example, in some embodiments, the method further comprises oxidizing at least a portion of the light hydrocarbon stream to provide a partially oxidized (pOX) stream containing CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream and / or the second feed stream. Figure 5 An example of such a process is schematically shown in , wherein the process 400, the first feed stream 411, the first product stream 412, the reverse water gas shift catalyst 413, the second feed stream 421, the second product stream 422 and the Fischer-Tropsch catalyst 423 can be as described elsewhere herein. Here, the process includes 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.

[0141] Other methods can be used to provide CO and / or CO2 from a light hydrocarbon stream. 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 stream to provide a reforming stream containing CO and / or CO2, and including at least a portion of the reforming stream in the first feed stream and / or the second feed stream. The water separated from the first and / or second product stream can be provided as part of the feed to the reforming described herein.

[0142] In addition, the light hydrocarbon stream can be burned to provide thermal energy, which can be used to heat various process streams, or to generate electricity. Thus, in various embodiments, the method includes burning at least a portion of the light hydrocarbon stream to provide energy, such as thermal energy or electrical energy. For example, in Figure 5 In the method 400, a portion of the light hydrocarbon stream 450 is combusted in a power generation area (here, in a generator 470) to generate electricity 472. In various embodiments, the thermal energy can be used to provide the required heat load for the reverse water gas shift process. For example, in Figure 5 In the method 400 of , a portion of the light hydrocarbon stream 450 is burned in the power generation zone (here, in the heat generator 480) to produce a heat stream 482. The heat stream 482 is directed to the heat exchange zone 490 to heat the first feed stream 411. Thermal energy can be similarly provided to the Fischer-Tropsch reaction. And as will be understood by those of ordinary skill in the art, other treatments of the light hydrocarbon stream (e.g., partial oxidation) can also provide energy, which can be used, for example, as described herein.

[0143] As with the first product stream, heat can be exchanged from the second product stream to provide heat to, for example, a feed stream or a steam generating zone. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the first feed stream. Figure 4 In the method 300, in the second heat exchange zone 330, heat is exchanged between at least a portion of the second product stream 322 and the first feed stream 311, thereby cooling the second product stream 322 and heating the first feed stream 311. Of course, heat can also be exchanged from the second product stream to the second feed stream. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the second feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the second feed stream. Figure 5In the method 400, heat is exchanged between at least a portion of the second product stream 422 and the second feed stream 421 in the second heat exchange zone 430, thereby cooling the second product stream 422 and heating the second feed stream 421. One of ordinary skill in the art will appreciate that a variety of heat exchangers may be used for this purpose.

[0144] Of course, any excess heat in the second product stream can additionally or alternatively be used for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and the steam generating zone, thereby cooling at least a portion of the second product stream and providing heat to the steam generating zone. This is shown in FIG. Figure 4 Here, after heat exchange with the first feed stream 311, the second product stream 322 is directed to the steam generating zone 332 to cool the second product stream 322 and provide heat to the steam generating zone 332. Steam can be generated from the provided heat, and electricity can be generated from the steam (not shown here).

[0145] 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 of the second product stream to the second feed stream. Figure 3 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the method includes recycling at least a portion of the H2 of the second product stream to the first feed stream 311. For example, in Figure 4 In the method of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336. In various embodiments, at least 75%, such as at least 90%, of the H2 of the second product stream is recycled to the first feed stream or the second feed stream.

[0146] In some cases, for example, when H2 is provided to the second feed stream from a source of H2 other than the first product stream, the H2 from the second product stream may constitute a majority of the H2 of the first feed stream, for example at least 90%, at least 95%, or at least 98% of the H2 of the first feed stream. This is shown, for example, in Figure 5 Here, the primary H2 input to the process is through stream 440, which becomes part of the second feed stream 421. The H2 of the second product stream is contained in recycle stream 442, which becomes part of the first feed stream 411.

[0147] Similarly, it may be desirable to recycle the CO of the second product stream to, for example, the first feed stream and / or the second feed stream. For example, in various embodiments, the method includes recycling at least a portion of the CO of the second product stream to the second feed stream. Figure 3 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO of the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the method includes recycling at least a portion of the CO of the second product stream to the first feed stream. For example, in Figure 4 In the method of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336. In various embodiments, at least 25%, such as at least 50%, of the CO of the second product stream is recycled to the first feed stream or the second feed stream. In various embodiments, at least 75%, such as at least 90% of the CO of the second product stream is recycled to the first feed stream or the second feed stream.

[0148] In many cases, the CO and H2 of the second product stream will be recycled.

[0149] In addition, when one or more inerts are used in the Fischer-Tropsch process steps, it may be desirable to recycle these inerts. For example, in various embodiments, the method includes recycling at least a portion of the inerts of the second product stream to the second feed stream. Figure 3 In the process of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inerts of the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the process includes recycling at least a portion of the inerts of the second product stream to the first feed stream. For example, in Figure 4 In the method of, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inerts of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336. In various embodiments, at least 25%, such as at least 50%, of the inerts of the second product stream are recycled to the first feed stream or the second feed stream. In various embodiments, at least 75%, such as at least 90% of the inerts of the second product stream are recycled to the first feed stream or the second feed stream. In various embodiments, the purge stream can be combined with the recycle stream to prevent uncontrolled accumulation of inerts in the recycle stream (not shown here).

[0150] In particular, since CO2 is the carbon source for the reverse water gas shift process step, it may be particularly desirable to recycle CO2 to the first feed stream. Thus, in various embodiments, the process includes recycling at least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the CO2 of 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 50%, at least 75%, or at least 90%) of the CO2 of the second product stream can be recycled to the first feed stream 311 via the recycle stream 336.

[0151] In some cases, for example, when CO2 is provided to the second feed stream from a CO2 source other than the first product stream, the CO2 from the second product stream may constitute a majority of the CO2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 of the first feed stream. This is shown, for example, in Figure 5 Here, the primary CO2 input to the process is through stream 440, which becomes part of the second feed stream 421. The CO2 of the second product stream is contained in a recycle stream 442, which becomes part of the first feed stream 411.

[0152] As described above, the Fischer-Tropsch process provides a 5+ A second product stream of hydrocarbons (e.g., unsubstituted hydrocarbons such as alkanes and olefins, and / or oxygenated hydrocarbons such as alcohols). Thus, in various embodiments, the second product stream is composed of C 5+ At least a portion of the hydrocarbons provides one or more products. 5+ Hydrocarbons can be used as the basis for various fuels, such as gasoline, diesel, and aviation fuel. Other products, such as waxes and lubricants, can also be made. And olefins and oxygenates can be used as feedstocks in various other processes.

[0153] A person skilled in the art will use conventional post-processing techniques to remove the C 5+ The product of the hydrocarbon is converted into a desirable product such as a desirable fuel. For example, in various embodiments, the method further comprises hydrotreating the C 5+ At least a portion of the hydrocarbons. As will be understood by one of ordinary skill in the art, hydroprocessing is the treatment of a hydrocarbon stream with hydrogen in the presence of a suitable catalyst. A variety of hydroprocessing techniques are known and one of ordinary skill in the art will apply them herein. For example, in Figure 4 In the method 300, the second product stream 322 is hydrotreated in the hydrotreating reactor 350 to provide a hydrotreated product stream 352.

[0154] As noted above, CO2 and H2 are substantial inputs to the claimed process. Advantageously, the inventors have recognized that each of these inputs can be derived from renewable or otherwise environmentally responsible sources.

[0155] CO2 can be captured from the environment in general, or more directly from the process of forming CO2 (especially in areas where it is difficult to reduce emissions). This can make the final hydrocarbon product essentially carbon neutral or have a lower carbon intensity. Therefore, in some embodiments of the present disclosure as described herein, at least a portion of the CO2 of the first feed stream and / or the second feed stream comes from a renewable source. In some embodiments, at least a portion of the CO2 of the first feed stream and / or the second feed stream (e.g., at least 25%, at least 50%, or at least 75%) comes from direct air capture. In some embodiments, at least a portion of the CO2 of the first feed stream and / or the second feed stream (e.g., at least 25%, at least 50%, or at least 75%) comes from a manufacturing plant such as a bioethanol plant (e.g., CO2 produced by fermentation), a steel plant, or a cement plant. Therefore, the rWGS-Fischer-Tropsch integrated process of the present disclosure as described herein can not only be carbon neutral, but can also be a net consumer of carbon dioxide in some cases. These benefits make the integrated approach particularly attractive for decarbonizing transportation fuels (for the automotive and aviation sectors), since the carbon monoxide produced in the rWGS reaction can be readily used to synthesize liquid hydrocarbon fuels via the Fischer-Tropsch process using established techniques.

[0156] Similarly, H2 can be provided by an environmentally responsible source. In some embodiments, at least a portion of the H2 of 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 of the first feed stream and / or the second feed stream can be so-called "green" hydrogen, such as produced by water electrolysis using renewable electricity (such as wind energy, solar energy or hydroelectric power generation). In some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the first feed stream and / or the second feed stream can come from a so-called "blue" source, such as from a natural gas reforming process with carbon capture. Of course, other sources of hydrogen can be used in part or in whole. For example, in some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of 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.

