Method for integrated syngas production using the water gas shift reaction

Abstract

The present disclosure relates generally to a process for performing an integrated Fischer-Tropsch process, the process comprising: providing a first feed stream comprising H2 and CO2, wherein at least a portion of the CO2 of the first feed stream is from a biogas, a CO2 emission source, and / or direct air capture; contacting a reverse water gas shift catalyst with the first feed stream at a first temperature in the range of 200-1100 °C and a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H2, the first product stream having a lower CO2 concentration and a higher CO concentration than the first feed stream; contacting a 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 second product stream comprising hydrocarbons. 5+ the second product stream comprising hydrocarbons.

Description

[0001] Cross-reference to related applications This application claims priority to European Patent Application No. 23209235.3, filed on November 10, 2023, the entire contents of which are hereby incorporated by reference.

[0002] Background of this disclosure 1. Field This disclosure also relates to integrating methods for performing reverse water-gas shift reactions with methods for performing Fischer-Tropsch reactions. 2. Technical Background Reverse water-gas shift reaction (rWGS) is an advantageous route to obtain carbon monoxide from carbon dioxide for further chemical processing. As shown in equation (1), this rWGS converts carbon dioxide and hydrogen into carbon monoxide and water.

[0004] CO2 + H2 CO + H2O H 0 298 = 42.1 kJmol -1 Eq. (1) This can be used, for example, to change the CO:H2 ratio of a gas mixture for further processing. The carbon monoxide and hydrogen thus formed are valuable feedstocks for many chemical processes, such as the well-known Fischer-Tropsch (FT) process, as shown in equation (2).

[0005] CO + 2 H2 [-CH2-] + H2O H 0 298 = -152 kJmol -1 Eq. (2) However, the rWGS reaction is not advantageous in all cases. For example, the competing reaction is the Sabatier reaction (Equation (3)), which reduces the carbon monoxide yield and favors methane production, which is not an active feedstock for FT.

[0006] CO2 + 4H2 CH4+ 2H2O H 0 298 = -165 kJmol -1 Eq. (3) At lower reaction temperatures, the strongly exothermic Sabatier reaction is thermodynamically more favorable than the endothermic rWGS reaction. Therefore, minimizing methanation during rWGS, especially at low temperatures, is a significant challenge.

[0007] Similarly, carbon monoxide products from rWGS can be hydrogenated to produce methane, as shown in formula (4).

[0008] CO + 3H2 CH4+ H2O H 0 298 = -206.5 kJmol -1 Eq. (4) The hydrogenation of carbon monoxide to methane is also an exothermic reaction, and therefore it is advantageous at lower temperatures. The stoichiometry of this reaction requires a hydrogen to carbon monoxide ratio of at least 3:1. This means that using a large excess of hydrogen to drive the equilibrium toward carbon monoxide (see Equation (1)) is not always ideal, as it risks hydrogenating the carbon monoxide product to form methane.

[0009] In conjunction with equations (3) and (4), other undesirable side reactions may occur. These side reactions can form undesirable carbon deposits on the surface of the catalyst used to promote rWGS. Examples of these carbon-generating side reactions are shown in equations (5), (6), and (7). All three reactions are endothermic and, as with the rWGS reaction, are favored at higher temperatures.

[0010] CO + H2 C + H2O H 0 298 = 131 kJmol -1 Eq. (5) CH4 2H2+ C H 0 298 = 75 kJmol -1 Eq. (6) 2CO CO2+ C H 0 298 = 171 kJmol -1 Eq. (7) Accordingly, since the side reactions that produce carbon (equations (5)-(7)) are also endothermic and are more favorable at higher temperatures, the operation at higher temperatures to favor the desired carbon monoxide products will severely affect the catalyst lifetime through carbon deposition.

[0011] Given the multiple reactions at play and the competing thermodynamics, new integrations with the Fischer-Tropsch process are still needed in this field.

[0012] Furthermore, CO2 is a significant input in these reactions. Carbon dioxide is a widely available gas (currently present in the atmosphere at approximately 400 ppm) and is inert to many transformations. Moreover, its tendency to absorb infrared radiation has led to its designation as a greenhouse gas. Therefore, there is a need to develop economical methods for utilizing carbon dioxide, especially waste carbon dioxide, which would otherwise contribute to the ever-increasing concentration of carbon dioxide in the atmosphere. Summary of the Invention

[0013] In one aspect, this disclosure provides a method for performing integrated Fischer-Tropsch methods, the method comprising: A first feed stream comprising H2 and CO2 is provided, wherein at least a portion of the CO2 in the first feed stream originates from biogas, a CO2 emission source, and / or direct air capture; At a first temperature and a first pressure within the range of 200-1100℃, the reverse water gas shift catalyst is brought into contact with the first feed stream to carry out a reverse water gas shift reaction to provide a first product stream containing CO and H2, which has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream (containing at least a portion of H2 and CO from the first product stream) at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons.

[0014] In another aspect, this disclosure provides a method for performing integrated Fischer-Tropsch methods, the method comprising: A first feed stream comprising H2 and CO2 is provided, wherein at least a portion of the CO2 in the first feed stream is derived from biogas and / or direct air capture; At a first temperature and a first pressure within the range of 200-1100℃, the reverse water-gas shift catalyst is contacted with the first feed stream to carry out the reverse water-gas shift reaction to provide a first product stream containing CO and H2, which has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream (containing at least a portion of H2 and CO from the first product stream) at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons.

[0015] In another aspect, this disclosure provides a method for performing integrated Fischer-Tropsch methods, the method comprising: A first feed stream comprising H2 and CO2 is provided, wherein at least a portion of the CO2 in the first feed stream originates from a CO2 emission source; At a first temperature and a first pressure within the range of 200-1100℃, the reverse water-gas shift catalyst is contacted with the first feed stream to carry out the reverse water-gas shift reaction to provide a first product stream containing CO and H2, which has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream (containing at least a portion of H2 and CO from the first product stream) at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons.

[0016] In another aspect, this disclosure provides a method for performing integrated Fischer-Tropsch methods, the method comprising: A first feed stream comprising H2 and CO2 is provided, wherein at least a portion of the CO2 in the first feed stream originates from biogas, and wherein at least a portion of the methane in the first feed stream originates from biogas; At a first temperature and a first pressure within the range of 200-1100℃, the reverse water-gas shift catalyst is contacted with the first feed stream to carry out the reverse water-gas shift reaction to provide a first product stream containing CO and H2, which has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream (containing at least a portion of H2 and CO from the first product stream) at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons. Brief description of the attached diagram Figure 1 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0018] Figure 2 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0019] Figure 3 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0020] Figure 4 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0021] Figure 5 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0022] Figure 6 This is a schematic diagram of the integrated Fischer-Tropsch method as described in this article.

[0023] Detailed description As discussed above, the reverse water-gas shift (rWGS) reaction, which reacts carbon dioxide with hydrogen to form carbon monoxide and water, can provide a feedstock containing carbon monoxide and hydrogen—often 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 interfere with this rWGS reaction. The Sabatier reaction and CO methanation are exothermic and favored at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and favored at higher temperatures. Furthermore, these reactions rely on CO2, a greenhouse gas. To prevent further waste of CO2 that would otherwise be released into the atmosphere, methods for utilizing CO2 still need to be developed. Advantageously, hydrocarbon synthesis methods using waste carbon dioxide as feedstock have the potential to be low-carbon, carbon-neutral, or even have a negative carbon footprint. One way to achieve this is by converting carbon dioxide to carbon monoxide via the rWGS reaction, as described herein. Therefore, there remains a need to integrate the rWGS method with the Fischer-Tropsch process, which uses renewable CO2 sources.

[0024] In one aspect, this disclosure provides a method for performing an integrated Fischer-Tropsch process, the method comprising: providing a first feed stream comprising H2 and CO2, wherein at least a portion of the CO2 in the first feed stream originates from biogas, a CO2 emission source, and / or direct air capture; contacting a reverse water-gas shift catalyst with the first feed stream at a first temperature and a first pressure in the range of 200-1100°C to perform a reverse water-gas shift reaction to provide a first product stream comprising CO and H2, the first product stream having a lower CO2 concentration and a higher CO concentration compared to the first feed stream; and contacting the Fischer-Tropsch catalyst with a second feed stream (which comprises H2 and at least a portion of the CO from the first product stream) at a second temperature and a second pressure to provide a product stream comprising C 5+ A second product stream of hydrocarbons. In one particular aspect, at least a portion of the CO2 in the first feed stream originates from biogas and / or direct air capture. In another particular aspect, at least a portion of the CO2 in the first feed stream originates from a CO2 emission source.

[0025] The method described herein includes contacting the reverse-flow gas shift catalyst with the first feed stream. There are no particular limitations on the reverse-flow gas shift catalyst, and those skilled in the art will be able to select a suitable catalyst. For example, those skilled in the art will be able to select catalysts such as those described in Daza et al., "CO2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO2 conversion to liquid fuels." RSC Adv., 2016, 6, 49675-49691; Zhu et al., "Catalytic Reduction of CO2 to CO via Reverse Water Gas Shift Reaction: Recent Advances in the Design of Active and Selective Supported Metal Catalyst." Transaction of Tianjin University, 2020, 26, 172-187; and Chen et al., "Recent Advances in Supported Metal Catalysts and Oxide Catalyst for the Reverse Water-Gas Shift Reaction." Front. Chem., 2020, 8, 709, each of which is hereby incorporated herein by reference in its entirety. These catalysts include rWGS active metals. For example, such active metals can be selected from copper, platinum, palladium, rhodium, rhenium, ruthenium, nickel, gold, and iridium, or combinations thereof.

[0026] The water-gas shift catalyst suitable for the methods described herein can be of various forms and is not particularly limited. For example, the water-gas shift catalyst can be a supported or unsupported catalyst. While the form of the catalyst is not particularly limited, in various desirable embodiments, the water-gas shift catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, alumina, silicon oxide, and zinc oxide. For example, in various embodiments, the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, and alumina. In some embodiments of this disclosure as described herein, the support is a titanium dioxide support. In some embodiments of this disclosure as described herein, the support is a zirconium dioxide support. In some embodiments of this disclosure as described herein, the support is a cerium dioxide support. In some embodiments of this disclosure as described herein, the support is an alumina support.

[0027] Those skilled in the art will understand that the countercurrent gas shift catalysts of this disclosure can be provided in many forms, particularly depending on the specific form of the reactor system in which they will be used, for example, in a fixed bed or as a fluidized bed. The support for the countercurrent gas shift catalyst itself can be provided as a discrete body of material, for example as porous particles, pellets, or shaped extrusions, with a metal disposed thereon to provide the countercurrent gas shift catalyst. However, in other embodiments, the countercurrent gas shift catalyst of this disclosure can itself be formed as a layer on an underlying substrate. This underlying substrate is not particularly limited. It can be formed of, for example, a metal or metal oxide, and can itself be provided in many forms, such as particles, pellets, shaped extrusions, or bulk materials. Those skilled in the art will select a suitable Fischer-Tropsch catalyst for a particular reactor system.

[0028] The method includes providing a first feed stream comprising H2 and CO2; contacting the first feed stream with a reverse water-gas shift catalyst, as described herein, at a first temperature and a first pressure within the range of 200-1100°C to perform a reverse water-gas shift reaction, thereby providing a first product stream comprising CO and H2, the first product stream having a lower CO2 concentration and a higher CO concentration compared to the first feed stream. Examples of such methods are schematically shown in… Figure 1 In. Figure 1In this method 100, a reverse water-gas shift reaction is carried out by providing a first feed stream 111 containing H2 and CO2 (hereintroduced to a first reaction zone, e.g., reactor 110). A reverse water-gas shift catalyst 113, as described herein, is contacted with the feed stream 111 at a first temperature and a first pressure in the range of 200-1100°C to provide a first product stream 112 containing CO and H2. This first product stream has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The method of this aspect of the present disclosure further includes contacting a Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream (which contains H2 and at least a portion of the CO from the first product stream) to provide a product stream containing C. 5+ The second product stream of hydrocarbons. Figure 1 In method 100, at least a portion of the CO in the first product stream 112 is included in a second feed stream 121, which is contacted with the Fischer-Tropsch catalyst 123 in a second reaction zone (e.g., reactor 120). This provides CO... 5+ The second product of hydrocarbons, stream 122.

[0029] As used herein, “feed stream” refers to the total material input into a process step, such as a reverse water-gas shift or Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams, and via a single inlet or multiple inlets. For example, H2 and CO from a first feed stream may be provided to the reverse water-gas shift catalyst in a single physical stream (e.g., in a single pipe to reactor 110) or in multiple physical streams (e.g., a separate inlet for CO and H2, or one inlet for fresh CO and H2 and another for recycled CO and / or H2). Similarly, “product stream” refers to the total material output from a process step, such as a reverse water-gas shift or Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams, and via a single outlet or multiple outlets.

[0030] As stated above, CO2 is a substantial input to the claimed method. Advantageously, the inventors have recognized that at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the CO2 in the first feed stream may originate from renewable or otherwise environmentally responsible sources. Thus, as stated above, at least a portion of the CO2 in the first feed stream originates from biogas, CO2 emission sources, and / or direct air capture.

[0031] In some embodiments, at least a portion of the CO2 in the first feed stream originates from biogas. Biogas is produced by the anaerobic digestion of organic matter (e.g., animal manure, food waste, plant matter) by microorganisms and comprises substantial amounts of CO2 and methane. In various embodiments, at least a portion of the CO2 in the first feed stream originates from biogas. In some embodiments as described herein, a majority (i.e., at least 50% by volume) of the CO2 in the first feed stream originates from biogas. In some embodiments as described herein, substantially all (e.g., at least 90% by volume) of the CO2 in the first feed stream originates from biogas. For example, in some embodiments, the CO2 in the first feed stream comprises at least 50% by volume (e.g., at least 75%, at least 90%, or at least 95% by volume) of CO2 derived from biogas.

[0032] In various embodiments, such as when at least a portion of the CO2 in the first feed stream originates from biogas, the methods described herein can operate with a significant amount of unreacted methane. Therefore, in another aspect, this disclosure provides a method comprising providing a first feed stream comprising H2, CO2, and methane, wherein at least a portion of the CO2 in the first feed stream originates from biogas, and wherein at least a portion of the methane in the first feed stream originates from biogas. In some embodiments as described herein, a majority (i.e., at least 50 vol%) of the methane in the first feed stream originates from biogas. In some embodiments as described herein, substantially all (e.g., at least 90 vol%) of the methane in the first feed stream originates from biogas. For example, in some embodiments, the methane in the first feed stream comprises at least 50 vol% (e.g., at least 75 vol%, at least 90 vol%, or at least 95 vol%) of methane originating from biogas.