[0157] The inventors have noted that electrolysis of water is a desirable way to provide hydrogen to the claimed method. Thus, in some embodiments, the method includes providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water. In some embodiments, the electrolysis of water is performed at least in part using electricity from a renewable source, for example to provide so-called "green hydrogen." However, the inventors have noted that electricity can be generated as part of the claimed method, for example using heat exchange from the first or second product stream, or by burning light hydrocarbons as described above. In some embodiments, the electrolysis of water is performed at least in part using electricity generated according to the method as described herein. For example, in Figure 3 In method 200, water 262 separated from the first product stream is electrolyzed in electrolyzer 260 using electricity 264 generated from steam produced by heat exchange from the first product stream in steam generating zone 232. H2 generated in the electrolysis is provided to the first feed stream via stream 265. In some embodiments, at least a portion of the O2 generated in the electrolysis is provided to a first feed stream as described herein and as described herein. Figure 7 The partial oxidation reaction zone shown in the embodiment of FIG. 4 is a partial oxidation reaction zone shown in FIG. 4. The hydrogen from the electrolysis can also be burned to provide thermal energy, for example, which can be used to heat the first feed stream.

[0158] The methods described herein can be operated in a variety of reactor systems. In some embodiments, the first reaction zone (i.e., where the reverse water gas shift process step is performed) includes a first reactor in which a reverse water gas shift catalyst is disposed, and the second reaction zone (i.e., where the Fischer-Tropsch process step is performed) includes a second reactor in which a Fischer-Tropsch catalyst is disposed. Examples of such methods are schematically shown in Figure 1 , 2 and 4. In these embodiments, the method (100, 200, 400) is carried out in a reactor system comprising a first reactor (110, 210, 410) in which a reverse water gas shift catalyst (113, 213, 413) is disposed and a second reactor (120, 220, 420) in which a Fischer-Tropsch catalyst (123, 223, 423) is disposed. The reactor used in the integrated process of the present disclosure as described herein is not particularly limited, and a person of ordinary skill in the art will be able to select an appropriate reactor.

[0159] However, other embodiments are possible. For example, in some embodiments, the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein the second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed. In some embodiments, the first reactor bed and the second reactor bed are disposed in the same reactor. Figure 4, where the reverse water gas shift catalyst 313 is disposed in a first catalyst bed 314 and the Fischer-Tropsch catalyst 323 is disposed in a second catalyst bed 324. Here, the catalyst beds 314 and 324 are in the same reactor 305 with the process gas flowing between them. Such a configuration may be particularly desirable when the first temperature and the second temperature are relatively close to each other.

[0160] In various embodiments, the method is carried out in a reactor system comprising a first catalyst container in which one or more reverse water gas shift catalysts are disposed, and wherein the second reaction zone comprises a second catalyst container in which one or more Fischer-Tropsch catalysts are disposed. These may be provided in the same reactor, as described above for the catalyst bed.

[0161] As described above, the reverse water gas shift process step and the Fischer-Tropsch process step using the nickel catalyst described herein can be carried out under similar conditions. Thus, in various embodiments, the reverse water gas shift catalyst and the Fischer-Tropsch catalyst can be provided together in the same catalyst bed, for example mixed together. Such embodiments are shown in Figure 6 Here, the method 500 is carried out in a reactor system including a reactor 505 in which a reverse water gas shift catalyst 513 and a Fischer-Tropsch catalyst 523 are mixed together in a single catalyst bed 524. Here, the first feed stream 511 and the second product stream 522 can be substantially as described herein. The first product stream and the second feed stream are understood to be a mixture of process gases within the mixed catalyst.

[0162] In the embodiments specifically described above, separate rWGS and Fischer-Tropsch catalysts are used in admixture, for example, in separate reactors, in separate zones of the same reactor, or even in the same zone of a reactor.

[0163] However, the inventors have also noted that there are certain commonalities between the rWGS catalysts described herein and certain Fischer-Tropsch catalysts. For example, as will be appreciated by one of ordinary skill in the art, manganese is a common modifier used in Fischer-Tropsch catalysts, particularly those based on cobalt. The inventors have also noted that similar supports can be used for each catalyst.

[0164] Therefore, in addition to the above-mentioned configuration, the inventors have contemplated providing a single bifunctional catalyst having reverse water gas shift activity and Fischer-Tropsch activity. This bifunctional catalyst comprises rWGS active catalyst metal and Fischer-Tropsch active catalyst metal in the same body. It will be understood by those skilled in the art that both rWGS catalyst and Fischer-Tropsch catalyst are supported catalysts, such as metal oxide supported catalysts. Therefore, in various embodiments of the present disclosure, rWGS active catalyst metal and Fischer-Tropsch active catalyst metal can be disposed together on the same carrier to provide a bifunctional catalyst. For example, in some embodiments, the carrier of the bifunctional catalyst itself is provided as a discrete body of material, such as a porous particle, pellet or shaped extrudate, wherein the rWGS active catalyst metal and the FT active catalyst metal are disposed thereon to provide a bifunctional catalyst. The rWGS active catalyst metal and the FT active catalyst metal can be uniformly distributed throughout the carrier, or can be distributed in discrete regions throughout the carrier. However, in other embodiments, the bifunctional catalyst of the present disclosure itself can be formed as a layer on the substrate below. For example, in some embodiments, the bifunctional catalyst is formed by a rWGS active catalyst metal layer and a FT active catalyst metal layer on the substrate below. The rWGS-active catalyst metal and the FT-active catalyst metal may be uniformly distributed on the underlying substrate. In other embodiments, the rWGS-active catalyst metal and the FT-active catalyst metal may be in discrete regions on the underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths.

[0165] 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, nickel, manganese, and at least one of cobalt, iron, rhodium, and ruthenium. In some embodiments of the present disclosure, the bifunctional catalyst comprises a support as a metal oxide support as described herein, nickel, manganese, and cobalt. In some embodiments of the present disclosure, the bifunctional catalyst comprises a support comprising at least one of titanium oxide, zirconium oxide, cerium oxide, or aluminum oxide, nickel, manganese, and cobalt. In some embodiments, the bifunctional catalyst comprises a titanium oxide support, nickel, manganese, and cobalt. For example, in some embodiments, the bifunctional catalyst comprises a titanium oxide support, nickel present in an amount ranging from 0.05 to 10 weight %, manganese present in an amount ranging from 0.5 to 20 weight %, and cobalt present in an amount ranging from 7-25 weight %.

[0166] The ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is not particularly limited, and one of ordinary skill in the art will be able to select an appropriate ratio. For example, in some embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.1: 1. In various embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.2: 1, or 0.5, or 1: 1.

[0167] Such catalysts can be used for Figure 6 In those embodiments described, one of ordinary skill in the art will select reaction conditions that provide an appropriate balance of reverse water gas shift activity and Fischer-Tropsch activity.

[0168] Figure 7 is a schematic depiction of another integrated process according to the present disclosure. Here, the reverse water gas shift and Fischer-Tropsch steps are integrated with partial oxidation of light hydrocarbons to provide CO and H2 to the Fischer-Tropsch step; electrolysis to provide H2 for the reverse water gas shift process step and O2 for partial oxidation; and various recycles and optional feeds, as described throughout this specification.

[0169] One of ordinary skill in the art will be able to provide the materials and perform the methods described herein based on the above general disclosure and with reference to the following examples. Example

[0170] The following examples illustrate specific embodiments of the catalysts and methods of the present disclosure and various uses thereof. They are set forth for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0171] Example 1. Modeling

[0172] The inventors have modeled various equilibrium conditions for the reverse water gas shift reaction. The predicted carbon dioxide conversion rate and product composition of the rWGS reaction (reaction formula 1) competing with the Sabatier reaction (reaction formula 3) and the CO methanation reaction (reaction formula 4) are calculated based on the temperature range of 400-800° C. for thermodynamic equilibrium. From the modeling, carbon monoxide selectivity increases at temperatures above 600° C., while methane selectivity decreases at higher temperatures.

[0173] It is clear from these results that the Sabatier reaction (equation (3)) and CO methanation (equation (4)) side reactions are exothermic and dominate at lower temperatures, while the rWGS reaction (equation (1)) is endothermic and dominates at higher temperatures. However, other carbon-producing side reactions that are not considered in the examples described may occur at high temperatures. Therefore, the inventors have studied catalysts that operate at moderate to high temperatures. These catalysts are discussed in more detail below.

[0174] Example 2 Catalyst Preparation

[0175] The catalysts were prepared using a conventional impregnation method before testing their feasibility for the reverse water gas shift reaction. The supports used are described in Table 1.

[0176] Table 1.

[0177] Chemicals supplier Pore ​​volume Cerium(IV) Oxide Sigma-Aldrich 0.1mL / g γ-Alumina Saint Gobain 0.83mL / g Titanium Dioxide P-25Aeroxide Evonik 0.5mL / g Zirconia SZ 6 Saint Gobain 0.38mL / g

[0178] To prepare the catalyst, a solution of nickel (II) nitrate hexahydrate (purity 99.9985%, VWR) and manganese acetate tetrahydrate (purity 99.9%, Fisher Chemicals) was prepared in deionized water. The nickel and manganese solutions were added to the support powder. The amount of support added was based on the amount of water by mass so that the ratio of water:support was 3:1. The slurry was then stirred at room temperature for 4 hours. Excess water was then evaporated using a stirred drying bath at a temperature of 60°C. The resulting catalyst precursor powder was then dried in a drying oven at 90°C for 24 hours.

[0179] The catalyst precursor powder was then subjected to calcination by spreading the powder evenly in a crucible. The crucible was placed in a calcining 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 and then increased from 120°C to 500°C at a rate of 2°C / min. The temperature was maintained at 500°C for 4 hours and then cooled to ambient temperature. The resulting catalyst was then tested for its feasibility for the reverse water gas shift reaction.

[0180] Example 3. Performance of Nickel Catalyst

[0181] The catalytic performance of the catalyst prepared by the method described herein was subsequently tested for the reverse water gas shift reaction. The catalyst tested was a titanium dioxide supported catalyst comprising 5 wt % nickel and 0 wt % or 5 wt % manganese. In order to test the catalytic performance of these catalysts, 20 μL of catalyst diluted with SiC F100 to provide a ratio of 1:10 was loaded into a 3 mm ID ceramic tube reactor to obtain a 0.22 mL catalyst bed with a zone height of 31.1 mm. Prior to the rWGS reaction, the catalyst was activated at 590°C in an atmosphere of 97% hydrogen and 3% argon for 5 hours. Subsequently, the catalyst was contacted with a feed stream comprising two different ratios of H2 and CO2 at two different temperatures. The total pressure was maintained at 10 bar. For tests 1 and 2, the GHSV was 100,000h -1 , and for tests 3-6 it is 120,000h -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 the following Table 2 and Tables 3-8, the amount of nickel and / or manganese present in the catalyst is shown in brackets. These figures are in weight percent and are based on the total weight of the catalyst. For example, CeO2Ni(5)Mn(5) corresponds to a catalyst with 5 wt % Ni, 5 wt % Mn and 90 wt % CeO2.

[0182] Table 2.

[0183]

[0184]

[0185] The addition of 5 wt % manganese to 5 wt % nickel supported on titania resulted in an increase in CO selectivity despite some loss in catalyst activity as shown by a decrease in CO 2 conversion.

[0186] At 600°C, H2:CO2 ratio 2:1, pressure 30 bar and GHSV 1,200,000h -1 Catalysts with 0.5 wt%, 1 wt% or 5 wt% nickel and 5 wt% manganese on a titania or ceria support were tested. These results are reported in Table 3.

[0187] Table 3.

[0188]

[0189] The results in Table 3 show that although increasing the nickel content does not improve the selectivity of CO, the conversion of CO2 is improved.

[0190] Example 4. Effect of carrier on catalyst performance

[0191] The effect of the support was also investigated by evaluating nickel and manganese supported catalysts on various catalytic supports (ceria, alumina, titania and zirconia). The catalysts contained 0.5 wt % nickel and 5 wt % manganese. The catalysts were prepared by the methods described herein and the reactor setup and catalyst activation as described in Example 3 were employed. The catalysts were subjected to 10 bar pressure, 800,000 h at two different temperatures. -1 The catalytic performance was analyzed by measuring the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 4.

[0192] Table 4.

[0193]

[0194]

[0195] Furthermore, these catalysts were tested at a temperature of 700°C with a feed stream having a H2 to CO2 ratio of 2:1 at a pressure of 20 bar and 800,000 h -1 The results are shown in Table 5.

[0196] Table 5.

[0197]

[0198] Tables 4 and 5 show that the performance of the nickel-manganese supported catalyst is reproduced with various support materials, where higher CO selectivity is observed at 10 bar and a H2:CO2 ratio of 1:1. The methane selectivity increases when the temperature is reduced from 760°C to 700°C. A further increase in methane selectivity is observed when the reaction pressure is doubled to 20 bar at 700°C. Of all the supports tested in this work, the titania-supported nickel-manganese catalyst shows the highest CO selectivity under the tested conditions, although it shows the lowest activity among all the supports.

[0199] The high selectivity of the nickel manganese supported catalyst makes it an attractive candidate for medium to high temperature reverse water gas shift. The high yield and selectivity for CO demonstrated in the above experiments provides an effluent stream suitable for integration with other processes.

[0200] Example 6. Effect of catalyst activation on catalyst performance

[0201] The effect of catalyst activation on catalyst performance of the catalyst prepared as described herein was evaluated. The catalyst used in this study was a titanium dioxide supported catalyst with 5 wt % nickel and 5 wt % manganese, an alumina supported catalyst with 5 wt % nickel and 5 wt % manganese, and a ceria supported catalyst with 5 wt % nickel and 5 wt % manganese. These supported catalysts were activated at three different temperatures (400°C, 590°C and 760°C) in a hydrogen atmosphere and subsequently used for the rWGS method. 20 μL of catalyst diluted with SiC F100 to provide a ratio of 1:10 was loaded into a 3mm ID ceramic tube reactor to obtain a 0.22 mL catalyst bed with a zone height of 31.1 mm. At 200,000 h -1 The catalyst was activated using pure H2 at a GHSV of 1.5 GHSV. The reactor pressure was set to 10 bar and the reactor was then heated to the desired activation temperature at a rate of 1 K / min and held at that temperature for 5 hours. After activation, the reactor was cooled to the temperature of the rWGS process. Four rWGS reaction temperatures were evaluated - 400°C, 500°C, 600°C and 700°C. When the rWGS reaction temperature was reached, the feed stream was introduced and the reaction pressure was set. The activated catalyst was incubated with a feed stream of H2 and CO2 in a molar ratio of 2:1 at a pressure of 30 bar and 1,200,000 h -1 The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Tables 6, 7 and 8.

[0202] Table 6.

[0203]

[0204] Table 7.

[0205]

[0206]

[0207] Table 8.

[0208]

[0209] For the titania-supported nickel and manganese catalysts, the alumina-supported nickel and manganese catalysts, and the ceria-supported nickel and nickel-manganese catalysts, the CO2 conversion increased with increasing reaction temperature and was consistent at all activation temperatures.

[0210] The results of Tables 6-8 show that activation temperature, reaction temperature, and support type affect CO selectivity. For activation at 400°C and 560°C, the CO selectivity of the titania-supported nickel and manganese catalysts increased with increasing reaction temperature. However, when activated at 760°C, the CO selectivity generally decreased with increasing reaction temperature. For the alumina-supported nickel and manganese catalysts, the CO selectivity peaked at a reaction temperature of 500°C at all activation temperatures, with higher activation temperatures having higher CO selectivity at all measured reaction temperatures. Similarly, for the ceria-supported nickel and manganese catalysts, the CO selectivity peaked at reaction temperatures between 500-600°C at all activation temperatures, with higher activation temperatures having higher CO selectivity at all measured reaction temperatures. Overall, the results of Tables 6-8 show that activation temperature is another variable for adjusting the resulting product stream.

[0211] Additional aspects of the disclosure are provided by the embodiments listed below, which may be combined in any number and in any combination that is not logically or technically inconsistent.

[0212] Embodiment 1. A supported reverse water gas shift catalyst comprising:

[0213] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0214] Nickel, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0215] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0216] Embodiment 2. The catalyst of Embodiment 1, wherein the support constitutes at least 70 wt % (e.g., at least 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %) of the catalyst on an oxide basis.

[0217] Embodiment 3. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a cerium oxide support.

[0218] Embodiment 4. The catalyst of Embodiment 3, wherein at least the surface layer of the cerium oxide support comprises at least 60 wt% cerium oxide, such as at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, based on oxide.

[0219] Embodiment 5. The catalyst of Embodiment 3, wherein at least the surface layer of the cerium oxide support comprises at least 90 wt% cerium oxide, such as at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, based on oxide.

[0220] Embodiment 6. The catalyst of any one of Embodiments 3-5, wherein the cerium oxide support comprises at least 50 wt% cerium oxide, such as at least 60 wt% cerium oxide, or at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, based on the oxide.

[0221] Embodiment 7. The catalyst of any one of Embodiments 3-5, wherein the cerium oxide support comprises at least 90 wt% cerium oxide, such as at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, based on the oxide.

[0222] Embodiment 8. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a titanium oxide support.

[0223] Embodiment 9. The catalyst of Embodiment 8, wherein at least the surface layer of the titanium oxide support comprises at least 60 wt% titanium oxide, for example at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, based on oxides.

[0224] Embodiment 10. The catalyst of Embodiment 8, wherein at least the surface layer of the titanium oxide support comprises at least 90 wt% titanium oxide, such as at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide.