[0033] As described above, one of the competing reactions in the reverse water-gas shift reaction is the Sabatier reaction, which produces methane. However, the inventors have discovered that by providing methane from biogas to the first feed stream, the equilibrium of the Sabatier reaction is shifted away from the hydrogenation of carbon monoxide. Therefore, without being bound by theory, the inventors hypothesize that a significant amount of methane in the first feed stream can provide improved CO2 conversion in the rWGS process. For example, in various embodiments where the first feed stream contains methane (e.g., from biogas), the first feed stream contains methane in amounts ranging from 10-70 mol%, or 10-50 mol%, or 20-70 mol%, or 20-50 mol%, or 30-70 mol%, or 30-50 mol%.

[0034] In some embodiments described herein, when the first feed stream contains methane from biogas, the molar ratio of H2 to methane in the first feed stream is at least 0.05:1. For example, in various embodiments described herein, the molar ratio of H2 to methane in the first feed stream is at least 0.25:1, or at least 0.5:1, or at least 0.75:1, or at least 1:1, or at least 1.25:1. In some embodiments described herein, the molar ratio of H2 to methane in the first feed stream does not exceed 50:1, for example, not exceeding 40:1, or 25:1. For example, in various embodiments, the molar ratio of H2 to methane in the first feed stream does not exceed 10:1, not exceeding 8:1, or not exceeding 5:1. In some embodiments described herein, the molar ratio of H2 to methane in the first feed stream is in the range of 0.25:1 to 5:1.

[0035] As described herein, the first feed stream may include methane and CO2 from biogas. In some embodiments described herein, the molar ratio of methane to CO2 in the first feed stream is at least 0.25:1, for example, at least 0.3:1, at least 0.4:1, or at least 0.5:1. For example, in various embodiments, the molar ratio of methane to CO2 in the first feed stream is in the range of 0.25:1 to 4:1, in the range of 0.3:1 to 3:1, in the range of 0.4:1 to 2.5:1, or in the range of 0.5:1 to 2:1. In some embodiments described herein, the molar ratio of methane to CO2 in the first feed stream is in the range of 0.8:1 to 1.2:1. For example, in some embodiments, the molar ratio of methane to CO2 in the first feed stream is in the range of 0.85:1 to 1.15:1, or in the range of 0.9:1 to 1.1:1. In some embodiments as described herein, the molar amount of methane in the first feed stream is approximately the same as the molar amount of CO2 in the first feed stream (e.g., in the range of 0.95:1 to 1.05:1).

[0036] As those skilled in the art will understand, biogas comprises a large amount of CO2 and methane, and smaller amounts of water and hydrogen sulfide. Removing water and / or hydrogen sulfide prior to the rWGS process may be advantageous. Therefore, in other embodiments as described herein, providing the first feed stream comprises: providing a biogas stream, separating at least a portion of water from the biogas stream to provide a water-lean biogas stream, and providing the CO2 and methane from the biogas from the water-lean biogas stream. For example, in various embodiments, the method includes separating at least 50%, at least 80%, or at least 90% of the water from the biogas stream to provide a water-lean biogas stream. In other embodiments as described herein, providing the first feed stream comprises providing a biogas stream, separating at least a portion of hydrogen sulfide from the biogas stream to provide a hydrogen sulfide-lean biogas stream, and providing the CO2 and methane from the biogas from the hydrogen sulfide-lean biogas stream. For example, in various embodiments, the method includes separating at least 50%, at least 80%, or at least 90% of the hydrogen sulfide from the biogas stream to provide a hydrogen sulfide-poor biogas stream.

[0037] In other embodiments as described herein, when the first feed stream contains methane from the biogas, the methane in the biogas can be separated before being added to the first feed stream. Therefore, in some embodiments, the method described herein can be operated with a small amount of unreacted methane. For example, in some embodiments further described herein, the first feed stream contains methane in an amount ranging from 0.1 to 10 mol%, or 0.1 to 5 mol%, or 0.1 to 1 mol%.

[0038] In some embodiments, at least a portion of the CO2 in the first feed stream is obtained from direct air capture. Carbon dioxide is a common waste material and is generally desirable to remove from waste streams rather than release into the atmosphere. This capture of carbon dioxide is crucial for the implementation of many renewable measures because it helps reduce the carbon footprint of the relevant methods. Advantageously, the carbon dioxide used in the methods described herein can be carbon dioxide collected from the atmosphere or otherwise released into the atmosphere, for example, from combustion or other industrial methods. Carbon dioxide can be captured, where it is collected or absorbed after being released from an industrial process, or captured directly from the atmosphere. By using captured carbon dioxide, the final hydrocarbon products can be substantially carbon-neutral or have a low carbon intensity. Methods for capturing carbon dioxide are known to those skilled in the art. In various embodiments, at least a portion of the CO2 in the first feed stream is obtained from direct air capture. In some embodiments as described herein, a substantial portion (i.e., at least 50% by volume) of the CO2 in the first feed stream is obtained from direct air capture. In some embodiments as described herein, substantially all (e.g., at least 90% by volume) of the CO2 in the first feed stream is obtained from direct air capture. For example, in some embodiments, the CO2 in the first feed stream contains at least 50% by volume (e.g., at least 75% by volume, at least 90% by volume, or at least 95% by volume) of CO2 from direct air capture.

[0039] In some embodiments, at least a portion of the CO2 in the first feed stream originates from a CO2 emission source. Carbon dioxide is frequently scrubbed from industrial effluents, particularly in methods that produce large amounts of carbon dioxide as a byproduct. As used herein, such a source of carbon dioxide byproducts from industrial processes is referred to as a CO2 emission source. Therefore, in the various embodiments described herein, at least a portion of the CO2 in the first feed stream originates from a CO2 emission source. In some embodiments described herein, a majority (i.e., at least 50% by volume) of the CO2 in the first feed stream originates from a CO2 emission source. In some embodiments described herein, substantially all (e.g., at least 90% by volume) of the CO2 in the first feed stream originates from a CO2 emission source. For example, in some embodiments, the CO2 in the first feed stream comprises at least 50% by volume (e.g., at least 75%, at least 90%, or at least 95% by volume) of CO2 from a CO2 emission source. This CO2 emission source is not particularly limited and can be derived from any industrial production known in the art. For example, in some embodiments as described herein, the CO2 emission source is a manufacturing plant, a bioethanol plant, a CO2-producing fermentation plant, a steel plant, or a cement plant. Therefore, in various other embodiments as described herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the CO2 in the first feed stream is captured from the manufacturing plant, such as a bioethanol plant (e.g., a CO2-producing fermentation plant), a steel plant, or a cement plant. In some embodiments as described herein, the CO2 emission source is a point source from fermentation, manufacturing, or other industrial methods. This point source can be a chimney or exhaust vent or other forms of structure known in the art for containing and / or transporting CO2.

[0040] Therefore, the rWGS-Fischer-Tropsch integrated method of this disclosure, as described herein, can not only be carbon neutral but, in some cases, a net consumer of carbon dioxide. These benefits make this integrated method particularly attractive for decarbonizing transportation fuels in both the automotive and aviation sectors, as the carbon monoxide produced in the rWGS reaction can be readily utilized by well-established technologies to synthesize liquid hydrocarbon fuels via the Fischer-Tropsch process.

[0041] As described above, the first feed stream contains H2 and CO2 (e.g., provided to the reaction zone in a single physical stream or multiple physical streams). In various embodiments as further described herein, 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. In some embodiments, the molar ratio of H2 to CO2 in the first feed stream is at least 0.9:1, for example, at least 1:1 or at least 1.5:1. In some embodiments, the molar ratio of H2 to CO2 in the first 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 first feed stream does not exceed 100:1, for example, not more than 75:1 or not more than 50:1. In some embodiments, the molar ratio of H2 to CO2 in the first feed stream does not exceed 20:1, for example, not more than 15:1 or not more than 10:1. For example, in some embodiments, the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:1. Based on the disclosure herein, those skilled in the art will provide a desired H2:CO2 ratio in the first feed stream that provides desirable conversion and selectivity; if consistent with desirable conversion and selectivity, excess H2 can be provided to flow through the system, providing a first product stream with a desirable H2 to CO ratio for downstream processes (e.g., Fischer-Tropsch process).

[0042] Other gases may also be included in the first feed stream. For example, in some embodiments, the first feed stream further comprises CO. In various embodiments described herein, the first feed stream comprises no more than 20 mol%, no more than 10 mol%, or no more than 5 mol%, or no more than 3 mol%, or no more than 1 mol% CO. In some embodiments of this disclosure as further described herein, the first feed stream further comprises one or more inert gases. For example, in some embodiments, the first feed stream further comprises nitrogen and / or methane. In various embodiments described herein, the first feed stream comprises no more than 10 mol%, no more than 6 mol%, or no more than 2 mol% nitrogen. In various embodiments described herein, the gases in the first feed stream may be separated to provide the amounts of carbon dioxide, methane, and / or nitrogen as described herein. For example, in some embodiments as described herein, methane is separated from the first feed stream to provide a first feed stream containing at least 50 mol% carbon dioxide (e.g., at least 60 mol% carbon dioxide, at least 70 mol% carbon dioxide, at least 80 mol% carbon dioxide, or at least 90 mol% carbon dioxide).

[0043] The methods described herein include contacting the rWGS catalyst with a first feed stream to carry out an rWGS reaction. It is noteworthy that the inventors have determined that the rWGS catalyst described herein can provide desirablely high CO selectivity. For example, in various embodiments of this disclosure as described herein, the reverse water-gas shift reaction has a CO selectivity of at least 70%, for example, at least 80%. In various embodiments, the reverse water-gas shift reaction has a CO selectivity of at least 85%, for example, or at least 90%. In various embodiments, the reverse water-gas shift reaction has a CO selectivity of at least 95%, for example, or at least 96%. As used herein, “selectivity” for a given reaction product is the mole fraction of the relevant component of the feed (here, CO2) that is converted to the product (CO for “CO selectivity”). The inventors have determined that the rWGS catalyst of the present invention, as described herein, can provide excellent CO selectivity even when operated at temperatures lower than many conventional reverse water-gas shift catalysts, despite the competing possibilities of the Sabatier reaction and CO methanation. For example, in some embodiments as described separately herein, the reverse water-gas shift reaction has at least 98%, for example, or at least 99% CO selectivity.

[0044] It is noteworthy that even over a wide temperature range, such as 200–1100 °C, the rWGS catalyst described herein can be operated to provide carbon monoxide with only a very small degree of methane formation. For example, in various embodiments of this disclosure as described herein, the reverse water-gas shift reaction has a methane selectivity of no more than 5%, for example, no more than 4%. For example, in some embodiments, the reverse water-gas shift reaction has a methane selectivity of no more than 2%, for example, no more than 1%. In some embodiments, the reverse water-gas shift reaction has a methane selectivity of no more than 0.5%, for example, no more than 0.2%.

[0045] The inventors have determined that the rWGS catalyst described herein can provide desirable high CO selectivity and desirable low methane selectivity at commercially relevant conversion rates. As used herein, “conversion rate” is the mole fraction of the relevant component feed (whether desirable product or undesirable species). In various embodiments of this disclosure as described herein, the reverse-flow gas shift reaction has a CO2 conversion rate of at least 5%, for example at least 10%, or at least 20%. For example, in some embodiments, the reverse-flow gas shift reaction has a CO2 conversion rate of at least 30%, for example at least 40%, or at least 50%, or at least 60%. In various embodiments of this disclosure as described herein, the reverse-flow gas shift reaction has a CO2 conversion rate of no more than 90%, for example no more than 80%, or no more than 70%. For example, in some embodiments, the reverse-flow gas shift reaction has a CO2 conversion rate of no more than 65%, for example no more than 60%. For example, in various embodiments as described separately herein, the CO2 conversion rate is in the range of 10-90%, such as 10-80%, or 10-70%, or 10-60%, or 10-65%, or 20-90%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30-90%, or 30-80%, or 30-70%, or 30-60%, or 30-65%, or 40-90%, or 40-80%, or 40-70%, or 40-60%, or 40-65%. Based on the disclosure herein, those skilled in the art will operate with the conversion level that provides the desired product. And of course, in other embodiments, such as when in a stacked bed or mixed bed system, the effective CO2 conversion rate can be even higher than that described herein.

[0046] Advantageously, the rWGS method described herein can be carried out at temperatures lower than those used in many conventional reverse water gas shift (RWS) methods. As mentioned above, the various methods of carrying out the rWGS reaction disclosed herein can be carried out at a first temperature in the range of 200-1100°C. For example, in some embodiments, the RWS reaction is carried out at a first temperature in the range of 200-1050°C, for example, in the ranges of 200-1000°C, or 200-950°C, or 200-900°C, or 200-850°C, or 200-800°C, or 200-750°C, or 200-700°C, or 200-650°C, or 200-600°C. In some embodiments of this disclosure as described herein, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 250-1100°C, for example, in the range of 250-1050°C, or 250-1000°C, or 250-950°C, or 250-900°C, or 250-850°C, or 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C. In some embodiments of this disclosure as described herein, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 300-1100°C, for example, in the range of 300-1050°C, or 300-1000°C, or 300-950°C, or 300-900°C, or 300-850°C, or 300-800°C, or 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C. In some embodiments of this disclosure as described herein, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 350-1100°C, for example, in the range of 350-1050°C, or 350-1000°C, or 350-950°C, or 350-900°C, or 350-850°C, or 350-800°C, or 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 400-1100°C, for example, in the range of 400-1050°C, or 400-1000°C, or 400-950°C, or 400-900°C, or 400-850°C, or 400-800°C, or 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 450-1100°C, for example, in the range of 450-1050°C, or 450-1000°C, or 450-950°C, or 450-900°C, or 450-850°C, or 450-800°C, or 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 500-1100°C, for example, in the range of 500-1050°C, or 500-1000°C, or 500-950°C, or 500-900°C, or 500-850°C, or 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 550-1100°C, for example, in the range of 550-1050°C, or 550-1000°C, or 550-950°C, or 550-900°C, or 550-850°C, or 550-800°C, or 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 600-1100°C, for example, in the range of 600-1050°C, or 600-1000°C, or 600-950°C, or 600-900°C, or 600-850°C, or 600-800°C, or 600-750°C, or 600-700°C, or 600-650°C. In some embodiments, the method for carrying out the reverse water-gas shift reaction is performed at a first temperature in the range of 700-1100°C, for example, in the range of 700-1050°C, or 700-1000°C, or 700-950°C, or 700-900°C, or 700-850°C, or 700-800°C, or 700-750°C.

[0047] In some embodiments, the reverse water-gas shift reaction is carried out at a first temperature within the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-350°C. The inventors have noted that operation at these temperatures provides lower energy requirements and facilitates easy integration with subsequent Fischer-Tropsch steps.

[0048] Furthermore, as those skilled in the art will understand, the rWGS method described herein can be carried out at a variety of pressures. In various embodiments of this disclosure, the method for performing the reverse water-gas shift reaction is carried out at a first pressure in the range of 1 to 100 barg. For example, the rWGS method is carried out at a first pressure in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 70 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg.