[0225] Embodiment 11. The catalyst of any one of Embodiments 8-10, wherein the titanium oxide support comprises at least 50 wt% titanium oxide, such as at least 60 wt% titanium oxide, or at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, based on the oxide.

[0226] Embodiment 12. The catalyst of any one of Embodiments 8-10, wherein the titanium oxide support comprises at least 90 wt% titanium oxide, such as at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, based on the oxide.

[0227] Embodiment 13. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is an alumina support.

[0228] Embodiment 14. The catalyst of Embodiment 13, wherein at least the surface layer of the alumina support comprises at least 60 wt% alumina, e.g., at least 70 wt% alumina, or at least 80 wt% alumina, on an oxide basis.

[0229] Embodiment 15. The catalyst of Embodiment 13, wherein at least the surface layer of the alumina support comprises at least 90 wt% alumina, e.g., at least 95 wt% alumina, or at least 98 wt% alumina, on an oxide basis.

[0230] Embodiment 16. The catalyst of any one of Embodiments 13-15, wherein the alumina support comprises at least 50 wt% alumina, e.g., at least 60 wt% alumina, or at least 70 wt% alumina, or at least 80 wt% alumina, on an oxide basis.

[0231] Embodiment 17. The catalyst of any one of Embodiments 13-15, wherein the alumina support comprises at least 90 wt% alumina, e.g., at least 95 wt% alumina, or at least 98 wt% alumina, on an oxide basis.

[0232] Embodiment 18. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a zirconia support.

[0233] Embodiment 19. The catalyst of Embodiment 18, wherein at least the surface layer of the zirconia support comprises at least 60 wt% zirconia, for example at least 70 wt% zirconia, or at least 80 wt% zirconia, based on oxides.

[0234] Embodiment 20. The catalyst of Embodiment 18, wherein at least the surface layer of the zirconia support comprises at least 90 wt% zirconia, e.g., at least 95 wt% zirconia, or at least 98 wt% zirconia, based on oxides.

[0235] Embodiment 21. The catalyst of any one of Embodiments 18-20, wherein the zirconia support comprises at least 50 wt% zirconia, such as at least 60 wt% zirconia, or at least 70 wt% zirconia, or at least 80 wt% zirconia, based on the oxide.

[0236] Embodiment 22. The catalyst of any one of Embodiments 18-20, wherein the zirconia support comprises at least 90 wt% zirconia, e.g., at least 95 wt% zirconia, or at least 98 wt% zirconia, on an oxide basis.

[0237] Embodiment 23. The catalyst of Embodiment 1 or Embodiment 2, wherein the support is a mixed oxide support having at least a surface layer comprising at least 50 wt. % of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide, based on the oxides.

[0238] Embodiment 24. The catalyst of any one of Embodiments 1-23, wherein the support does not contain more than 2 wt% of the total amount of the added metal, such as more than 1 wt% or more than 0.5 wt% of the added metal, based on the oxide.

[0239] Embodiment 25. The catalyst of any one of Embodiments 1-23, wherein the support comprises at least one additional metal.

[0240] Embodiment 26. The catalyst of Embodiment 25, wherein the total amount of the at least one additional metal is 0.5-20 wt%, for example 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, based on the oxide.

[0241] Embodiment 27. The catalyst of any one of Embodiments 1-26, wherein the support has a pore volume of at least 0.05 mL / g.

[0242] Embodiment 28. The catalyst of any one of Embodiments 1-27, wherein the support has a pore volume of at most 1.5 mL / g.

[0243] Embodiment 29. The catalyst of any one of Embodiments 1-28, wherein the support has a pore volume in the range of 0.05-1.5 mL / g.

[0244] Embodiment 30. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.1 to 10 wt%, for example, ranging from 0.5 to 10 wt%, or 1 to 10 wt%, or 2 to 10 wt%, or 5 to 10 wt%, based on the total weight of the catalyst.

[0245] Embodiment 31. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 7 wt %, for example, ranging from 0.1 to 7 wt %, or 0.5 to 7 wt %, or 1 to 7 wt %, or 2 to 7 wt %, based on the total weight of the catalyst.

[0246] Embodiment 32. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 5 wt%, for example, ranging from 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, or 2 to 5 wt%, based on the total weight of the catalyst.

[0247] Embodiment 33. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 2 wt%, for example, ranging from 0.1 to 2 wt%, or 0.3 to 2 wt%, or 0.5 to 2 wt%, or 1 to 2 wt%, based on the total weight of the catalyst.

[0248] Embodiment 34. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 1.5 wt. %, for example, ranging from 0.1 to 1.5 wt. %, or 0.3 to 1.5 wt. %, or 0.5 to 1.5 wt. %, based on the total weight of the catalyst.

[0249] Embodiment 35. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 1 wt %, for example, ranging from 0.1 to 1 wt %, or 0.3 to 1 wt %, or 0.5 to 1 wt %, based on the total weight of the catalyst.

[0250] Embodiment 36. The catalyst of any one of Embodiments 1-29, wherein nickel is present in the catalyst in an amount ranging from 0.05 to 0.8 wt%, for example, ranging from 0.1 to 0.8 wt%, or 0.3 to 0.8 wt%, or 0.5 to 0.8 wt%, based on the total weight of the catalyst.

[0251] Embodiment 37. The catalyst of any one of Embodiments 1-36, wherein manganese is present in the catalyst in an amount ranging from 0.5 to 15 wt %, for example, ranging from 0.5 to 12 wt %, or 0.5 to 10 wt %, based on the total weight of the catalyst.

[0252] Embodiment 38. The catalyst of any one of Embodiments 1-36, wherein manganese is present in the catalyst in an amount ranging from 1 to 20 wt %, for example, ranging from 1 to 15 wt %, or 1 to 12 wt %, or 1 to 10 wt %, based on the total weight of the catalyst.

[0253] Embodiment 39. The catalyst of any one of Embodiments 1-36, wherein manganese is present in the catalyst in an amount ranging from 2 to 20 wt%, for example, ranging from 2 to 15 wt%, or 2 to 12 wt%, or 2 to 10 wt%, based on the total weight of the catalyst.

[0254] Embodiment 40. The catalyst of any one of Embodiments 1-36, wherein manganese is present in the catalyst in an amount ranging from 4 to 20 wt %, for example, ranging from 4 to 15 wt %, or 4 to 12 wt %, or 4 to 10 wt %, based on the total weight of the catalyst.

[0255] Embodiment 41. The catalyst of any one of Embodiments 1-40, wherein the weight ratio of nickel to manganese is at least 0.05:1, e.g., at least 0.1:1.

[0256] Embodiment 42. The catalyst of any one of Embodiments 1-41, wherein the weight ratio of nickel to manganese is at most 5:1, e.g., at most 2:1, or 1:1, or 0.5:1.

[0257] Embodiment 43. The catalyst of any one of Embodiments 1-42, wherein the ratio of nickel to manganese is in the range of 0.05:1 to 5:1 (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).

[0258] Embodiment 44. The catalyst of any one of Embodiments 1-43, wherein the total amount of cerium, titanium, aluminum, zirconium, manganese, and nickel in the catalyst, on a metal basis, is at least 90 weight percent, e.g., at least 95 weight percent, or at least 98 weight percent, of the catalyst.

[0259] Embodiment 45. The catalyst of any one of Embodiments 1-44, wherein the catalyst has an additional metal (i.e., non-Mn, Ni, Ce, Ti, Al, or Zr) content of no more than 10 wt.% (e.g., no more than 5 wt.%, or no more than 2 wt.%, or no more than 1 wt.%) based on the total weight of the catalyst.

[0260] Embodiment 46. The catalyst of any one of Embodiments 1-45, wherein the catalyst has a Cu content of no more than 10 wt.% (e.g., no more than 5 wt.%, or no more than 2 wt.%, or no more than 1 wt.%) based on the total weight of the catalyst.

[0261] Embodiment 47. The catalyst of any one of Embodiments 1-46, wherein the catalyst has an alkali metal content of no more than 10 wt. % (e.g., no more than 5 wt. %, or no more than 2 wt. %, or no more than 1 wt. %) based on the total weight of the catalyst.

[0262] Embodiment 48. The catalyst of any one of Embodiments 1-47, wherein the catalyst has an alkaline earth metal content of no more than 10 wt. % (e.g., no more than 5 wt. %, or no more than 2 wt. %, or no more than 1 wt. %) based on the total weight of the catalyst.

[0263] Embodiment 49. A method of making the catalyst of any one of Embodiments 1-48, the method comprising:

[0264] providing a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0265] contacting the support with one or more liquids, the one or more liquids each comprising one or more nickel-containing compounds and / or one or more manganese-containing compounds dispersed in a solvent;

[0266] allowing the solvent to evaporate to provide a catalyst precursor; and

[0267] The catalyst precursor is calcined.

[0268] Embodiment 50. The method of Embodiment 49, wherein contacting the support with the liquid comprises adding the liquid in an amount equal to the pore volume of the support.

[0269] Embodiment 51. The method of Embodiment 49, wherein contacting the support with the liquid comprises adding the liquid in an amount greater than the pore volume of the support.

[0270] Embodiment 52. The method of any one of Embodiments 49-51, wherein the ratio of the amount of liquid to the amount of carrier on a mass basis is in the range of 1:1 to 5:1 (e.g., in the range of 1:1 to 3:1).

[0271] Embodiment 53. The method of any one of Embodiments 49-52, wherein contacting the support with the liquid provides a slurry.

[0272] Embodiment 54. The method of any one of Embodiments 49-53, wherein the solvent is allowed to evaporate at ambient temperature.

[0273] Embodiment 55. The method of any one of Embodiments 49-53, wherein the solvent is allowed to evaporate at an elevated temperature (eg, in the range of 50-150° C.) for a drying time (eg, 24 hours).

[0274] Embodiment 56. The method of any one of Embodiments 49-53, wherein the solvent is allowed to evaporate under vacuum and elevated temperature (eg, in the range of 50-150° C.) for a drying time (eg, 24 hours).

[0275] Embodiment 57. The method of any one of Embodiments 49-53, wherein the solvent is allowed to evaporate at an elevated temperature (eg, in the range of 30-100° C.) in a stirred drying bath.

[0276] Embodiment 58. The method of any one of Embodiments 49-53, 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).

[0277] Embodiment 59. The method of any one of Embodiments 49-58, wherein calcining the catalyst precursor is carried out at a temperature in the range of 100-600°C (eg, in the range of 120-500°C).

[0278] Embodiment 60. The catalyst of any one of Embodiments 1-48, prepared by the method according to Embodiments 49-59.

[0279] Embodiment 61. A method of performing a reverse water gas shift reaction, the method comprising:

[0280] A catalyst according to any one of embodiments 1-48 and 60 is contacted with a feed stream comprising CO2 and H2 at a temperature in the range of 500-900°C to provide a product stream comprising CO and H2, wherein the product stream has a lower concentration of CO2 and a higher concentration of CO than the feed stream.

[0281] Embodiment 62. The method of Embodiment 61, wherein the reverse water gas shift reaction has a CO selectivity of at least 50%, for example at least 60%, or 70%, or 80%, or 90%.

[0282] Embodiment 63. The method described in Embodiment 61, wherein the reverse water gas shift reaction has a CO selectivity in the range of 50-99 wt. % (for example, in the range of 50-90 wt. %, or 50-80 wt. %, or 50-70 wt. %, or 50-60 wt. %, or 60-99 wt. %, or 60-90 wt. %, or 60-80 wt. %, or 60-70 wt. %, or 70-99 wt. %, or 70-90 wt. %, or 70-80 wt. %).

[0283] Embodiment 64. The method of any one of Embodiments 61-63, 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%.

[0284] Embodiment 65. The method of any one of Embodiments 61-63, wherein the reverse water gas shift reaction has a methane selectivity of no more than 10%, for example no more than 8%.

[0285] Embodiment 66. The method of any one of Embodiments 61-63, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example no more than 4%.

[0286] Embodiment 67. The method of any one of Embodiments 61-63, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, for example no more than 1%.

[0287] Embodiment 68. The method of any one of Embodiments 61-63, wherein the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, for example no more than 0.4%.

[0288] Embodiment 69. The method of any one of Embodiments 61-68, having a CO2 conversion rate of at least 5%, for example at least 10%, or 20%.

[0289] Embodiment 70. The method of any one of Embodiments 61-68, having a CO2 conversion rate of at least 30%, such as at least 40%.

[0290] Embodiment 71. The method of any one of Embodiments 61-70, having a CO2 conversion rate of not more than 90%, for example, not more than 80%, or not more than 70%.

[0291] Embodiment 72. The method described in any one of Embodiments 61-70, having a CO2 conversion rate of not more than 65%, for example not more than 60%.

[0292] Embodiment 73. The method described in any one of Embodiments 61-72 is carried out at a temperature in the range of 500-850°C, for example, in the range of 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.

[0293] Embodiment 74. The method described in any one of Embodiments 61-72 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.

[0294] Embodiment 75. The method described in any one of Embodiments 61-72 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.

[0295] Embodiment 76. The method described in any one of Embodiments 61-72 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.

[0296] Embodiment 77. The method of any one of Embodiments 61-72 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.

[0297] Embodiment 78. The method of any one of Embodiments 61-77, wherein at least a portion of the H2 of the feed stream is from a renewable source.

[0298] Embodiment 79. The method of any one of Embodiments 61-78, wherein at least a portion of the H2 of the feed stream is green hydrogen.

[0299] Embodiment 80. The method of any one of Embodiments 61-78, wherein at least a portion of the H2 of the feed stream is blue hydrogen.

[0300] Embodiment 81. The method of any one of Embodiments 61-78, wherein at least a portion of the H2 of the feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0301] Embodiment 82. The method of any one of Embodiments 61-81, wherein at least a portion of the CO2 of the feed stream comes from a renewable source.

[0302] Embodiment 83. The method of any one of Embodiments 61-81, wherein at least a portion of the CO2 of the feed stream comes from direct air capture.

[0303] Embodiment 84. The method of any one of Embodiments 61-81, wherein at least a portion of the CO2 of the feed stream is captured from a manufacturing plant, such as a bioethanol plant, a steel plant, or a cement plant.

[0304] Embodiment 85. The method of any one of Embodiments 61-84, 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.

[0305] Embodiment 86. The method of any one of Embodiments 61-84, wherein the molar ratio of H2 to CO2 in the feed stream is at least 0.9:1, e.g., at least 1:1 or at least 1.5:1.

[0306] Embodiment 87. The method of any one of Embodiments 61-84, wherein the molar ratio of H2 to CO2 in the feed stream is at least 2:1, for example at least 2.5:1.

[0307] Embodiment 88. The method of any one of Embodiments 61-87, wherein the molar ratio of H2 to CO2 in the feed stream is no more than 100:1, e.g., no more than 75:1, or 50:1.

[0308] Embodiment 89. The method of any one of Embodiments 61-87, wherein the molar ratio of H2 to CO2 in the feed stream is no more than 20:1, eg, no more than 15:1, or 10:1.

[0309] Embodiment 90. The method of any one of Embodiments 61-87, wherein the molar ratio of H2 to CO2 in the feed stream is in the range of 0.5:1 to 10:1.

[0310] Embodiment 91. The method of any one of Embodiments 61-90, carried out at a pressure in the range of 1 to 100 bar, for example in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 80 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar.

[0311] Embodiment 92. The method of any one of Embodiments 61-91, wherein the -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0312] Embodiment 93. The method of any one of Embodiments 61-92, wherein the product stream contains no more than 95 mol % CO2 (e.g., no more than 90 mol % CO2).

[0313] Embodiment 94. The method of any one of Embodiments 61-92, wherein the product stream contains no more than 85 mol % CO2 (e.g., no more than 80 mol % CO2).

[0314] Embodiment 95. The method of any one of Embodiments 61-92, wherein the product stream contains no more than 75 mol% CO2 (e.g., no more than 70 mol% CO2).

[0315] Embodiment 96. The method of any one of Embodiments 61-95, wherein the product stream further comprises CO2, and wherein the method further comprises recycling at least a portion of the CO2 of the product stream to the feed stream.

[0316] Embodiment 97. The method of any one of Embodiments 61-96, wherein the product stream further comprises hydrogen, and wherein the method further comprises recycling at least a portion of the hydrogen of the product stream to the feed stream.

[0317] Embodiment 98. The method of any one of Embodiments 61-97, wherein the ratio of H2:CO in the product feed stream is in the range of 0.1:1 to 100:1 (for example, 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).

[0318] Embodiment 99. The method of any one of Embodiments 61-98, wherein the product feed stream contains no more than 40 mol% methane, for example, no more than 35 mol%, or 30 mol%, or 25 mol%, or 20 mol%, or 15 mol% methane.

[0319] Embodiment 100. The method of any one of Embodiments 61-98, wherein the product stream contains no more than 10 mol% methane, for example, no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

[0320] Embodiment 101. The method of any one of Embodiments 61-100, wherein the method comprises activating the catalyst prior to contacting the catalyst with the feed stream.

[0321] Embodiment 102. The method of Embodiment 101, wherein activating the catalyst comprises contacting the catalyst with a reducing feed stream comprising a reducing gas (eg, hydrogen).

[0322] Embodiment 103. The method of Embodiment 101 or Embodiment 102, wherein the reducing feed stream comprises hydrogen in an amount of at least 25 mol % (e.g., at least 50 mol %, or 75 mol %, or 90 mol %).

[0323] Embodiment 104. The method of any one of Embodiments 101-103, wherein activating the catalyst is performed at a temperature in the range of 300 to 800°C, such as in the range of 400 to 700°C.

[0324] Embodiment 105. The method of any one of Embodiments 101-104, wherein activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or 50% reduced).