[0049] As will be understood by those skilled in the art, the rWGS method described herein can be carried out at various GHSVs (gas hourly space velocities). Therefore, there is no particular limitation on the GHSV used for the reverse water-gas shift reaction. For example, in some embodiments of this disclosure, the method for carrying out the reverse water-gas shift reaction is performed at 1,000 to 2,000,000 h⁻¹. -1 The reaction is carried out under GHSV conditions ranging from 1,000 to 1,200,000 h⁻¹. In various embodiments, the method for performing the reverse water-gas shift reaction is carried out at GHSV conditions ranging from 1,000 to 1,200,000 h⁻¹. -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000 h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The process is carried out under GHSV conditions ranging from 1,000 to 50,000 h⁻¹. In various embodiments of this disclosure, the method for carrying out the reverse water-gas shift reaction is performed under GHSV conditions ranging from 1,000 to 50,000 h⁻¹. -1 Or 2,000 to 50,000 h -1 Or 5,000 to 50,000 h -1 Or 10,000 to 50,000 h -1 Or 1,000 to 40,000 h -1 Or 2,000 to 40,000 h-1 Or 5,000 to 40,000 h -1 Or 10,000 to 40,000 h -1 Or 1,000 to 30,000 h -1 Or 2,000 to 30,000 h -1 Or 5,000 to 30,000 hours -1 Or 10,000 to 30,000 h -1 Performed within the range of GHSV.

[0050] It is generally desirable, for example, to activate the rWGS catalyst before contacting it with a first feed stream. Thus, in some embodiments of this disclosure as described herein, the method includes activating the rWGS catalyst before contacting it with the feed stream. For example, in some embodiments, activating the catalyst includes contacting the catalyst with a reducing feed stream containing a reducing gas (e.g., hydrogen). In various embodiments of this disclosure, the reducing feed stream contains hydrogen in an amount of at least 25 mol%, for example, at least 50 mol%, or 75 mol%, or 90 mol%. Those skilled in the art will determine the conditions suitable for the reduction activation of the rWGS catalyst. Therefore, those skilled in the art will be able to select appropriate temperature, pressure, and time for activating the rWGS catalyst. For example, in various embodiments, the activation of the rWGS catalyst is carried out at a temperature in the range of 200°C to 1000°C. For example, in various embodiments, the activation of the rWGS catalyst is carried out at temperatures ranging from 250°C to 1000°C, or 300°C to 1000°C, or 200°C to 900°C, or 250°C to 900°C, or 300°C to 900°C, or 200°C to 800°C, or 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C. In some embodiments of this disclosure as described herein, the activation of the rWGS catalyst provides at least 10% reduced (e.g., at least 25%, or at least 50% reduced) of the rWGS catalyst.

[0051] The inventors have discovered that contacting an rWGS catalyst, as described herein, with a first feed stream can provide a first product stream with advantageously high CO selectivity and low methane selectivity. As mentioned above, the amount of CO in the first product stream can be further controlled by the rWGS reaction conditions. However, typically, the methods for carrying out rWGS reactions as described herein provide a first product stream comprising H2 and CO, wherein the first product stream has a lower concentration of CO2 and a higher concentration of CO than the first feed stream, consistent with the conversion and selectivity levels described herein. For example, in various embodiments, the first product stream comprises no more than 95 mol% CO2 or no more than 90 mol% CO2. In some embodiments, the first product stream comprises no more than 85 mol% CO2 or no more than 80 mol% CO2. In other examples, the first product stream comprises no more than 75 mol% or no more than 70 mol% CO2.

[0052] However, as stated above, the inventors have determined that conducting the method at an intermediate level of conversion to provide desirable high CO selectivity and desirable low methane selectivity may be desirable. Furthermore, the inventors have noted that downstream Fischer-Tropsch processes with relatively high levels of inert matter may be advantageous, and thus envision that feeding a significant amount of CO2 into the Fischer-Tropsch steps may be beneficial. Therefore, in various embodiments as further described herein, the first product stream comprises a certain amount of CO2 as well as CO. In various embodiments, the first product stream contains CO2 in the range of 5-95 mol% CO2, for example 5-90 mol%, or 5-85 mol%, or 5-80 mol%, or 5-75 mol%, or 5-70 mol%, or 10-95 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol%.

[0053] The first product stream may also include other gases. In some embodiments of this disclosure, as described separately herein, the first product stream further includes one or more inert gases. These inert gases may be included in the first feed stream or provided from sources other than the first feed stream. For example, in some embodiments, the first product stream further includes nitrogen and / or methane.

[0054] Depending on the degree of conversion, CO selectivity, the relative amounts of H2 and CO2 in the first feed stream, and the reaction conditions, the first product stream may include H2 combined with CO in various ratios. For example, in some embodiments, the H2:CO ratio in the first product stream is in the range of 0.1:1 to 100:1 (e.g., in the ranges of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0055] Those skilled in the art will understand that, based on the methods described herein, the first product stream may include H2, CO, and CO2, as well as various amounts of other components. The components of the first product stream can be separated and used for various purposes in the integrated method.

[0056] For example, in various embodiments of this disclosure as described herein, the method further includes separating a first product stream to recycle at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of one or more components of the first product stream to a first feed stream. For example, when the first product stream comprises CO2, the method may include recycling at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the CO2 in the first product stream to the first feed stream. The first product stream may also comprise H2; in some embodiments, the method further includes recycling at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the H2 in the first product stream to the first feed stream.

[0057] Such recycles are displayed Figure 1 In method 100, at least a portion of CO2 (stream 114) is separated from the first product stream 112 for recycling to the first feed stream 111. Similarly, method 100 includes separating at least a portion of H2 (stream 115) from the first product stream 112 for recycling to the first product stream 111. Although stream 115 is depicted as entering reactor 110 through an inlet different from the remainder of the first feed stream 111, it is considered part of the first feed stream because it is part of the material input to the method steps.

[0058] Furthermore, as described below, Fischer-Tropsch catalysts typically require activation with a reducing gas. As those skilled in the art will understand, different Fischer-Tropsch catalysts require different activation conditions (e.g., gas composition, temperature, pressure, time). For example, iron-based Fischer-Tropsch catalysts require activation with H2 and CO, while cobalt-based Fischer-Tropsch catalysts require activation with only H2. Therefore, H2 and CO, or only H2, from the first product stream can be used for this activation. Thus, in various embodiments as separately described herein, the method includes separating at least a portion of H2 and CO (desirably in a ratio of at least 1:1 or at least 3:1) from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. In various other embodiments as separately described herein, the method includes separating at least a portion of H2 from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. For example, in… Figure 1 In this method, feed stream 125 separates H2 or H2 with CO and directs it to reactor 120. This separation does not need to be continuous; rather, it only needs to take place for a period of time to provide the Fischer-Tropsch catalyst with reducing gas for activation. Of course, as those skilled in the art will understand, other sources of H2 or CO can be used to provide the Fischer-Tropsch catalyst with reducing gas for activation.

[0059] As shown above, water is a product of the reverse water-gas shift reaction. Therefore, the first product stream will typically contain water. In many cases, it may be desirable to reduce the amount of water supplied to the Fischer-Tropsch process step. Therefore, in various embodiments as described separately herein, the method further includes removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream. Figure 1 In one embodiment, dewatering zone 116 is used to remove water and provide a water-containing feed stream 117. Those skilled in the art will understand that various methods can be used to remove water from the first product stream. For example, the first product stream can be contacted with a dewatering agent to remove water therefrom. For example, a molecular sieve guard bed can be used to remove water from the first product stream; water can be recovered from the molecular sieve in the guard bed, for example, by heating and vacuum. In other embodiments, a knockout vessel can be used. However, using a knockout vessel in some cases allows for sufficient cooling of the first product stream, making it desirable for reheating for introduction into the Fischer-Tropsch process.

[0060] As described above, a competing reaction in the countercurrent water-gas shift reaction is the Sabatier reaction, which produces methane. While the countercurrent water-gas shift method described herein can be carried out without the formation of significant amounts of methane in various embodiments, some methane may be formed in some embodiments. Therefore, in various embodiments of the method described herein, the first product stream comprises one or more light hydrocarbons. For example, in some embodiments, the first product stream may comprise one or more of methane, ethane, propane, or combinations thereof. When the first product stream contains methane, a significant portion of this methane may originate from biogas supplied to the first feed stream (e.g., at least 50%, at least 75%, or at least 90%). As those skilled in the art will understand, it may be desirable to operate the countercurrent water-gas shift reaction to provide a higher amount of light hydrocarbons in the first product feed. For example, such light hydrocarbons may be inert in further processing of the first product stream and are therefore acceptable at higher amounts, particularly when biogas is used in the first feed stream. Those skilled in the art will be able to select suitable reaction conditions (e.g., temperature, pressure, first feed stream composition) to provide a first product stream containing a desired amount of methane. For example, in various embodiments further described herein, the first product stream contains methane in the range of 10-70 mol%, or 50 mol%, or 20-70 mol%, or 20-50 mol%, or 30-70 mol%, or 30-50 mol%. In various other embodiments further described herein, the first product stream contains no more than 20 mol% methane or no more than 15 mol%. As mentioned above, the rWGS catalyst of this disclosure can provide very low methane selectivity when a low amount of methane is desired in the first product stream. Furthermore, when biogas is present in the first feed stream, methane can be separated before contact with the reverse water gas shift catalyst to provide a first feed stream and a first product stream with low amounts of methane. Thus, in various embodiments further described herein, the first product stream contains no more than 10 mol% methane. For example, in various embodiments, the first product stream contains no more than 5 mol%, or no more than 1 mol%, or no more than 0.5 mol%, or no more than 0.1 mol% of methane. Typically, light hydrocarbons (e.g., C1-C5 hydrocarbons) may be present in the product stream. For example, in various embodiments as further described herein, the product stream contains no more than 20 mol% of light hydrocarbons (e.g., no more than 15 mol%, no more than 10 mol%, no more than 5 mol%, no more than 1 mol%, no more than 0.5 mol%, or no more than 0.1 mol% of light hydrocarbons).

[0061] These light hydrocarbons (e.g., C1-C5 hydrocarbons) can be separated and used for other purposes. For example, in various embodiments, the method further includes separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream. For example, in Figure 1 In method 100, at least a portion of one or more light hydrocarbons is separated from a first product stream 112 to provide a light hydrocarbon stream 118. The light hydrocarbon stream may, for example, be used to provide other products, may be partially oxidized to form CO, may be steam-reformed to provide hydrogen, and / or may be combusted to provide heat or other energy (e.g., electricity for electrolysis) for use in the integration method or other methods. In some embodiments as described herein, the light hydrocarbon stream contains methane from biogas, which may be combusted to provide energy (e.g., thermal or electrical energy) for use in the integration method (e.g., for heating the first feed stream).

[0062] Of course, as those skilled in the art will understand, light hydrocarbon feed streams can also be used in other processes. For example, as those skilled in the art will understand, some rWGS catalysts can have reforming capabilities. Without being bound by theory, the inventors hypothesize that one explanation for the low methane yield observed using the rWGS catalysts described herein is the formation of methane, which is then immediately reformed into CO and H2. Therefore, in some embodiments as described herein, the light hydrocarbons of the process feed stream are recycled to the feed stream used for the rWGS reaction.

[0063] As described above, the reverse-flow gas shift method can be provided at a variety of temperatures. In some cases, these temperatures can be relatively close to the temperatures of subsequent Fischer-Tropsch steps (typically 150-400°C, e.g., 200-350°C, or other temperatures as described below). In other cases, the reverse-flow gas shift method can be carried out at temperatures significantly higher than the Fischer-Tropsch step temperatures. The inventors have noted that it may be desirable to provide heat exchange with the relatively hot first product stream to cool the first product stream to a temperature more suitable for the Fischer-Tropsch step and, in other ways, to provide heat to the integrated method. For example, in various embodiments of the method as separately described herein, the method further includes exchanging heat between at least a portion of the first product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the first product stream and heating at least a portion of the first feed stream. Figure 2 The diagram illustrates an instance of such a method. Figure 2In this embodiment, method 200, first reactor 210, first feed stream 211, first product stream 212, reverse water-gas shift catalyst 213, second reactor 220, second feed stream 221, second product stream 222, and Fischer-Tropsch catalyst 223 are generally as described above. Here, method 200 includes exchanging heat between at least a portion of the first product stream 212 and at least a portion of the first feed stream 211 in a first heat exchange zone 230, thereby cooling at least a portion of the first product stream 212 and heating at least a portion of the first feed stream 211. Those skilled in the art will understand that various heat exchangers can be used for this purpose.

[0064] Of course, any excess heat in the first product stream can be used additionally or alternatively for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the first product stream and the steam generation zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generation zone. This shows Figure 2 In this context, after heat exchange with the first feed stream 211, the first product stream 212 is guided to the steam generation zone 232 to cool the first product stream 212 and provide heat to the steam generation zone 232. Steam can be generated from the provided heat, and electricity can be generated from the steam. For example, in... Figure 2 In one embodiment, current 264 is provided by generating electricity using steam produced in steam generation zone 232. Of course, as those skilled in the art will understand, the steam produced in the steam generation zone can be used for other processes. In various embodiments, the steam can be used to heat the first feed stream. For example, in… Figure 2 In one implementation, the steam stream 266 generated in the steam generation zone 232 is guided to the heat exchange zone 290 to heat the first feed stream 211.

[0065] As described above, at least a portion of the CO in the first product stream is included in the second feed stream for the reaction in the Fischer-Tropsch process. For example, in various embodiments as further described herein, at least 25% of the CO in the first product stream, such as at least 50%, at least 75%, or at least 90% of the CO in the first product stream, is included in the second feed stream. Of course, as described above, some of the CO in the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0066] In some embodiments, substantially all CO in the second feed stream originates from the first product stream. However, in other embodiments, CO may be supplied to the second feed stream from other sources. For example, in various embodiments, CO is supplied to the second feed stream from a CO source other than the first product stream. Figure 2In this process, CO stream 226a from several other sources is included in the second feed stream 221. Those skilled in the art will understand that CO can be provided from various sources, such as gasification, reforming, or electrochemical CO2 reduction. Furthermore, as described in more detail below, CO can be recycled from the second product stream to the second feed stream.

[0067] As described above, the second feed stream comprises H2. It is noteworthy that the first product stream will typically comprise H2, such as unreacted H2 from the first feed stream. In various embodiments, the first product stream comprises H2, wherein the second feed stream comprises at least a portion of the H2 from the first product stream. For example, in various embodiments as further described herein, at least 25%, such as at least 50%, at least 75%, or at least 90%, of the H2 from the first product stream is included in the second feed stream. Of course, as described above, some of the H2 from the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0068] In some embodiments, substantially all the H2 in the second feed stream originates from the first product stream. In fact, those skilled in the art can provide more H2 in the first feed stream than is required for the reverse water-gas shift reaction, thus providing an excess of H2 in the first product stream, which can then be supplied to the second feed stream in the required amount for the Fischer-Tropsch step. However, in other embodiments, H2 can be supplied to the second feed stream from other sources. For example, in various embodiments, H2 is supplied to the second feed stream from sources other than the first product stream. Figure 2 In this process, H2 stream 226b from several other sources is included in the second feed stream 221. Those skilled in the art will understand that H2 can be supplied from various sources, such as gasification, reforming, or H2O electrolysis. Furthermore, as described in more detail below, H2 can be recycled from the second product stream to the second feed stream.