[0325] Embodiment 106. A method of performing an integrated Fischer-Tropsch process, the method comprising:

[0326] Providing a first feed stream comprising H2 and CO2;

[0327] contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 500-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream;

[0328] contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a catalyst comprising C 5+ a second product stream of hydrocarbons,

[0329] The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising:

[0330] a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia;

[0331] Nickel, present in an amount ranging from 0.05 to 10 weight percent of the catalyst based on the total weight of the catalyst; and

[0332] Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

[0333] Embodiment 107. The method of Embodiment 106, 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.

[0334] Embodiment 108. The method of any one of Embodiments 106, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 0.9:1, eg, at least 1:1 or at least 1.5:1.

[0335] Embodiment 109. The method of Embodiment 106, 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.

[0336] Embodiment 110. The method of any one of Embodiments 106-109, wherein the molar ratio of H2 to CO2 in the first feed stream is no more than 100:1, eg, no more than 75:1, or 50:1.

[0337] Embodiment 111. The method of any one of Embodiments 106-109, wherein the molar ratio of H2 to CO2 in the first feed stream is no more than 20:1, eg, no more than 15:1, or 10:1.

[0338] Embodiment 112. The method of any one of Embodiments 106-109, wherein the molar ratio of H2 to CO2 in the first feed stream ranges from 0.5:1 to 10:1.

[0339] Embodiment 113. A method according to any one of Embodiments 106-112, wherein the first feed stream further comprises CO.

[0340] Embodiment 114. The method of any one of Embodiments 106-113, wherein the first feed stream further comprises one or more inert gases (e.g., nitrogen and / or methane).

[0341] Embodiment 115. The method of any one of Embodiments 106-114, wherein the reverse water gas shift reaction has a CO selectivity of at least 50%, such as at least 60%, or 70%, or 80%, or 90%.

[0342] Embodiment 116. A method as described in any one of Embodiments 106-114, wherein the reverse water gas shift reaction has a CO selectivity in the range of 50-99 wt. % (for example, in the range of 50-90 wt. %, or 50-80 wt. %, or 50-70 wt. %, or 50-60 wt. %, or 60-99 wt. %, or 60-90 wt. %, or 60-80 wt. %, or 60-70 wt. %, or 70-99 wt. %, or 70-90 wt. %, or 70-80 wt. %).

[0343] Embodiment 117. The method of any one of Embodiments 106-116, 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%.

[0344] Embodiment 118. The method of any one of Embodiments 106-116, wherein the reverse water gas shift reaction has a methane selectivity of no more than 10%, for example no more than 8%.

[0345] Embodiment 119. The method of any one of Embodiments 106-116, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, for example no more than 4%.

[0346] Embodiment 120. The method of any one of Embodiments 106-116, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, for example no more than 1%.

[0347] Embodiment 121. The method of any one of Embodiments 106-116, wherein the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0348] Embodiment 122. The method of any one of Embodiments 106-121, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 5%, such as at least 10%, or 20%.

[0349] Embodiment 123. The method of any one of Embodiments 106-121, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 30%, such as at least 40%.

[0350] Embodiment 124. The method of any one of Embodiments 106-123, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 90%, eg, no more than 80%, or no more than 70%.

[0351] Embodiment 125. The method of any one of Embodiments 106-123, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 65%, for example no more than 60%.

[0352] Embodiment 126. The method of any one of Embodiments 106-125 is carried out at a first temperature in the range of 500-850°C, for example, in the range of 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.

[0353] Embodiment 127. The method described in any one of Embodiments 106-125 is carried out at a first 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.

[0354] Embodiment 128. The method of any one of Embodiments 106-125 is carried out at a first 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.

[0355] Embodiment 129. The method of any one of Embodiments 106-125 is performed at a first 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.

[0356] Embodiment 130. The method of any one of Embodiments 106-125 is performed at a first temperature in the range of 700-900°C, such as in the range of 700-850°C, or 700-800°C, or 700-750°C.

[0357] Embodiment 131. A method according to any one of Embodiments 106-130, wherein the reverse water gas shift reaction is carried out at a pressure in the range of 1 to 100 bar (for example, in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 80 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar).

[0358] Embodiment 132. The method of any one of Embodiments 106-131, wherein the reverse water gas shift reaction is carried out at 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0359] Embodiment 133. The method of any one of Embodiments 106-132, wherein the method comprises activating the reverse water gas shift catalyst, for example, before contacting the reverse water gas shift catalyst with the first feed stream.

[0360] Embodiment 134. The method of Embodiment 133, wherein activating the rWGS catalyst comprises contacting the rWGS catalyst with a reducing feed stream comprising a reducing gas (eg, hydrogen).

[0361] Embodiment 135. The method of Embodiment 133 or Embodiment 134, wherein the reducing feed stream comprises hydrogen in an amount of at least 25 mol % (e.g., at least 50 mol %, or 75 mol %, or 90 mol %).

[0362] Embodiment 136. The method of any one of Embodiments 133-135, wherein 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 800°C, or 300°C to 700°C).

[0363] Embodiment 137. The method of any one of Embodiments 133-136, wherein activation of the rWGS catalyst provides a catalyst that is at least 10% reduced (eg, at least 25%, or 50% reduced).

[0364] Embodiment 138. The method of any one of Embodiments 106-137, wherein the first product stream contains no more than 95 mol % CO2 (e.g., no more than 90 mol % CO2).

[0365] Embodiment 139. The method of any one of Embodiments 106-137, wherein the first product stream contains no more than 85 mol % CO2 (e.g., no more than 80 mol % CO2).

[0366] Embodiment 140. The method of any one of Embodiments 106-137, wherein the first product stream contains no more than 75 mol % CO2 (e.g., no more than 70 mol % CO2).

[0367] Embodiment 141. The method of any one of Embodiments 106-137, wherein the first product feed 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 10-90 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% CO2 in the range of.

[0368] Embodiment 142. The method of any one of Embodiments 106-141, wherein the first product feed stream contains no more than 40 mol% methane, for example, no more than 35 mol%, or 30 mol%, or 25 mol%, or 20 mol%, or 15 mol%, or 10 mol% methane.

[0369] Embodiment 143. The method of any one of Embodiments 106-141, wherein the first product feed stream contains no more than 10 mol% methane, for example, no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

[0370] Embodiment 144. The method of any one of Embodiments 106-143, wherein the ratio of H2:CO 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.

[0371] Embodiment 145. The method of any one of Embodiments 106-143, wherein the ratio of H2:CO in the first product feed stream is in the range of 0.1:1 to 100:1 (for example, in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0372] Embodiment 146. The method of any one of Embodiments 106-145, wherein the method further comprises separating the first product stream so as to recycle at least a portion of one or more components of the first product stream to the first feed stream.

[0373] Embodiment 147. The method of any one of Embodiments 106-146, wherein the method further comprises separating the first product stream so as to recycle at least a portion of the CO2 of the first product stream (e.g., at least 5 mole%, at least 10 mole%, at least 25 mole%, at least 50 mole%, at least 75 mole%, or at least 90 mole%) to the first feed stream.

[0374] Embodiment 148. The method of any one of Embodiments 106-147, wherein the method further comprises separating the first product stream so as to recycle at least a portion of the 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%) to the first feed stream.

[0375] Embodiment 149. The method of any one of Embodiments 106-148, wherein the method comprises separating at least a portion of H2 and / or CO from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst.

[0376] Embodiment 150. The method of any one of Embodiments 106-149, wherein the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream.

[0377] Embodiment 151. The method of any one of Embodiments 106-150, wherein the first product stream comprises one or more light hydrocarbons (e.g., methane, ethane, propane).

[0378] Embodiment 152. The method of Embodiment 151 further comprises separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream.

[0379] Embodiment 153. The method of any one of Embodiments 106-152, 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.

[0380] Embodiment 154. The method of any one of Embodiments 106-153, wherein the method further comprises exchanging heat between at least a portion of the first product stream and a steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone.

[0381] Embodiment 155. The method of Embodiment 154, further comprising generating steam from the heat provided to the steam generating zone, and generating electricity from the steam.

[0382] Embodiment 156. The method of Embodiment 154 or 155, wherein the steam is used to heat the first feed stream and / or the second feed stream.

[0383] Embodiment 157. The method of any one of Embodiments 106-156, wherein at least 25% of the CO of the first product stream, for example, at least 50% of the CO, at least 75% of the CO, or at least 90% of the CO of the first product stream is contained in the second feed stream.

[0384] Embodiment 158. The method of any one of Embodiments 106-157, wherein CO is provided to the second feed stream from a CO source other than the first product stream.

[0385] Embodiment 159. The method of any one of Embodiments 106-159, 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.

[0386] Embodiment 160. The method of any one of Embodiments 106-159, wherein at least 25% of the H2 of the first product stream, for example, at least 50% of the H2 of the first product stream, at least 75% of the H2, or at least 90% of the H2 of the first product stream is contained in the second feed stream.

[0387] Embodiment 161. The method of any one of Embodiments 106-160, wherein H2 is provided to the second feed stream from a hydrogen source other than the first product stream.