[0069] As described above, it may be desirable to perform the Fischer-Tropsch process in the presence of a significant level of inert material. One such inert material, CO2, may be derived from the counter-water gas shift reaction, for example via the first product stream. Thus, in various embodiments as described separately herein, the second feed stream comprises at least a portion of the CO2 from the first product stream. For example, in various embodiments, at least 10%, such as at least 25%, at least 50%, at least 75%, or at least 90%, of the CO2 from the first product stream is included in the second feed stream. Of course, in other embodiments, the second feed stream may not contain any significant amount of CO2 from the first product stream. Thus, in various embodiments, the second feed stream does not contain a significant amount of CO2 from the first product stream. While it may generally be desirable to recycle CO2 to the first feed stream for use in the counter-water gas shift reaction, unreacted CO2 can be recycled from the second product stream to the first feed stream, as described in more detail below.

[0070] However, additionally or alternatively, it may be desirable to include an additional inert content in the second feed stream, whether it be CO2 or other inert substances such as nitrogen and methane. For example, in various embodiments, one or more inert substances (e.g., CO2, nitrogen, and / or methane) are supplied to the second feed stream from a source other than the first product stream. Figure 2 In the second feed stream 221, there is an inert material stream 226c from one or more other sources. Those skilled in the art will understand that inert materials can be provided from a variety of sources. Furthermore, as described in more detail below, the inert material can be recycled from the second product stream to the second feed stream.

[0071] As mentioned above, it may be desirable to carry out the Fischer-Tropsch process in the presence of an inert substance. Therefore, in various embodiments as described separately herein, a portion of the first product stream contained in the second feed stream has a CO2 content in the range of 10-95 mol%, for example 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol%.

[0072] As mentioned above, other gases may also be included in the second feed stream. For example, as mentioned above, it may be desirable to carry out the Fischer-Tropsch process in the presence of a significant amount of inert material (i.e., a component that is not H2 or CO). For example, in various embodiments, the second feed stream contains up to 80 mol% of one or more inert materials, such as in the range of 3-80 mol%, or 5-80 mol%, or 10-80 mol%, or 15-80 mol%, or 30-80 mol%. In various embodiments, the second feed stream contains up to 70 mol% inert material, up to 60 mol% inert material, or up to 50 mol% inert material, for example, 3-70 mol%, or 5-70 mol%, or 10-70 mol%, or 15-70 mol%, or 30-70 mol%, or 3-60 mol%, or 5-60 mol%, or 10-60 mol%, or 15-60 mol%, or 30-60 mol%, or 3-50 mol%, or 5-50 mol%, or 10-50 mol%, or 15-50 mol%, or 30-50 mol% inert material. In various embodiments, the second feed stream contains up to 80% of one or more inert materials selected from CO2, methane, and nitrogen, such as up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%. In various embodiments, the second feed stream contains up to 80 mol% CO2, such as up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%.

[0073] Those skilled in the art can adjust the portion of the first product stream contained in the second feed stream to provide a desirable H2:CO ratio. For example, in various embodiments, the portion of the first product stream contained in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 10:1, such as in the range of 1:1 to 2.5:1. Of course, regardless of the H2:CO ratio of the portion of the first product stream contained in the second feed stream, those skilled in the art can add H2 or CO as needed as described above to provide the desired overall ratio in the second feed stream.

[0074] As described above, the second feed stream contains both H2 and CO, and the second feed stream includes all the feed to the Fischer-Tropsch reactor, whether the second feed stream is provided as a mixture of feeds or as a separate feed to the reaction zone. In various embodiments of this disclosure as described herein, the second feed stream has an H2:CO ratio in the range of 0.5:1 to 6:1. In some embodiments, the second feed stream has an H2:CO ratio in the range of 1:1 to 3:1, or 1:1 to 2.5:1. In some embodiments, the second feed stream has an H2:CO ratio of at least 1.4:1. For example, in some embodiments, the second feed stream has an H2:CO ratio in the range of 1.4:1 to 3:1, or 1.4:1 to 2:1. Based on the disclosure herein, those skilled in the art will provide desirable H2:CO ratios in the second feed stream that provide desirable conversion and selectivity in the Fischer-Tropsch process.

[0075] As mentioned above, it may be desirable to reduce the amount of water introduced into the Fischer-Tropsch process step. Therefore, in various embodiments as described separately herein, the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 0.5 mol%.

[0076] As mentioned above, it may be desirable to carry out the Fischer-Tropsch process in the presence of a relatively small amount of water. Therefore, in various embodiments, the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 0.5 mol%.

[0077] The method described herein involves contacting a Fischer-Tropsch catalyst with a second feed stream as described herein. There are no particular limitations on the Fischer-Tropsch catalyst used in the method described herein, and those skilled in the art will be able to select a catalyst suitable for their desired Fischer-Tropsch product. In some embodiments, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or combinations thereof.

[0078] For example, in some embodiments of this disclosure as described herein, the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount ranging from 5 to 25 wt% as Co(O). The terms “as Co(O)” and similar terms refer to the weight of the cobalt atoms / ions themselves used in the calculation, rather than the total amount of any compounds or polynuclear ions in which those cobalt atoms / ions may be bound. For example, in various embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount ranging from 7 to 25 wt%, or 10 to 25 wt%, or 5 to 20 wt%, or 7 to 20 wt%, or 10 to 20 wt% as Co(O). As will be understood by those skilled in the art, cobalt-based catalysts are typically provided to the reaction zone in the form of cobalt oxide on a support; cobalt can be in-situ reduced and activated (e.g., with H2) to provide an active catalyst species with a significant concentration of Co(O).

[0079] In some embodiments, the Fischer-Tropsch catalyst comprises iron, for example, in an amount ranging from 5 to 95 wt% as Fe(O). For instance, in various embodiments, the Fischer-Tropsch catalyst comprises iron 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%. As will be understood by those skilled in the art, iron-based catalysts are typically provided to the reaction zone in the form of metallic iron or iron oxide optionally on a support; the iron can be activated (e.g., by reaction with H2 and CO) to provide an active catalyst species with a significant concentration of iron carbide.

[0080] In various embodiments of this disclosure as described herein, particularly when the catalyst is a cobalt-based catalyst, the Fischer-Tropsch catalyst further comprises manganese. For example, in various embodiments, the Fischer-Tropsch catalyst contains manganese in an amount of up to 15% by weight, such as up to 12% by weight, or up to 10% by weight, or up to 7% by weight, calculated as Mn(0). In some such embodiments, the catalyst material contains manganese in an amount ranging from 0.1 to 15% by weight, such as 0.1 to 10% by weight, or 0.1 to 5% by weight, 0.5 to 15% by weight, or 0.5 to 10% by weight, or 0.5 to 5% by weight, calculated as Mn(0). Of course, in other embodiments, manganese is substantially absent (e.g., less than 0.1% by weight or less than 0.5% by weight).

[0081] The Fischer-Tropsch catalyst suitable for the methods described herein can be of various forms and is not particularly limited. For example, the Fischer-Tropsch catalyst can be a supported or unsupported catalyst. While the form of the catalyst is not particularly limited, in various desirable embodiments, the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, alumina, silica, and zinc oxide. For example, in various embodiments, the support comprises at least one of titanium oxide, alumina, and silica. In some embodiments of this disclosure as described herein, the support is a titanium dioxide support.

[0082] Those skilled in the art will understand that the Fischer-Tropsch catalysts of this disclosure can be provided in many forms, particularly depending on the specific form of the reactor system in which they are to be used, such as in a fixed bed or as a fluidized bed. The support for the Fischer-Tropsch catalyst itself can be provided as a discrete body of material, for example as porous particles, pellets, or shaped extrusions, with a metal provided thereon to provide the Fischer-Tropsch catalyst. However, in other embodiments, the Fischer-Tropsch catalyst of this disclosure can itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It can be formed of, for example, a metal or a metal oxide, and can itself be provided in a variety of forms, such as particles, pellets, shaped extrusions, or bulk materials. Those skilled in the art will select a suitable Fischer-Tropsch catalyst for a particular reactor system.

[0083] Similar to rWGS catalysts, Fischer-Tropsch catalysts are typically activated before use to, for example, provide cobalt(O) species on cobalt-based catalysts or iron carbide species on iron-based catalysts. Such activation can take place before the Fischer-Tropsch catalyst comes into contact with the second feed stream.

[0084] For example, in some embodiments, the Fischer-Tropsch catalyst is activated by contacting it with a reducing gas. Hydrogen, for example, can be a gas particularly suitable for activating Fischer-Tropsch catalysts, such as when activation is a reduction to a metal (O) species, as is the case for many cobalt-based catalysts. In various embodiments of this disclosure as described separately herein, the reducing gas comprises at least a portion of H2 from the first product stream. For example, in some embodiments, the method further comprises separating at least a portion of the H2 from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. Figure 1 In the schematically illustrated method 100, at least a portion of the hydrogen stream 125 is separated from the first product stream 112 and contacted with the Fischer-Tropsch catalyst 123 to activate it. In other embodiments, H2 present in the second feed stream can be used to activate the catalyst. As those skilled in the art will understand, the activation temperature can vary depending on the Fischer-Tropsch catalyst used. Therefore, those skilled in the art will be able to select an appropriate temperature for activating the catalyst, for example, in the range of 200-400°C.

[0085] In various embodiments, the Fischer-Tropsch catalyst is activated by contacting it with H2 and CO. This may be particularly suitable when activation provides a conversion to carbides, for example, for many iron-based catalysts. In various embodiments of this disclosure, as described separately herein, the reducing gas comprises at least a portion of H2 and CO from the first product stream. For example, in some embodiments, the method further includes separating at least a portion of the H2 and at least a portion of the CO from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the catalyst. Figure 2 In the schematically illustrated method 200, at least a portion of the H2 and CO stream 227 is separated from the first product stream 212 and contacted with the Fischer-Tropsch catalyst 223 to activate it. In other embodiments, H2 and CO present in the second feed stream can be used to activate the catalyst. The activation temperature can vary, for example, in the range of 200-400°C.

[0086] As described above, the method involves contacting a Fischer-Tropsch catalyst with a second feed stream at a second temperature and a second pressure. Those skilled in the art will select appropriate reaction conditions by combining the specific feed and catalyst used to provide the desired Fischer-Tropsch process. In some embodiments of this disclosure as described herein, the second temperature is in the range of 150-400°C. For example, in various embodiments, the second temperature is in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C. In some specific embodiments, the second temperature is in the range of 200-350°C.

[0087] It is worth noting that in many embodiments, the first temperature and the second temperature can be relatively close to each other. The inventors have noted that the reverse water-gas shift catalyst described herein can provide suitable activity and CO selectivity even at relatively low temperatures. Therefore, the first product stream can be provided with a temperature suitable for or at least close to that suitable for the Fischer-Tropsch reaction step. This can desirablely provide improved method 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.

[0088] However, in other embodiments, the first and second temperatures are not very close to each other. The inventors have noted that in many cases, the desired reverse water-gas shift process temperature will be significantly higher than the desired Fischer-Tropsch process temperature. For example, in various embodiments, the first temperature is at least 100°C higher than the second temperature, such as at least 150°C or at least 200°C higher. The excess heat in the first product stream can be used for various purposes, such as preheating at least a portion of the first feed stream or generating steam for power generation, as described above.

[0089] In some embodiments of this disclosure as described herein, the second pressure is in the range of 10-50 barg. For example, in various embodiments, the second pressure is in the range of 20-50 barg, or 25-50 barg, or 10-40 barg, or 20-40 barg, or 25-40 barg, or 10-35 barg, or 20-35 barg, or 25-35 barg. In some embodiments, the second pressure is in the range of 20-50 barg.

[0090] As will be understood by those skilled in the art, the Fischer-Tropsch process described herein can be carried out at a variety of GHSV (gas hourly space velocity) values. Therefore, there is no particular limitation on the GHSV at which the Fischer-Tropsch reaction takes place. For example, in some embodiments of this disclosure, the Fischer-Tropsch reaction is carried out at 1,000 to 2,000,000 h⁻¹. -1 The process is carried out under GHSV within a certain range. In various implementation schemes, the reverse water-gas shift reaction is carried out over a period of 1,000 to 1,200,000 h. -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The process is carried out under GHSV conditions ranging from 1,000 to 50,000 h. In various embodiments of this disclosure, the Fischer-Tropsch reaction is performed over a period of 1,000 to 50,000 h. -1 Or 2,000 to 50,000 h -1 Or 5,000 to 50,000 h -1 Or 10,000 to 50,000 h -1Or 1,000 to 40,000 h -1 Or 2,000 to 40,000 h -1 Or 5,000 to 40,000 h -1 Or 10,000 to 40,000 h -1 Or 1,000 to 30,000 h -1 Or 2,000 to 30,000 h -1 Or 5,000 to 30,000 h -1 Or 10,000 to 30,000 h -1 Performed under the range of GHSV.

[0091] The Fischer-Tropsch process is commonly used to prepare C 5+ Hydrocarbons, such as unsubstituted C 5+ Hydrocarbons (such as alkanes and alkenes) and oxygenated C 5+ Hydrocarbons (e.g., C) 5+ (Alcohols, aldehydes, ketones, carboxylic acids). In various embodiments of this disclosure as described herein, the Fischer-Tropsch catalyst is contacted with a second feed stream to provide a second product stream with at least 30%, for example at least 50%, or at least 70% C. 5+ Selectivity (i.e., for all C) 5+ (Species). For example, in some implementations, C 5+ The selectivity for alkanes is at least 30%, for example at least 50%, or at least 70%. In some embodiments, the selectivity for C... 5+ Alkanes and C 5+ The selectivity of the alcohol is at least 30%, for example at least 50%, or at least 70%.

[0092] Additional components may be present in the second product stream. For example, in some embodiments, the second product stream contains water, which is another product of the Fischer-Tropsch reaction. One or more light hydrocarbons (i.e., C1-C4) may also be present as byproducts. CO and / or H2 may be present, such as unreacted CO and / or H2 from the second feed stream. CO2 or other inert substances described herein may also be present. Such components of the second product stream can be separated and / or recycled in various ways. When the second product stream includes methane, the methane may be substantially derived from the biogas supplied to the first feed stream (e.g., at least 50%, at least 75%, or at least 90%).

[0093] For example, in various embodiments, the method further includes separating at least a portion of water from the second method stream. This is illustratively shown Figure 3 In. Figure 3In one embodiment, the reverse water-gas shift catalyst 313 and the Fischer-Tropsch catalyst 323 are provided in separate beds within the same reactor. Thus, the first reaction zone 310 is the volume of reactor 305 comprising a bed 314 containing the reverse water-gas shift catalyst 313, and the second reaction zone 320 is the volume of reactor 305 comprising a bed 324 containing the Fischer-Tropsch catalyst 323. A first feed stream 311 contacts the reverse water-gas shift catalyst 313 to provide a first product stream 312, which is then fed directly to the Fischer-Tropsch catalyst 323 as a second feed stream 321 to provide a second product stream 322. Optionally, the method further includes separating at least a portion of the water (e.g., at least 50%, at least 75%, or at least 90%) from the second product stream 322 to provide a water-containing stream 334.

[0094] Light hydrocarbons, while not typically the desired component of Fischer-Tropsch products used as fuels or lubricants, can be used for many purposes. Therefore, in various embodiments, the method further includes separating at least a portion of C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. This light hydrocarbon stream can, for example, be recycled to either the first or second feed stream. Figure 2 In method 200, light hydrocarbons may be provided as part of a recycle stream 236, which becomes part of a second feed stream 221. Figure 3 In method 300, light hydrocarbons may be provided as part of a recycle stream 336, which becomes part of a first feed stream 311. Figure 4 In method 400, light hydrocarbons are recycled to the first feed stream 411 via recirculation stream 442.

[0095] Light hydrocarbon feed streams also have other uses. For example, in some embodiments, the method further includes oxidizing at least a portion of the light hydrocarbon feed stream to provide a partially oxidized (pOX) feed stream containing CO and / or CO2, and including at least a portion of the pOX feed stream in a first feed stream and / or a second feed stream. In some embodiments as described herein, the light hydrocarbon feed stream contains methane from biogas. In some embodiments herein, at least 50% of the methane in the light hydrocarbon feed stream is methane from biogas. Figure 4The diagram schematically illustrates an example of such a method, wherein method 400, a first feed stream 411, a first product stream 412, a reverse water-gas shift catalyst 413, a second feed stream 421, a second product stream 422, and a Fischer-Tropsch catalyst 423 may be described separately herein. Here, the method comprises oxidizing at least a portion of the light hydrocarbon stream 450 in a partial oxidation reaction zone 452 to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream 454 in the first feed stream 411 and / or the second feed stream 421.

[0096] As described above, at least a portion of the CO2 in the first feed stream may originate from biogas. In some embodiments as described herein, the method includes providing biogas comprising CO2 and methane, providing at least a portion of the CO2 to the first feed stream, and providing at least a portion of the methane to at least a portion of the oxidation of the light hydrocarbon stream, such as... Figure 6 The implementation scheme is shown below.

[0097] Furthermore, light hydrocarbon streams can be burned to provide thermal energy, which can be used to heat streams of various types or for power generation. Therefore, in various embodiments, the method includes burning at least a portion of the light hydrocarbon stream to provide energy, such as thermal or electrical energy. For example, in… Figure 4 In method 400, a portion of the light hydrocarbon feedstock 450 is burned in the power generation zone (here, in generator 470) to generate current 472. In various embodiments, thermal energy can be used to provide the required heat load for the reverse water-gas shift process. For example, in... Figure 4 In method 400, a portion of the light hydrocarbon feed stream 450 is burned in the power generation zone (here, in the heat generator 480) to generate heat stream 482. Heat stream 482 is directed to heat exchange zone 490 to heat the first feed stream 411.

[0098] Similar to the first product stream, heat can be exchanged from the second product stream to provide heat to, for example, the feed stream or a steam generation zone. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the first feed stream. Figure 3In method 300, heat is exchanged between at least a portion of the second product stream 322 and the first feed stream 311 in the second heat exchange zone 330, thereby cooling the second product stream 322 and heating the first feed stream 311. Of course, heat can also be exchanged from the second product stream to the second feed stream. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and at least a portion of the second feed stream, thereby cooling at least a portion of the second product stream and heating at least a portion of the second feed stream. Figure 4 In method 400, heat is exchanged between at least a portion of the second product stream 422 and the second feed stream 421 in a second heat exchange zone 430, thereby cooling the second product stream 422 and heating the second feed stream 421. Those skilled in the art will understand that various heat exchangers can be used for this purpose.

[0099] Of course, any excess heat in the second product stream can be used additionally or alternatively for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the second product stream and the steam generation zone, thereby cooling at least a portion of the second product stream and providing heat to the steam generation zone. This shows Figure 3 In this process, after heat exchange with the first feed stream 311, the second product stream 322 is directed to the steam generation zone 332 to cool the second product stream 322 and provide heat to the steam generation zone 332. Steam can be generated from the provided heat, and electricity can be generated from the steam (not shown here).

[0100] It may be desirable to recycle hydrogen from the second product stream to, for example, the first feed stream and / or the second feed stream. For example, in various embodiments, the method includes recycling at least a portion of the H2 from the second product stream to the second feed stream. Figure 2 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the second product stream can be recycled to the second feed stream 221 via the recycling stream 236. In various embodiments, the method includes recycling at least a portion of the H2 of the second product stream to the first feed stream 311. For example, in Figure 3 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the second product stream can be recycled back to the first feed stream 311 via the recycling stream 336. In various embodiments, at least 25%, for example, at least 50%, of the H2 in the second product stream is recycled back to the first feed stream or the second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the H2 in the second product stream is recycled back to the first feed stream or the second feed stream.

[0101] In some cases, for example, when H2 is supplied to the second feed stream from a source other than the first product stream, the H2 from the second product stream can constitute a large portion of the H2 in the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the H2 in the first feed stream. This is shown, for example, in... Figure 4 In this context, the primary H2 input of the method is through feed stream 440, which becomes part of the second feed stream 421. The H2 of the second product stream is included in the recirculation stream 442, which becomes part of the first feed stream 411.

[0102] Similarly, it may be desirable to recycle the CO from the second product stream to, for example, the first feed stream and / or the second feed stream. For example, in various embodiments, the method includes recycling at least a portion of the CO from the second product stream to the second feed stream. Figure 2 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO in the second product stream can be recycled to the second feed stream 221 via the recycle stream 236. In various embodiments, the method includes recycling at least a portion of the CO in the second product stream to the first feed stream. For example, in... Figure 3 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO in the second product stream can be recycled back to the first feed stream 311 via the recycling stream 336. In various embodiments, at least 25%, for example, at least 50%, of the CO in the second product stream is recycled back to the first feed stream or the second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the CO in the second product stream is recycled back to the first feed stream or the second feed stream.

[0103] In many cases, both CO and H2 from the second product stream will be recycled.

[0104] Furthermore, when one or more inert materials are used in the Fischer-Tropsch process, it may be desirable to recycle these inert materials. For example, in various embodiments, the method includes recycling at least a portion of the inert materials from the second product stream to the second feed stream. For example, in Figure 2 In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inert material in the second product stream can be recycled to the second feed stream 221 via the recycling stream 236. In various embodiments, the method includes recycling at least a portion of the inert material in the second product stream to the first feed stream. For example, in... Figure 3In the method, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the inert material in the second product stream can be recycled back to the first feed stream 311 via the recirculation stream 336. In various embodiments, at least 25%, for example, at least 50%, of the inert material in the second product stream is recycled back to the first or second feed stream. In various embodiments, at least 75%, for example, at least 90%, of the inert material in the second product stream is recycled back to the first or second feed stream. In various embodiments, the purge stream can be combined with the recirculation stream to prevent uncontrolled accumulation of inert material in the recirculation stream (not shown here).

[0105] Specifically, since CO2 is the carbon source for the reverse water-gas shift process steps, it may be particularly desirable to recycle the CO2 back to the first feed stream. Therefore, in various embodiments, the method includes recycling at least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the CO2 from the second product stream back to the first feed stream. For example, in… Figure 3 In the method, at least a portion (e.g., at least 50%, at least 75%, or at least 90%) of the CO2 in the second product stream can be recycled to the first feed stream 311 via the recycle stream 336.

[0106] In some cases, such as when CO2 is supplied to the second feed stream from a source other than the first product stream, the CO2 from the second product stream can constitute a large portion of the CO2 in the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 in the first feed stream. This is illustrated, for example, in... Figure 4 In this method, the primary CO2 input is through stream 440, which becomes part of the second feed stream 421. The CO2 of the second product stream is contained in the recycle stream 442, which becomes part of the first feed stream 411.

[0107] As described above, the Fischer-Tropsch process provides a method containing C 5+ A second product stream of hydrocarbons (e.g., unsubstituted hydrocarbons such as alkanes and alkenes, and / or oxygen-containing hydrocarbons such as alcohols). Therefore, in various embodiments, the C2O3 of the second product stream... 5+ At least a portion of the hydrocarbon provides one or more products. The C 5+ Hydrocarbons can be used as a base for various fuels, such as gasoline, diesel, and aviation fuel. They can also be used to manufacture other products, such as waxes and lubricants. Furthermore, olefins and oxygenated compounds can be used as raw materials in a variety of other processes.

[0108] Those skilled in the art will use conventional post-processing techniques to process C 5+The hydrocarbon product is converted into a desirable product, such as a desirable fuel. For example, in various embodiments, the method further includes hydrotreating the second product stream with C... 5+ At least a portion of hydrocarbons. As those skilled in the art will understand, hydrotreatment is the treatment of a hydrocarbon feed stream with hydrogen in the presence of a suitable catalyst. A wide variety of hydrotreatment technologies are known, and those skilled in the art will apply them herein. For example, in Figure 3 In method 300, the second product stream 322 is hydrogenated in a hydrotreating reactor 350 to provide a hydrotreated product stream 352.

[0109] As stated above, CO2 and H2 are essential inputs to the claimed method. Advantageously, the inventors have recognized that each of these inputs can originate from renewable or otherwise environmentally responsible sources. As stated above, at least a portion of the CO2 in the first feed stream originates from biogas, CO2 emission sources, and / or direct air capture. A portion of the CO2 in the second feed stream may also originate from biogas, CO2 emission sources, and / or direct air capture.

[0110] Therefore, in some embodiments of this disclosure as described herein, at least a portion of the CO2 in the second feed stream originates from a renewable source. In some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO2 in the second feed stream originates from direct air capture. In some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the CO2 in the second feed stream originates from a manufacturing plant such as a bioethanol plant (e.g., a CO2-producing fermentation), a steel plant, or a cement plant.

[0111] Similarly, H2 can be provided from environmentally responsible sources. In some embodiments, at least a portion of the H2 in the first feed stream and / or the second feed stream comes from a renewable source. For example, in various embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream can be so-called "green" hydrogen, such as that produced by water electrolysis operated using renewable electricity (e.g., wind, solar, or hydropower). In some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream can come from so-called "blue" sources, such as those from natural gas reforming processes with carbon capture. Of course, other hydrogen sources can be used in part or in whole. For example, in some embodiments, at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the H2 in the first feed stream and / or the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0112] The inventors have noted that water electrolysis is a desirable method for providing hydrogen to the claimed method. Therefore, in some embodiments, the method includes providing at least a portion of H2 to a first feed stream and / or a second feed stream via water electrolysis. In some embodiments, water electrolysis is performed at least partially using electricity from a renewable source, for example, to provide so-called "green hydrogen." However, the inventors have noted that electricity can be generated as part of the claimed method, for example, using heat exchange from a first or second product stream, or by burning light hydrocarbons as described above. In some embodiments, water electrolysis is performed at least partially using electricity generated according to the methods described herein. For example, in Figure 2 In method 200, electricity 264 generated from steam produced by heat exchange from a first product stream in a steam generation zone 232 is used to electrolyze water 262 separated from the first product stream in an electrolyzer 260. 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 the feed stream as described herein and as... Figure 6 The partial oxidation reaction zone is shown in the implementation scheme.

[0113] The methods described herein can be operated in a wide variety of reactor systems. In some embodiments, a first reaction zone (i.e., in which the reverse water-gas shift process steps are performed) comprises a first reactor in which a reverse water-gas shift catalyst is disposed, and a second reaction zone (i.e., in which the Fischer-Tropsch process steps are performed) comprises a second reactor in which a Fischer-Tropsch catalyst is disposed. Illustrative examples of such methods are shown in [illustrative examples]. Figure 1 , 2 In embodiments 100, 200, and 400, the methods (100, 200, 400) are carried out in a reactor system comprising a first reactor (110, 210, 410) in which a counter-current water-gas shift catalyst (113, 213, 413) is disposed, and a second reactor (120, 220, 420) in which a Fischer-Tropsch catalyst (123, 223, 423) is disposed. There are no particular limitations on the reactors used for the integrated methods of this disclosure as described herein, and those skilled in the art will be able to select appropriate reactors.

[0114] However, other implementations are also possible. For example, in some implementations, the method is carried out in a reactor system comprising a first catalyst bed in which a 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. In some implementations, the first and second reactor beds are disposed within the same reactor. Figure 3This configuration is illustrated in the image, where a reverse water-gas shift catalyst 313 is disposed in a first catalyst bed 314, and a Fischer-Tropsch catalyst 323 is disposed in a second catalyst bed 324. Here, catalyst beds 314 and 324 are in the same reactor, and the process gas flows between them. This configuration may be particularly desirable when the first and second temperatures are relatively close to each other.

[0115] In various embodiments, the method is carried out in a reactor system comprising a first catalyst vessel in which one or more counter-current water-gas shift catalysts are disposed, and a second reaction zone comprising a second catalyst vessel in which one or more Fischer-Tropsch catalysts are disposed. These can be provided in the same reactor, such as those described above regarding catalyst beds.

[0116] As described above, the reverse water-gas shift process steps and the Fischer-Tropsch process steps using the catalysts described herein can be carried out under similar conditions. Therefore, in various embodiments, the reverse water-gas shift catalyst and the Fischer-Tropsch catalyst can be provided together in the same catalyst bed, for example, mixed together. Such embodiments are shown... Figure 5 In this context, method 500 is carried out in a reactor system including reactor 505, in which the reverse water-gas shift catalyst 513 and the Fischer-Tropsch catalyst 523 are mixed together in a single catalyst bed 524. Here, the first feed stream 511 and the second product stream 522 can be substantially as described herein. The first product stream and the second feed stream are understood as mixtures of method gases within the mixed catalyst.

[0117] In the embodiments specifically described above, individual rWGS and Fischer-Tropsch catalysts may be used, for example, in separate reactors, in separate areas of the same reactor, or even mixed in the same area of ​​the reactor.

[0118] However, the inventors also note that the rWGS catalyst described herein shares certain commonalities with some Fischer-Tropsch catalysts. For example, as those skilled in the art will understand, manganese is a common modifier used in Fischer-Tropsch catalysts, especially those based on cobalt. The inventors also note that similar supports can be used for each catalyst.