[0388] Embodiment 162. The method of any one of Embodiments 106-161, wherein the second feed stream comprises at least a portion of the CO2 of the first product stream.

[0389] Embodiment 163. The method of any one of Embodiments 106-162, wherein at least 10% of the CO2 of the first product stream, for example, at least 25% of the CO2 of the first product stream, at least 50% of the CO2, at least 75% of the CO2, or at least 90% of the CO2 of the first product stream is contained in the second feed stream.

[0390] Embodiment 164. The method of any one of Embodiments 106-162, wherein the second feed stream does not contain a significant amount of CO2 of the first product stream.

[0391] Embodiment 165. The method of any one of Embodiments 106-164, wherein 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, for example, in the range of 1:1 to 3:1.

[0392] Embodiment 166. The method of any one of Embodiments 106-165, wherein the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, for example, or no more than 2 mol%, or no more than 0.5 mol%.

[0393] Embodiment 167. The method of any one of Embodiments 106-166, wherein the portion of the first product stream contained in the second feed stream has a CO2 content in the range of 10-95 mol% CO2, 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% CO2.

[0394] Embodiment 168. The method of any one of Embodiments 106-167, wherein the second feed stream has a H2:CO ratio in a range of 0.5:1 to 6:1.

[0395] Embodiment 169. The method of any one of Embodiments 106-167, wherein the second feed stream has a H2:CO ratio in a range from 1:1 to 3:1, for example, from 1:1 to 2.5:1.

[0396] Embodiment 170. The method of any one of Embodiments 106-167, wherein the second feed stream has a H2:CO ratio of at least 1.4:1, e.g., in a range of 1.4:1 to 3:1, or 1.4:1 to 2.5:1.

[0397] Embodiment 171. The method of any one of Embodiments 106-170, wherein the second feed stream comprises up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% of one or more inerts.

[0398] Embodiment 172. The method of any one of Embodiments 106-170, wherein the second feed stream contains up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%, of one or more inerts selected from CO2, methane, and nitrogen.

[0399] Embodiment 173. The method of any one of Embodiments 106-172, wherein the second feed stream contains 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% CO2.

[0400] Embodiment 174. The method of any one of Embodiments 106-173, wherein the second feed stream has a water content of no more than 10 mol%, eg, or no more than 2 mol%, or no more than 0.5 mol%.

[0401] Embodiment 175. The method of any one of Embodiments 106-174, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0402] Embodiment 176. The method of any one of Embodiments 106-174, wherein the Fischer-Tropsch catalyst contains cobalt in an amount in the range of 5-25 wt%, calculated as Co(0), for example 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt%.

[0403] Embodiment 177. The method of any one of Embodiments 106-174, wherein the Fischer-Tropsch catalyst contains iron in an amount in the range of 5-95 wt.%, calculated as Fe(0), for example 10-95 wt.%, or 25-95 wt.%, or 50-95 wt.%, or 5-85 wt.%, or 10-85 wt.%, or 25-85 wt.%, or 50-85 wt.%, or 5-75 wt.%, or 10-75 wt.%, or 25-75 wt.%.

[0404] Embodiment 178. The method of any one of Embodiments 175-178, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0405] Embodiment 179. The method described in Embodiment 178, wherein manganese is present in an amount of up to 15 wt%, calculated as Mn(0), for example up to 12 wt%, or up to 10 wt%, or up to 7 wt%, or in the range of 0.1-15 wt%, for example 0.1-10 wt%, or 0.1-5 wt%, 0.5-15 wt%, or 0.5-10 wt%, or 0.5-5 wt%.

[0406] Embodiment 180. The method of any one of Embodiments 106-179, 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.

[0407] Embodiment 181. The method of any one of Embodiments 106-179, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0408] Embodiment 182. The method of any one of Embodiments 106-179, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titanium dioxide support.

[0409] Embodiment 183. The method of any one of Embodiments 106-182, wherein the Fischer-Tropsch catalyst is activated by contact with a reducing gas, such as hydrogen.

[0410] Embodiment 184. The method of Embodiment 183, wherein the reducing gas comprises at least a portion of the hydrogen from the first product stream.

[0411] Embodiment 185. The method of any one of Embodiments 106-182, wherein the Fischer-Tropsch catalyst is activated by contact with H2 and CO.

[0412] Embodiment 186. The method of Embodiment 185, wherein the reducing gas comprises at least a portion of H2 and CO from the first product stream.

[0413] Embodiment 187. The method of any one of Embodiments 183-185, wherein the activation is performed at a temperature in the range of 200-400°C.

[0414] Embodiment 188. The method of any one of Embodiments 106-187, wherein the second temperature is in the range of 150-400°C (for example, in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0415] Embodiment 189. The method of any one of Embodiments 106-188, wherein the second temperature is in the range of 200-350°C.

[0416] Embodiment 190. The method of any one of Embodiments 106-189, wherein the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

[0417] Embodiment 191. The method of any one of Embodiments 106-189, wherein the first temperature is at least 100°C higher than the second temperature, for example at least 150°C higher than the second temperature, or at least 200°C higher than the second temperature.

[0418] Embodiment 192. The method of any one of Embodiments 106-191, wherein the second pressure is in the range of 10-50 bar (e.g., 20-50 bar, or 25-50 bar, or 10-40 bar, or 20-40 bar, or 25-40 bar, or 10-35 bar, or 20-35 bar, or 25-35 bar).

[0419] Embodiment 193. The method of any one of Embodiments 106-192, wherein the second pressure is in the range of 20-50 bar.

[0420] Embodiment 194. The method of any one of Embodiments 106-193, wherein the Fischer-Tropsch reaction is carried out at a temperature of 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0421] Embodiment 195. The method of any one of Embodiments 106-194, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% C 5+ Selective.

[0422] Embodiment 196. The method of any one of Embodiments 106-195, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ The selectivity of alkanes is carried out.

[0423] Embodiment 197. The method of any one of Embodiments 106-196, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ Alkanes and C 5+ The selectivity of alcohol is carried out.

[0424] Embodiment 198. The method of any one of Embodiments 106-197 further comprises separating at least a portion of the water from the second product stream.

[0425] Embodiment 199. The method of any one of Embodiments 106-198, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0426] Embodiment 200. The method described in Embodiment 199 further comprises including at least a portion of a light hydrocarbon stream in the first feed stream and / or the second feed stream.

[0427] Embodiment 201. The method of Embodiment 199 or Embodiment 200 further comprises oxidizing at least a portion of the light hydrocarbon stream to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream and / or the second feed stream.

[0428] Embodiment 202. The method described in any one of Embodiments 199-201 further includes reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon stream to provide a reforming stream containing CO and / or CO2, and including at least a portion of the reforming stream in the first feed stream and / or the second feed stream.

[0429] Embodiment 203. The method of Embodiment 201 or Embodiment 202, wherein the oxidation or reforming provides energy, thermal energy or electrical energy.

[0430] Embodiment 204. The method of any one of Embodiments 199-203 further comprises combusting at least a portion of the light hydrocarbon stream to provide energy, such as heat or electricity.

[0431] Embodiment 205. The method of Embodiment 204, wherein thermal energy is provided and the thermal energy is used to heat the first feed stream.

[0432] Embodiment 206. The method of any one of Embodiments 106-205, wherein the method further comprises exchanging heat between at least a portion of the second product stream and a steam generating zone, thereby cooling at least a portion of the first feed stream and providing heat to the steam generating zone.

[0433] Embodiment 207. The method of Embodiment 206 further comprises generating steam from heat provided to the steam generating zone, and generating electricity from the steam.

[0434] Embodiment 208. The method of Embodiment 206 or 207, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0435] Embodiment 209. The method of any one of Embodiments 106-208, 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.

[0436] Embodiment 210. The method of any one of Embodiments 106-209 further comprises recycling at least a portion of the H2 of the second product stream to the second feed stream.

[0437] Embodiment 211. The method of any one of Embodiments 106-210 further comprises recycling at least a portion of the H2 of the second product stream to the first feed stream.

[0438] Embodiment 212. The method of Embodiment 211 further comprises providing H2 to the second feed stream from a H2 source other than the first product stream.

[0439] Embodiment 213. The method of Embodiment 212, wherein the H2 from the second product stream constitutes a majority of the H2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the H2 of the first feed stream.

[0440] Embodiment 214. The method of any one of Embodiments 106-213 further comprises recycling at least a portion of the CO of the second product stream to the second feed stream.

[0441] Embodiment 215. The method of any one of Embodiments 106-214 further comprises recycling at least a portion of the CO of the second product stream to the first feed stream.

[0442] Embodiment 216 The method of any one of Embodiments 106-215, further comprising recycling at least a portion of the inerts of the second product stream to the second feed stream.

[0443] Embodiment 217 The method of any one of Embodiments 106-216, further comprising recycling at least a portion of the inerts of the second product stream to the first feed stream.

[0444] Embodiment 218. The method of any one of Embodiments 106-217 further comprises recycling at least a portion of the CO2 of the second product stream to the first feed stream.