[0119] Therefore, in addition to the above-described structure, the inventors envision providing a single bifunctional catalyst possessing both reverse water-gas shift activity and Fischer-Tropsch activity. This bifunctional catalyst comprises both an rWGS active catalyst metal and a Fischer-Tropsch active catalyst metal within the same bulk. Those skilled in the art will understand that both the rWGS catalyst and the Fischer-Tropsch catalyst are supported catalysts, such as metal oxide supported catalysts. Therefore, in various embodiments of this disclosure, the rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal can be disposed together on the same support to provide a bifunctional catalyst. For example, in some embodiments, the support for the bifunctional catalyst is itself provided as a discrete material, such as porous particles, pellets, or shaped extrusions, on which the rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal are disposed to provide a bifunctional catalyst. The rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal can be uniformly distributed throughout the support, or they can be distributed in discrete regions throughout the support. However, in other embodiments, the bifunctional catalyst of this disclosure can itself be formed as a layer on an underlying substrate. For example, in some embodiments, the bifunctional catalyst is formed of an rWGS active catalyst metal layer and an FT active catalyst metal layer on an underlying substrate. The rWGS active catalyst metal and the FT active catalyst metal can be uniformly distributed on the underlying substrate. In other embodiments, the rWGS active catalyst metal and the FT active catalyst metal can be in discrete regions on the underlying substrate. The underlying substrate is not particularly limited. It can be formed of, for example, a metal or a metal oxide, and can be provided in various forms, such as particles, pellets, shaped extrusions, or monolithic materials.

[0120] 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, which is a metal oxide support, including at least one of titanium oxide, zirconium oxide, cerium oxide, or alumina. There are no particular limitations on the rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal, and those skilled in the art will be able to select appropriate metals. For example, those skilled in the art or of ordinary skill will be able to select appropriate rWGS active metals as described in: Daza et al., “CO2conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO2conversion to liquid fuels.” RSCAdv., 2016, 6, 49675-49691; Zhu et al., “Catalytic Reduction of CO2 to CO via Reverse Water Gas Shift Reaction: Recent Advances in the Design of Active and Selective Supported Metal Catalyst.” Journal of Tianjin University, 2020, 26, 172-187; and Chen et al., “Recent Advances in Supported Metal Catalysts and Oxide Catalyst for the Reverse Water-Gas Shift Reaction.” Front. Chem., 2020, 8, 709. For example, the rWGS active metal can be selected from copper, platinum, palladium, rhodium, rhenium, ruthenium, nickel, gold, and iridium, or combinations thereof. Similarly, those skilled in the art will be able to select suitable Fischer-Tropsch active metals as described herein. For example, the Fischer-Tropsch active metal can be selected from cobalt, iron, rhodium, ruthenium, manganese, or combinations thereof.

[0121] There are no particular limitations on the ratio of the rWGS active catalyst metal to the FT active catalyst metal in the bifunctional catalyst, and those skilled in the art will be able to select an appropriate ratio. For example, in some embodiments, the ratio of the rWGS active catalyst metal to the FT active catalyst metal in the bifunctional catalyst is at least 0.1:1. In various embodiments, the ratio of the rWGS active catalyst metal to the FT active catalyst metal in the bifunctional catalyst is at least 0.2:1, or 0.5, or 1:1.

[0122] Such catalysts can be used for, for example, regarding Figure 5 The aforementioned implementation schemes. Those skilled in the art will select reaction conditions that provide a suitable balance between the reverse water-gas shift activity and the Fischer-Tropsch activity.

[0123] Figure 6 This is a schematic depiction of another integrated method according to this disclosure. Here, the reverse water gas shift and Fischer-Tropsch process steps are integrated with the partial oxidation of light hydrocarbons to provide CO and H2 to the Fischer-Tropsch process steps; electrolysis is used to provide H2 for the reverse water gas shift process steps and O2 for the partial oxidation; and various recycles and optional feeds are included, as described throughout this specification.

[0124] Additional aspects of this disclosure are provided by the following enumerated embodiments, which can be combined in any number and in any combination that is logically or technically inconsistent.

[0125] Implementation Scheme 1. A method for performing integrated Fischer-Tropsch method, the method comprising: A first feed stream comprising H2 and CO2 is provided, wherein at least a portion of the CO2 in the first feed stream originates from biogas, a CO2 emission source, and / or direct air capture; At a first temperature and a first pressure within the range of 200-1100℃, the reverse water gas shift catalyst is brought into contact with the first feed stream to carry out a reverse water gas shift reaction to provide a first product stream containing CO and H2, which has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream (containing at least a portion of H2 and CO from the first product stream) at a second temperature and a second pressure to provide a product containing C. 5+ The second product stream of hydrocarbons.

[0126] Implementation Scheme 2. The method according to Implementation Scheme 1, wherein the CO2 of the first feed stream comprises at least 50% by volume (e.g., at least 75% by volume, at least 90% by volume, or at least 95% by volume) of CO2 from biogas, CO2 from CO2 emission sources, and / or CO2 from direct air capture.

[0127] Implementation Scheme 3. The method of claim 1, wherein at least a portion of the CO2 in the first feed stream originates from biogas.

[0128] Implementation Scheme 4. The method according to Implementation Scheme 3, wherein the CO2 of the first feed stream comprises at least 50% by volume (e.g., at least 75% by volume, at least 90% by volume, or at least 95% by volume) CO2 from biogas.

[0129] Implementation Scheme 5. The method of claim 1, wherein at least a portion of the CO2 in the first feed stream is derived from direct air capture.

[0130] Implementation Scheme 6. The method according to Implementation Scheme 5, wherein the CO2 of the first feed stream comprises at least 50% by volume (e.g., at least 75% by volume, at least 90% by volume, or at least 95% by volume) CO2 from direct air capture.

[0131] Implementation Scheme 7. The method according to Implementation Scheme 1, wherein at least a portion of the CO2 in the first feed stream originates from a CO2 emission source (e.g., from a manufacturing plant, such as a bioethanol plant, steel plant, or cement plant).

[0132] Implementation Scheme 8. The method according to Implementation Scheme 7, wherein the CO2 of the first feed stream contains at least 50% by volume (e.g., at least 75% by volume, at least 90% by volume, or at least 95% by volume) CO2 from a CO2 emission source.

[0133] Implementation Scheme 9. The method according to Implementation Scheme 1, wherein the method includes providing a first feed stream comprising H2, CO2 and methane, wherein at least a portion of the CO2 in the first feed stream originates from biogas, and wherein at least a portion of the methane in the first feed stream originates from biogas.

[0134] Implementation Scheme 10. The method according to Implementation Scheme 9, wherein the CO2 of the first feed stream comprises at least 50% by volume (e.g., at least 75% by volume, at least 80% by volume, at least 85% by volume, or at least 90% by volume) CO2 from biogas.

[0135] Implementation Scheme 11. The method according to Implementation Scheme 9, wherein the CO2 of the first feed stream comprises at least 95% by volume CO2 from biogas.

[0136] Implementation Scheme 12. The method according to any one of Implementation Schemes 9-11, wherein the methane in the first feed stream comprises at least 50% by volume (e.g., at least 75% by volume, at least 80% by volume, at least 85% by volume, or at least 90% by volume) methane from biogas.

[0137] Implementation Scheme 13. The method according to any one of Implementation Schemes 9-11, wherein the methane in the first feed stream comprises at least 95% by volume methane from biogas.

[0138] Implementation Scheme 14. The method according to any one of Implementation Schemes 9-13, wherein the amount of methane in the first feed stream is in the range of 10-70 mol%, or 10-50 mol%, or 20-70 mol%, or 20-50 mol%, or 30-70 mol%, or 30-50 mol%.

[0139] Implementation Scheme 15. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream is at least 0.05:1, for example, at least 0.25:1.

[0140] Implementation Scheme 16. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream is at least 0.5:1, for example, at least 0.75:1.

[0141] Implementation Scheme 17. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream is at least 1:1, for example, at least 1.25:1.

[0142] Implementation Scheme 18. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream does not exceed 50:1, for example, not exceeding 40:1 or not exceeding 25:1.

[0143] Implementation Scheme 19. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream does not exceed 10:1, for example, not exceeding 8:1 or not exceeding 5:1.

[0144] Implementation Scheme 20. The method according to any one of Implementation Schemes 9-14, wherein the molar ratio of H2 to methane in the first feed stream is in the range of 0.25:1 to 5:1.

[0145] Implementation Scheme 21. The method according to any one of Implementation Schemes 9-20, wherein the molar ratio of methane to CO2 in the first feed stream is at least 0.25:1 (e.g., at least 0.3:1, at least 0.4:1 or at least 0.5:1).

[0146] Implementation Scheme 22. The method according to any one of Implementation Schemes 9-20, wherein the molar ratio of methane to CO2 in the first feed stream is in the range of 0.25:1 to 4:1 (e.g., in the range of 0.3:1 to 3:1, in the range of 0.4:1 to 2.5:1, or in the range of 0.5:1 to 2:1).

[0147] Implementation Scheme 23. The method according to any one of Implementation Schemes 9-20, wherein the molar ratio of methane to CO2 in the first feed stream is in the range of 0.8:1 to 1.2:1.

[0148] Implementation Scheme 24. The method according to any one of Implementation Schemes 9-20, wherein the molar ratio of methane to CO2 in the first feed stream is in the range of 0.85:1 to 1.15:1 (e.g., in the range of 0.9:1 to 1.1:1).

[0149] Implementation Scheme 25. The method according to any one of Implementation Schemes 9-24, wherein the molar amount of methane in the first feed stream is approximately the same as the molar amount of CO2 in the first feed stream (e.g., in the range of 0.95:1 to 1.05:1).

[0150] Implementation Scheme 26. The method according to any one of Implementation Schemes 9-25, wherein providing the first feed stream comprises providing a biogas stream, separating at least a portion of water (e.g., at least 50%, at least 80%, or at least 90% of the water) from the biogas stream to provide a water-poor biogas stream, and providing CO2 from the biogas and methane from the biogas stream from the water-poor biogas stream.

[0151] Implementation Scheme 27. The method according to any one of Implementation Schemes 9-26, wherein providing the first feed stream comprises providing a biogas stream, separating at least a portion of the hydrogen sulfide (e.g., at least 50%, at least 80%, or at least 90% of the hydrogen sulfide) from the biogas stream to provide a hydrogen sulfide-poor biogas stream, and providing the CO2 from the biogas and the methane from the biogas from the hydrogen sulfide-poor biogas stream.

[0152] Implementation Scheme 28. The method according to any one of Implementation Schemes 1-27, 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.

[0153] Implementation Scheme 29. The method according to any one of Implementation Schemes 1-28, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 0.9:1, for example, at least 1:1 or at least 1.5:1.

[0154] Implementation Scheme 30. The method according to any one of Implementation Schemes 1-29, 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.

[0155] Implementation Scheme 31. The method according to any one of Implementation Schemes 1-30, wherein the molar ratio of H2 to CO2 in the first feed stream does not exceed 100:1, for example, not exceeding 75:1 or 50:1.

[0156] Implementation Scheme 32. The method according to any one of Implementation Schemes 1-30, wherein the molar ratio of H2 to CO2 in the first feed stream does not exceed 20:1, for example, not exceeding 15:1 or 10:1.

[0157] Implementation Scheme 33. The method according to any one of Implementation Schemes 1-32, wherein the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:1.

[0158] Implementation Scheme 34. The method according to any one of Implementation Schemes 1-33, wherein the first feed stream further comprises CO.

[0159] Implementation Scheme 35. The method according to any one of Implementation Schemes 1-34, wherein the first feed stream contains no more than 20 mol% (e.g., no more than 10 mol%, or no more than 5 mol%, or no more than 3 mol%, or no more than 1 mol%) of CO.

[0160] Implementation Scheme 36. The method according to any one of Implementation Schemes 1-35, wherein the first feed stream further comprises one or more inert gases (e.g., nitrogen and / or methane).

[0161] Implementation Scheme 37. The method according to Implementation Scheme 36, wherein the first feed stream contains no more than 50 mol% (e.g., no more than 30 mol%, no more than 20 mol%, or no more than 10 mol%) of methane.

[0162] Implementation Scheme 38. The method according to Implementation Scheme 36 or Implementation Scheme 37, wherein the first feed stream contains no more than 10 mol% (e.g., no more than 6 mol% or no more than 2 mol%) of nitrogen.

[0163] Implementation Scheme 39. The method according to any one of Implementation Schemes 1-38, wherein the reverse water-gas shift reaction has a CO selectivity of at least 70% (e.g., at least 80%).

[0164] Implementation Scheme 40. The method according to any one of Implementation Schemes 1-38, wherein the reverse water-gas shift reaction has a CO selectivity of at least 85% (e.g., or at least 90%).

[0165] Implementation Scheme 41. The method according to any one of Implementation Schemes 1-40, wherein the reverse water-gas shift reaction has a CO selectivity of at least 95% (e.g., at least 96%).

[0166] Implementation Scheme 42. The method according to any one of Implementation Schemes 1-41, wherein the reverse water-gas shift reaction has a CO selectivity of at least 98% (e.g., or at least 99%).

[0167] Implementation Scheme 43. The method according to any one of Implementation Schemes 1-42, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 5% (e.g., no more than 4%).

[0168] Implementation Scheme 44. The method according to any one of Implementation Schemes 1-42, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 2% (e.g., no more than 1%).

[0169] Implementation Scheme 45. The method according to any one of Implementation Schemes 1-42, wherein the reverse water-gas shift reaction has a methane selectivity of not more than 0.5% (e.g., not more than 0.2%).

[0170] Implementation Scheme 46. The method according to any one of Implementation Schemes 1-45, wherein the reverse water-gas shift reaction has a CO2 conversion rate of at least 5% (e.g., at least 10% or 20%).

[0171] Implementation Scheme 47. The method according to any one of Implementation Schemes 1-45, wherein the reverse water-gas shift reaction has a CO2 conversion rate of at least 30% (e.g., at least 40%).

[0172] Implementation Scheme 48. The method according to any one of Implementation Schemes 1-47, wherein the reverse water-gas shift reaction has a CO2 conversion rate of not more than 90% (e.g., not more than 80% or not more than 70%).

[0173] Implementation Scheme 49. The method according to any one of Implementation Schemes 1-47, wherein the reverse water-gas shift reaction has a CO2 conversion rate of not more than 65% (e.g., not more than 60%).

[0174] Implementation Scheme 50. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 250-1050°C, for example, in the range of 250-1000°C or 250-950°C.

[0175] Implementation Scheme 51. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 250-900°C, for example, in the range of 250-850°C, or 250-800°C, or 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C.

[0176] Implementation Scheme 52. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 300-1100°C, for example, in the range of 300-1050°C, or 300-1000°C, or 300-950°C.

[0177] Implementation Scheme 53. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 300-900°C, for example, in the range of 300-850°C, or 300-800°C, or 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.

[0178] Implementation Scheme 54. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 350-1100°C, for example, in the range of 350-1050°C, or 350-1000°C, or 350-950°C.

[0179] Implementation Scheme 55. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 350-900°C, for example, in the range of 350-850°C, or 350-800°C, or 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C.

[0180] Implementation Scheme 56. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 400-1100°C, for example, in the range of 400-1050°C, or 400-1000°C, or 400-950°C.

[0181] Implementation Scheme 57. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 400-900°C, for example, in the range of 400-850°C, or 400-800°C, or 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.

[0182] Implementation Scheme 58. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 450-1100°C, for example, in the range of 450-1050°C, or 450-1000°C, or 450-950°C.

[0183] Implementation Scheme 59. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 450-900°C, for example, in the range of 450-850°C, or 450-800°C, or 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C.

[0184] Implementation Scheme 60. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 500-1100°C, for example, in the range of 500-1050°C, or 500-1000°C, or 500-950°C.

[0185] Implementation Scheme 61. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 500-900°C, for example, in the range of 500-850°C, or 500-800°C, or 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.

[0186] Implementation Scheme 62. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 550-1100°C, for example, in the range of 550-1050°C, or 550-1000°C, or 550-950°C.

[0187] Implementation Scheme 63. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 550-900°C, for example, in the range of 550-850°C, or 550-800°C, or 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.

[0188] Implementation Scheme 64. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 600-1100°C, for example, in the range of 600-1050°C, or 600-1000°C, or 600-950°C.

[0189] Implementation Scheme 65. The method according to any one of Implementation Schemes 1-49, wherein 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.

[0190] Implementation Scheme 66. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 650-1100°C, for example, in the range of 650-1050°C, or 650-1000°C, or 650-950°C.

[0191] Implementation Scheme 67. The method according to any one of Implementation Schemes 1-49, wherein 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.

[0192] Implementation Scheme 68. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 700-1100°C, for example, in the range of 700-1050°C, or 700-1000°C, or 700-950°C.

[0193] Implementation Scheme 69. The method according to any one of Implementation Schemes 1-49, wherein 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.

[0194] Implementation Scheme 70. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, for example, 250-450°C, or 250-400°C, or 250-350°C.

[0195] Implementation Scheme 71. The method according to any one of Implementation Schemes 1-49, wherein the reverse water-gas shift reaction is carried out at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, for example, 250-450°C, or 250-400°C, or 250-350°C.

[0196] Implementation Scheme 72. The method according to any one of Implementation Schemes 1-71, wherein the reverse water-gas shift reaction is carried out at a pressure in the range of 1 to 100 barg (e.g., in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 80 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg).

[0197] Implementation Scheme 73. The method according to any one of Implementation Schemes 1-72, wherein the reverse water-gas shift reaction is carried out at 1,000 to 2,000,000 h. -1 Performed under GHSV within the range (e.g., 1,000 to 1,200,000 h). -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000 h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 (within the range).

[0198] Implementation Scheme 74. The method according to any one of Implementation Schemes 1-73, wherein the method includes activating the reverse water gas shift catalyst, for example before contacting the reverse water gas shift catalyst with the first feed stream.

[0199] Implementation Scheme 75. The method according to Implementation Scheme 74, wherein activating the rWGS catalyst comprises contacting the rWGS catalyst with a reducing feed stream containing a reducing gas (e.g., hydrogen).

[0200] Implementation Scheme 76. The method according to Implementation Scheme 74 or Implementation Scheme 75, wherein the reducing agent stream contains at least 25 mol% (e.g., at least 50 mol%, or 75 mol%, or 90 mol%) of hydrogen.

[0201] Implementation Scheme 77. The method according to any one of Implementation Schemes 74-76, wherein the activation of the rWGS catalyst is carried out at a temperature in the range of 200°C to 1000°C (e.g., in the range of 250°C to 1000°C, or 300°C to 1000°C, 200°C to 900°C, 250°C to 900°C, or 300°C to 900°C, 200°C to 800°C, or 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 700°C, or 300°C to 700°C).

[0202] Implementation Scheme 78. The method according to any one of Implementation Schemes 74-77, wherein activating the rWGS catalyst provides at least 10% of the catalyst to be reduced (e.g., at least 25% or 50%).

[0203] Implementation Scheme 79. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains no more than 95 mol% CO2 (e.g., no more than 90 mol% CO2).

[0204] Implementation Scheme 80. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains no more than 85 mol% CO2 (e.g., no more than 80 mol% CO2).

[0205] Implementation Scheme 81. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains no more than 75 mol% CO2 (e.g., no more than 70 mol% CO2).

[0206] Implementation Scheme 82. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains CO2 in the range of 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%.

[0207] Implementation Scheme 83. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains methane in an amount in the range of 10-70 mol% (e.g., in the range of 10-50 mol%, or 20-70 mol%, or 20-50 mol%, or 30-70 mol%, or 30-50 mol%).

[0208] Implementation Scheme 84. The method according to any one of Implementation Schemes 1-78, wherein the first product stream contains no more than 20 mol% methane, for example, no more than 15 mol% methane.

[0209] Implementation Scheme 85. The method according to any one of Implementation Schemes 1-78, wherein the first 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.

[0210] Implementation Scheme 86. The method according to any one of Implementation Schemes 1-85, wherein the H2:CO ratio in the first product stream is at most 100:1, for example, at most 50:1, or at most 25:1, or at most 10:1.

[0211] Implementation Scheme 87. The method according to any one of Implementation Schemes 1-85, wherein the H2:CO ratio in the first product stream is in the range of 0.1:1 to 100:1 (e.g., in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0212] Implementation Scheme 88. The method according to any one of Implementation Schemes 1-87, wherein the method further comprises separating the first product stream to recycle at least a portion of one or more components of the first product stream to the first feed stream.

[0213] Implementation Scheme 89. The method according to any one of Implementation Schemes 1-88, wherein the method further comprises separating the first product stream to recycle at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of CO2 from the first product stream back to the first feed stream.

[0214] Implementation Scheme 90. The method according to any one of Implementation Schemes 1-89, wherein the method further comprises separating the first product stream to recycle at least a portion of H2 (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) back to the first feed stream.

[0215] Implementation Scheme 91. The method according to any one of Implementation Schemes 1-90, wherein the method further comprises separating at least a portion of H2 and / or CO from the first product stream and contacting it with the Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst.

[0216] Implementation Scheme 92. The method according to any one of Implementation Schemes 1-91, wherein the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of water from the first product stream.

[0217] Implementation Scheme 93. The method according to any one of Implementation Schemes 1-92, wherein the first product stream further comprises one or more light hydrocarbons (e.g., methane, ethane, propane).

[0218] Implementation Scheme 94. The method according to Implementation Scheme 93 further includes separating at least a portion of the one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream.

[0219] Implementation Scheme 95. The method according to Implementation Scheme 93 or 94, wherein the light hydrocarbon feed stream comprises methane from biogas.

[0220] Implementation Scheme 96. The method according to Implementation Scheme 95 further includes burning at least a portion of the light hydrocarbon feed stream to provide energy, such as thermal or electrical energy.

[0221] Implementation Scheme 97. The method according to Implementation Scheme 91 or 94, wherein the thermal energy is used to heat the first feed stream.

[0222] Implementation Scheme 98. The method according to any one of Implementation Schemes 1-97, 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.

[0223] Implementation Scheme 99. The method according to any one of Implementation Schemes 1-98, wherein the method further comprises 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.

[0224] Implementation Scheme 100. The method according to Implementation Scheme 99 further includes generating steam from heat supplied to the steam generating zone and generating electricity from the steam.

[0225] Implementation Scheme 101. The method according to Implementation Scheme 99 or 100, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0226] Implementation Scheme 102. The method according to any one of Implementation Schemes 1-101, wherein at least 25% of the CO of the first product stream, for example at least 50%, at least 75%, or at least 90% of the CO, is included in the second feed stream.

[0227] Implementation Scheme 103. The method according to any one of Implementation Schemes 1-102, wherein CO is supplied to the second feed stream from a CO source other than the first product stream.

[0228] Implementation Scheme 104. The method according to any one of Implementation Schemes 1-102, 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.

[0229] Implementation Scheme 105. The method according to any one of Implementation Schemes 1-104, wherein at least 25% of H2 of the first product stream, for example at least 50%, at least 75%, or at least 90% of H2, is included in the second feed stream.

[0230] Implementation Scheme 106. The method according to any one of Implementation Schemes 1-105, wherein H2 is supplied to the second feed stream from a hydrogen source other than the first product stream.

[0231] Implementation Scheme 107. The method according to any one of Implementation Schemes 1-106, wherein the second feed stream comprises at least a portion of the CO2 of the first product stream.

[0232] Implementation Scheme 108. The method according to any one of Implementation Schemes 1-107, wherein at least 10% of the CO2 in the first product stream, for example at least 25%, at least 50%, at least 75%, or at least 90% of the CO2, is included in the second feed stream.

[0233] Implementation Scheme 109. The method according to any one of Implementation Schemes 1-107, wherein the second feed stream does not include a significant amount of CO2 from the first product stream.

[0234] Implementation Scheme 110. The method according to any one of Implementation Schemes 1-109, wherein a 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, for example in the range of 1:1 to 3:1.

[0235] Implementation Scheme 111. The method according to any one of Implementation Schemes 1-110, wherein the portion of the first product stream included in the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 0.5 mol%.

[0236] Implementation Scheme 112. The method according to any one of Implementation Schemes 1-111, wherein a portion of the first product stream included 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%.

[0237] Implementation Scheme 113. The method according to any one of Implementation Schemes 1-112, wherein the second feed stream has an H2:CO ratio in the range of 0.5:1 to 6:1.

[0238] Implementation Scheme 114. The method according to any one of Implementation Schemes 1-112, wherein the second feed stream has an H2:CO ratio in the range of 1:1 to 3:1, for example, 1:1 to 2.5:1.

[0239] Implementation Scheme 115. The method according to any one of Implementation Schemes 1-112, wherein the second feed stream has an H2:CO ratio of at least 1.4:1, for example, in the range of 1.4:1 to 3:1 or 1.4:1 to 2.5:1.

[0240] Implementation Scheme 116. The method according to any one of Implementation Schemes 1-115, wherein the second feed stream comprises up to 80% of one or more inert materials, 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%.

[0241] Implementation Scheme 117. The method according to any one of Implementation Schemes 1-115, wherein the second feed stream comprises up to 80% of one or more inert substances 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%.

[0242] Implementation Scheme 118. The method according to any one of Implementation Schemes 1-117, wherein the second feed stream contains up to 80% 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%.

[0243] Implementation Scheme 119. The method according to any one of Implementation Schemes 1-119, wherein the second feed stream has a water content of not more than 10 mol%, for example, not more than 2 mol%, or not more than 0.5 mol%.

[0244] Implementation Scheme 120. The method according to any one of Implementation Schemes 1-119, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0245] Implementation Scheme 121. The method according to any one of Implementation Schemes 1-120, wherein the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount in the range of 5-25 wt%, for example, 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt%, calculated as Co(0).

[0246] Implementation Scheme 122. The method according to any one of Implementation Schemes 1-120, wherein the Fischer-Tropsch catalyst comprises iron, for example, in an amount ranging from 5 to 95 wt%, for example, 10 to 95 wt%, or 25 to 95 wt%, or 50 to 95 wt%, or 5 to 85 wt%, or 10 to 85 wt%, or 25 to 85 wt%, or 50 to 85 wt%, or 5 to 75 wt%, or 10 to 75 wt%, or 25 to 75 wt%, calculated as Fe(0).

[0247] Implementation Scheme 123. The method according to any one of Implementation Schemes 120-122, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0248] Implementation Scheme 124. The method according to Implementation Scheme 123, wherein the manganese is present in an amount of up to 15 wt%, 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%, calculated as Mn(0).

[0249] Implementation Scheme 125. The method according to any one of Implementation Schemes 1-124, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one selected from titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide, and zinc oxide.

[0250] Implementation Scheme 126. The method according to any one of Implementation Schemes 1-124, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, alumina and silica.

[0251] Implementation Scheme 127. The method according to any one of Implementation Schemes 1-124, wherein the Fischer-Tropsch catalyst is a supported catalyst and wherein the support is a titanium dioxide support.

[0252] Implementation Scheme 128. The method according to any one of Implementation Schemes 1-127, wherein the Fischer-Tropsch catalyst is activated by contact with a reducing gas (e.g., hydrogen).

[0253] Implementation Scheme 129. The method according to Implementation Scheme 129, wherein the reducing gas comprises at least a portion of hydrogen from the first product stream.

[0254] Implementation Scheme 130. The method according to any one of Implementation Schemes 1-127, wherein the Fischer-Tropsch catalyst is activated by contact with H2 and CO.

[0255] Implementation Scheme 131. The method according to Implementation Scheme 130, wherein the reducing gas comprises at least a portion of H2 and CO from the first product stream.

[0256] Implementation Scheme 132. The method according to any one of Implementation Schemes 128-130, wherein the activation is carried out at a temperature in the range of 200-400°C.

[0257] Implementation Scheme 133. The method according to any one of Implementation Schemes 1-132, wherein the second temperature is in the range of 150-400°C (e.g., in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0258] Implementation Scheme 134. The method according to any one of Implementation Schemes 1-133, wherein the second temperature is in the range of 200-350°C.

[0259] Implementation Scheme 135. The method according to any one of Implementation Schemes 1-134, wherein the first temperature is within 100°C of the second temperature, for example within 50°C of the second temperature, or within 25°C of the second temperature.

[0260] Implementation Scheme 136. The method according to any one of Implementation Schemes 1-135, wherein the first temperature is at least 100°C higher than the second temperature, for example at least 150°C higher, or at least 200°C higher.

[0261] Implementation Scheme 137. The method according to any one of Implementation Schemes 1-136, wherein the second pressure is in the range of 10-50 barg (e.g., 20-50 barg, or 25-50 barg, or 10-40 barg, or 20-40 barg, or 25-40 barg, or 10-35 barg, or 20-35 barg, or 25-35 barg).

[0262] Implementation Scheme 138. The method according to any one of Implementation Schemes 1-137, wherein the second pressure is in the range of 20-50 barg.

[0263] Implementation Scheme 139. The method according to any one of Implementation Schemes 1-138, wherein the Fischer-Tropsch reaction is carried out at 1,000 to 2,000,000 h. -1Within the range (e.g., from 1,000 to 1,200,000 h) -1 Or 1,000 to 500,000 h -1 Or 1,000 to 100,000 h -1 Or 5,000 to 1,200,000 h -1 Or 5,000 to 500,000 h -1 Or 5,000 to 100,000h -1 Or 10,000 to 1,200,000 h -1 Or 10,000 to 500,000 h -1 Or 10,000 to 100,000 h -1 The process is performed under GHSV within the specified range.