[0445] Embodiment 219. The method of Embodiment 218 further comprises providing CO2 to the second feed stream from a CO2 source other than the first product stream.

[0446] Embodiment 220. The method of Embodiment 219, wherein the CO2 from the second product stream constitutes a majority of the CO2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 of the first feed stream.

[0447] Embodiment 221. The method of any one of Embodiments 106-220, wherein the C of the second product stream 5+ At least a portion of the hydrocarbons provides one or more products.

[0448] Embodiment 222. The method of Embodiment 221, wherein the one or more products include fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants, and waxes.

[0449] Embodiment 223. The method of any one of Embodiments 106-222, further comprising hydrotreating the C of the second product stream. 5+ at least a portion of a hydrocarbon.

[0450] Embodiment 224. The method of any one of Embodiments 106-223, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream is from a renewable source.

[0451] Embodiment 225. The method of any one of Embodiments 106-224, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream comes from direct air capture.

[0452] Embodiment 226. The method of any one of Embodiments 106-225, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream is captured from a manufacturing plant such as a bioethanol plant, a steel plant, or a cement plant.

[0453] Embodiment 227. The method of any one of Embodiments 106-226, wherein at least a portion of the H2 of the first feed stream or the second feed stream is from a renewable source.

[0454] Embodiment 228. The method of any one of Embodiments 106-227, wherein at least a portion of the H2 of the first feed stream or the second feed stream is green hydrogen.

[0455] Embodiment 229. The method of any one of Embodiments 106-228, wherein at least a portion of the H2 of the first feed stream or the second feed stream is blue hydrogen.

[0456] Embodiment 230. The method of any one of Embodiments 106-299, wherein at least a portion of the H2 of 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.

[0457] Embodiment 231. The method of any one of Embodiments 106-230 further comprises providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water.

[0458] Embodiment 232. The method of Embodiment 231, wherein the electrolysis of water is performed at least in part using electricity from a renewable source.

[0459] Embodiment 233. The method of Embodiment 231 or Embodiment 232, wherein the electrolysis of water is carried out at least in part using electricity generated by steam produced by heat exchange from the first product stream and / or the second product stream or by burning a light hydrocarbon stream.

[0460] Embodiment 234. The method of any one of Embodiments 232-233 further includes providing at least a portion of the O2 produced in the electrolysis to partial oxidation.

[0461] Embodiment 235. The method of any one of Embodiments 106-234, 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.

[0462] Embodiment 236. The method described in any one of Embodiments 106-234, wherein the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein a second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0463] Embodiment 237. The method described in Embodiment 236, wherein the first reactor bed and the second reactor bed are arranged in the same reactor.

[0464] Embodiment 238. The method of any one of Embodiments 106-234, wherein the method is performed in a reactor system comprising a first catalyst container having one or more reverse water gas shift catalysts disposed therein, and wherein a second reaction zone comprises a second catalyst container having one or more Fischer-Tropsch catalysts disposed therein.

[0465] Embodiment 239. The method of Embodiment 238, wherein the one or more first catalyst containers and the one or more second catalyst containers are disposed in the same reactor.

[0466] Embodiment 240. The method of any one of Embodiments 106-239, wherein the method is carried out in a reactor system comprising a reverse water gas shift catalyst and a Fischer-Tropsch catalyst, for example, disposed in admixture therein.

[0467] The details shown herein are presented as examples only and for the purpose of illustrative discussion of the preferred embodiments of the present invention, and are presented in order to provide the most useful and easily understood descriptions of the principles and concepts of the various embodiments of the present invention. In this regard, no attempt is made to show the structural details of the present invention in more detail than is required for a basic understanding of the present invention. The description in conjunction with the drawings and / or embodiments makes it clear to those skilled in the art how several forms of the present invention can be embodied in practice. Thus, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, equipment or configurations, and therefore can certainly vary. It should also be understood that the terms used herein are only used for the purpose of describing specific aspects, and are not intended to be restrictive unless specifically defined herein.

[0468] The terms "a", "an", "the" and similar referents used in the context of describing the present invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of numerical ranges herein is intended merely to serve as a shorthand process for individually referring to each individual value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into this specification as if it were individually referenced herein. It will be further understood that the endpoints of each range are significant both relative to the other endpoint and independently of the other endpoint.

[0469] Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order of steps. The use of any and all embodiments or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the present invention, rather than to limit the scope of the present invention otherwise claimed. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the present invention.

[0470] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise", "comprising", etc. should be interpreted in an inclusive sense and not in an exclusive or exhaustive sense; that is, in the sense of "including but not limited to". Words using the singular or plural number also include the plural and singular, respectively. In addition, when used in this application, the words "herein", "above", and "below" and words of similar meaning shall refer to this application as a whole and not to any particular parts of this application.

[0471] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of the elements, steps, ingredients, or components specifically stated therein. As used herein, the transitional terms "comprise" or "comprises" are meant to include, but are not limited to, and allow for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of excludes any elements, steps, ingredients, or components that are not specified. The transitional phrase "consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiment.

[0472] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0473] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0474] The grouping of the alternative elements of the present invention disclosed herein or embodiments should not be construed as limiting. Each group member can be mentioned and claimed individually or in any combination with other members of the group or other elements found herein. For reasons of convenience and / or patentability, it is contemplated that one or more members in the group may be included in the group or deleted from the group. When any such inclusion or deletion occurs, this specification is considered to contain the group modified, thereby satisfying the written specifications of all Markush groups used in the appended claims.

[0475] Some embodiments of the present invention are described herein, including the best mode of implementing the present invention known to the inventor. Of course, after reading the foregoing description, changes in the embodiments described will become apparent to those of ordinary skill in the art. The inventor expects those skilled in the art to appropriately adopt these changes, and the inventor intends to practice the present invention in a manner different from that specifically described herein. Therefore, the present invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, the present invention encompasses any combination of the above-mentioned elements in all possible variations thereof.

[0476] In addition, it should be understood that the embodiments of the present invention disclosed herein illustrate the principles of the present invention. Other modifications that may be adopted are within the scope of the present invention. Therefore, by way of example and not limitation, alternative configurations of the present invention may be utilized according to the teachings herein. Therefore, the present invention is not limited to what is precisely shown and described.

Claims

1. A method for performing a reverse water gas shift reaction, the method comprising: contacting a supported reverse water gas shift catalyst with a feed stream comprising CO2 and H2 at a temperature in the range of 500-900°C to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2 and a higher concentration of CO than the feed stream; The catalyst comprises: a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia; Nickel, present in an amount ranging from 0.05 to 10% by weight of the catalyst based on the total weight of the catalyst; and Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

2. The method of claim 1, wherein the reverse water gas shift reaction has a CO selectivity of at least 50%.

3. The method of claim 1, wherein the reverse water gas shift reaction has a methane selectivity of no more than 40%.

4. The method of claim 1 having a CO2 conversion rate of at least 30%.

5. The method of claim 1, having a CO2 conversion rate of no more than 90%.

6. The method of claim 1, carried out at a temperature in the range of 600-800°C.

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

1.

8. The process of claim 1, wherein the product stream comprises no more than 75 mol % CO2.

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

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

11. The process of claim 1 , wherein the product stream comprises no more than 40 mole percent methane.

12. The process of claim 1, wherein the product stream comprises no more than 10 mole % methane.

13. A method for performing an integrated Fischer-Tropsch process, the method comprising: Providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 500-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream; contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a product comprising C 5+ a second product stream of hydrocarbons, The reverse water-gas shift catalyst is a supported reverse water-gas shift catalyst comprising: a support which is a ceria support, a titania support, an alumina support, a zirconia support, or a mixed oxide support comprising a mixture of two or more of ceria, titania, alumina, and zirconia; Nickel, present in an amount ranging from 0.05 to 10% by weight of the catalyst based on the total weight of the catalyst; and Manganese is present in an amount ranging from 0.5 to 20 wt % of the catalyst based on the total weight of the catalyst.

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

15. The process of claim 13, wherein nickel is present in the catalyst in an amount ranging from 0.1 to 10 wt%.

16. The process of claim 13, wherein manganese is present in the catalyst in an amount ranging from 2 to 20 weight percent.

17. The method of claim 13, wherein the ratio of nickel to manganese is in the range of 0.05:1 to 1:

1.

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

1.

19. The method of claim 13, wherein the reverse water gas shift reaction has a methane selectivity of no more than 10%.

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

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

22. The process of claim 13, wherein the first product stream comprises no more than 40 mole percent methane.

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

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

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

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

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

1.

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

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

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

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

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

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

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

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

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

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

38. The catalyst of claim 37, wherein at least the surface layer of the ceria support comprises at least 90 wt% ceria, such as at least 95 wt% ceria, or at least 98 wt% ceria, based on oxide.

39. The catalyst of claim 37, wherein the total amount of cerium, titanium, aluminum, zirconium, manganese and nickel in the catalyst, based on the metals, is at least 90 wt%, such as at least 95 wt%, or at least 98 wt% of the catalyst.

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