[0264] Implementation Scheme 140. The method according to any one of Implementation Schemes 1-139, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50% or at least 70% C 5+ Selective implementation.

[0265] Implementation Scheme 141. The method according to any one of Implementation Schemes 1-140, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50% or at least 70% C 5+ Alkanes are selectively processed.

[0266] Implementation Scheme 142. The method according to any one of Implementation Schemes 1-141, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, for example at least 50% or at least 70% C 5+ Alkanes and C 5+ Alcohols are selectively processed.

[0267] Implementation Scheme 143. The method according to any one of Implementation Schemes 1-142, further comprising separating at least a portion of water from the second product stream.

[0268] Implementation Scheme 144. The method according to any one of Implementation Schemes 1-143, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0269] Implementation Scheme 145. The method according to Implementation Scheme 144 further includes including at least a portion of the light hydrocarbon feed stream in the first feed stream and / or the second feed stream.

[0270] Implementation Scheme 146. The method according to Implementation Scheme 144 or Implementation Scheme 145 further includes oxidizing at least a portion of the light hydrocarbon feed stream to provide a pOX feed stream containing CO and / or CO2, and including at least a portion of the pOX feed stream in the first feed stream and / or the second feed stream.

[0271] Implementation Scheme 147. The method according to any one of Implementation Schemes 144-146, wherein the light hydrocarbon feed stream comprises methane from biogas.

[0272] Implementation Scheme 148. The method according to Implementation Scheme 147, comprising providing a biogas comprising CO2 and methane, providing at least a portion of the CO2 to the first feed stream, and providing at least a portion of the methane to the oxidation of at least a portion of the light hydrocarbon stream.

[0273] Implementation Scheme 149. The method according to any one of Implementation Schemes 144-148 further comprises burning at least a portion of the light hydrocarbon feed stream to provide energy, such as thermal or electrical energy.

[0274] Implementation Scheme 150. The method according to Implementation Scheme 149, wherein the thermal energy is used to heat the first feed stream.

[0275] Implementation Scheme 151. The method according to any one of Implementation Schemes 1-150, wherein the method further comprises 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 first feed stream and providing heat to the steam generating zone.

[0276] Implementation Scheme 152. The method according to Implementation Scheme 151 further includes generating steam from heat supplied to the steam generating zone and generating electricity from the steam.

[0277] Implementation Scheme 153. The method according to Implementation Scheme 151 or 152, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0278] Implementation Scheme 154. The method according to any one of Implementation Schemes 1-153, 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.

[0279] Implementation Scheme 155. The method according to any one of Implementation Schemes 1-154, further comprising recycling at least a portion of the H2 of the second product stream to the second feed stream.

[0280] Implementation Scheme 156. The method according to any one of Implementation Schemes 1-155, further comprising recycling at least a portion of the H2 of the second product stream to the first feed stream.

[0281] Implementation Scheme 157. The method according to Implementation Scheme 156 further includes providing H2 from an H2 source other than the first product stream to the second feed stream.

[0282] Implementation Scheme 158. The method according to Implementation Scheme 157, wherein H2 from the second product stream constitutes a majority of H2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of H2 of the first feed stream.

[0283] Implementation Scheme 159. The method according to any one of Implementation Schemes 1-158, further comprising recycling at least a portion of the CO of the second product stream to the second feed stream.

[0284] Implementation Scheme 160. The method according to any one of Implementation Schemes 1-159, further comprising recycling at least a portion of the CO of the second product stream to the first feed stream.

[0285] Implementation Scheme 161. The method according to any one of Implementation Schemes 1-160, further comprising recycling at least a portion of the inert material of the second product stream to the second feed stream.

[0286] Implementation Scheme 162. The method according to any one of Implementation Schemes 1-161, further comprising recycling at least a portion of the inert material of the second product stream to the first feed stream.

[0287] Implementation Scheme 163. The method according to any one of Implementation Schemes 1-162, further comprising recycling at least a portion of the CO2 from the second product stream to the first feed stream.

[0288] Implementation Scheme 164. The method according to Implementation Scheme 163 further includes providing CO2 from a CO2 source other than the first product stream to the second feed stream.

[0289] Implementation Scheme 165. The method according to Implementation Scheme 164, 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 product stream.

[0290] Implementation Scheme 166. The method according to any one of Implementation Schemes 1-165, wherein C from the second product stream 5+At least a portion of the hydrocarbons provides one or more products.

[0291] Implementation Scheme 167. The method according to Implementation Scheme 166, wherein the one or more products include fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants, and waxes.

[0292] Implementation Scheme 168. The method according to any one of Implementation Schemes 1-167, further comprising hydrogenating the C of the second product stream. 5+ At least a portion of hydrocarbons.

[0293] Implementation Scheme 169. The method according to any one of Implementation Schemes 1-168, wherein at least a portion of the CO2 in the second feed stream comes from a renewable source.

[0294] Implementation Scheme 170. The method according to any one of Implementation Schemes 1-169, wherein at least a portion of the CO2 in the second feed stream originates from biogas, CO2 emission sources, and / or direct air capture.

[0295] Implementation Scheme 171. The method according to any one of Implementation Schemes 1-170, wherein at least a portion of the CO2 in the second feed stream originates from biogas.

[0296] Implementation Scheme 172. The method according to any one of Implementation Schemes 1-171, wherein at least a portion of the CO2 in the second feed stream is derived from direct air capture.

[0297] Implementation Scheme 173. The method according to any one of Implementation Schemes 1-171, wherein at least a portion of the CO2 in the second feed stream originates from a CO2 emission source (e.g., from a manufacturing plant, such as a bioethanol plant, steel plant, or cement plant).

[0298] Implementation Scheme 174. The method according to any one of Implementation Schemes 1-173, wherein at least a portion of H2 of the first feed stream or the second feed stream originates from a renewable source.

[0299] Implementation Scheme 175. The method according to any one of Implementation Schemes 1-174, wherein at least a portion of the hydrogen in the first feed stream or the second feed stream is green hydrogen.

[0300] Implementation Scheme 176. The method according to any one of Implementation Schemes 1-175, wherein at least a portion of the hydrogen in the first feed stream or the second feed stream is blue hydrogen.

[0301] Implementation Scheme 177. The method according to any one of Implementation Schemes 1-176, wherein at least a portion of the hydrogen in the first feed stream or the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0302] Implementation Scheme 178. The method according to any one of Implementation Schemes 1-177, further comprising providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolyzing water.

[0303] Implementation Scheme 179. The method according to Implementation Scheme 178, wherein the electrolysis of water is carried out using electricity from at least a portion of a renewable source.

[0304] Implementation Scheme 180. The method according to Implementation Scheme 178 or Implementation Scheme 179, wherein the water electrolysis is carried out using steam generated from heat exchange of the first product stream and / or the second product stream, or electricity generated by burning a light hydrocarbon stream (e.g., methane from biogas).

[0305] Implementation Scheme 181. The method according to any one of Implementation Schemes 176-180, further comprising providing at least a portion of the O2 generated in the electrolysis to partial oxidation.

[0306] Implementation Scheme 182. The method according to any one of Implementation Schemes 1-181, wherein the method is carried out in a reactor system comprising a first reactor in which the reverse water-gas shift catalyst is disposed, and a second reactor in which the Fischer-Tropsch catalyst is disposed.

[0307] Implementation Scheme 183. The method according to any one of Implementation Schemes 1-182, wherein the method is carried out in a reactor system comprising a first catalyst bed wherein the reverse water-gas shift catalyst is disposed, and wherein a second reaction zone comprises a second catalyst bed wherein the Fischer-Tropsch catalyst is disposed.

[0308] Implementation Scheme 184. The method according to Implementation Scheme 183, wherein the first reactor bed and the second reactor bed are disposed in the same reactor.

[0309] Implementation Scheme 185. The method according to any one of Implementation Schemes 1-184, wherein the method is carried out in a reactor system comprising one or more first catalyst vessels in which the reverse water-gas shift catalyst is disposed, and wherein the second reaction zone comprises one or more second catalyst vessels in which the Fischer-Tropsch catalyst is disposed.

[0310] Implementation Scheme 186. The method according to Implementation Scheme 185, wherein the one or more first catalyst containers and the one or more second catalyst containers are disposed in the same reactor.

[0311] Implementation Scheme 187. The method according to any one of Implementation Schemes 1-186, wherein the method is carried out in a reactor system comprising a reactor wherein the reverse water gas shift catalyst and the Fischer-Tropsch catalyst (e.g., a mixture) are disposed.

[0312] The details shown herein are merely illustrative and for the purpose of discussing preferred embodiments of the invention in an illustrative manner, and are intended to provide the most useful and readily understood description of the principles and concepts believed to be among the various embodiments of the invention. In this respect, no attempt is made to show the structural details of the invention in more detail than is necessary for a basic understanding of the invention. The description, taken in conjunction with the accompanying drawings and / or embodiments, makes it clear to those skilled in the art how several forms of the invention can be embodied in practice. Therefore, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, devices, or constructions, and therefore, variations are naturally possible. It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting unless specifically defined herein.

[0313] Unless otherwise stated herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar designations used in the context of describing the invention (particularly in the context of the following claims) shall be interpreted to cover both the singular and the plural. The description of numerical ranges herein is intended only as a shorthand method of individually referring to each individual value falling within the range. Unless otherwise stated herein, each individual value is incorporated into this specification as if it were individually referenced herein. It will be further understood that the endpoints of each range are significant both relative to and independent of the other endpoint.

[0314] Unless otherwise stated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order of steps. The use of any and all embodiments or exemplary language (e.g., “for example”) provided herein is intended only to better illustrate the invention and not to limit the scope of the separately claimed invention. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0315] Unless the context explicitly requires otherwise, throughout the specification and claims, the terms "comprise," "comprising," etc., shall be interpreted in an inclusive sense, rather than an exclusive or exhaustive sense; that is, in the sense of "including but not limited to." The use of singular or plural terms shall also include both singular and plural forms, respectively. Furthermore, when used in this application, the terms "this article," "above," and "below," and similar terms, shall refer to the entire application and not any particular part thereof.

[0316] As will be understood by those skilled in the art, each embodiment disclosed herein may include, consist of, or be substantially composed of the elements, steps, ingredients, or components specifically stated herein. As used herein, the transitional terms “comprise” or “comprises” mean, but are not limited to, and allow the inclusion of unspecified elements, steps, ingredients, or components, even in substantial quantities. The transitional phrase “consisting of” excludes any unspecified elements, steps, ingredients, or components. The transitional phrase “substantially composed of” limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not substantially affect the embodiment.

[0317] Unless otherwise stated, the numerical parameters listed in the specification and appended claims are approximate values ​​and may vary depending on the desired properties sought to be obtained according to the invention. At least, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter shall be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0318] Although the wide range of numerical values ​​and parameters described in this invention are approximate, the values ​​described in the specific embodiments are reported as accurately as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in their respective test measurements.

[0319] The grouping of alternative elements or embodiments of the invention disclosed herein should not be construed as limiting. Each member of a group may be mentioned and claimed individually or in any combination with other members of that group or other elements found herein. For convenience and / or patentability reasons, it is contemplated that one or more members of a group may be included in or removed from the group. When any such inclusion or removal occurs, this specification is deemed to contain the modified group, thereby satisfying the written description of all Markush groups used in the appended claims.

[0320] This document describes some embodiments of the invention, including the inventors' known best mode for carrying out the invention. Of course, variations of these described embodiments will become apparent to those skilled in the art after reading the foregoing specification. The inventors expect those skilled in the art to appropriately adopt these variations, and the inventors intend to practice the invention in ways other than those specifically described herein. Therefore, the invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the invention covers any combination of the foregoing elements in all possible variations.

[0321] Extensive references have been made to patents and print publications throughout this specification. Each of the cited references and print publications is individually incorporated herein by reference in its entirety.

[0322] Furthermore, it should be understood that the embodiments of the invention disclosed herein illustrate the principles of the invention. Other modifications may be employed within the scope of the invention. Therefore, alternative configurations of the invention can be utilized based on the teachings herein, by way of example and not limitation. Thus, the invention is not limited to what is precisely shown and described.

Claims

1. A method for performing integrated Fischer-Tropsch analysis, the method comprising: A first feed stream comprising H2, CO2 and methane is provided, wherein at least a portion of the CO2 in the first feed stream originates from biogas, and wherein at least a portion of the methane in the first feed stream originates from biogas. At a first temperature and a first pressure within the range of 200-1100°C, the reverse water gas shift catalyst is brought into contact with the first feed stream to carry out a reverse water gas shift reaction to provide a first product stream containing CO and H2, wherein the first product stream has a lower CO2 concentration and a higher CO concentration compared to the first feed stream. The Fischer-Tropsch catalyst is contacted with a second feed stream containing H2 and at least a portion of CO from the first product stream at a second temperature and a second pressure to provide C. 5+ The second product stream of hydrocarbons.

2. The method of claim 1, wherein the CO2 in the first feed stream comprises at least 75% by volume CO2 from biogas.

3. The method according to claim 1 or claim 2, wherein the methane in the first feed stream comprises at least 75% by volume methane from biogas.

4. The method according to any one of claims 1-3, wherein the molar ratio of H2 to methane in the first feed stream is in the range of 0.25:1 to 5:

1.

5. The method according to any one of claims 1-4, wherein the molar ratio of methane to CO2 in the first feed stream is in the range of 0.25:1 to 4:1 (e.g., in the range of 0.3:1 to 3:1, in the range of 0.4:1 to 2.5:1, or in the range of 0.5:1 to 2:1).

6. The method according to any one of claims 1-5, wherein the molar amount of methane in the first feed stream is approximately the same as the molar amount of CO2 in the first feed stream (e.g., in the range of 0.95:1 to 1.05:1).

7. The method according to any one of claims 1-6, wherein providing the first feed stream comprises providing a biogas stream, separating at least a portion of water from the biogas stream to provide a water-poor biogas stream, and providing CO2 from the biogas and methane from the biogas stream.

8. The method according to any one of claims 1-7, wherein providing the first feed stream comprises providing a biogas stream, separating at least a portion of hydrogen sulfide from the biogas stream to provide a hydrogen sulfide-poor biogas stream, and providing CO2 from the biogas and methane from the biogas stream.

9. The method according to any one of claims 1-8, wherein the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:

1.

10. The method according to any one of claims 1-9, wherein the reverse water-gas shift reaction has at least 95% CO selectivity, no more than 2% methane selectivity and / or at least 30% CO2 conversion rate.

11. The method according to any one of claims 1-10, wherein the method further comprises separating the first product stream to recycle at least a portion of the CO2 of the H2 in the first product stream back to the first feed stream.

12. The method according to any one of claims 1-11, wherein at least 25% of the CO in the first product stream is included in the second feed stream, wherein the first product stream includes H2, and wherein at least 25% of the H2 in the first product stream is included in the second feed stream.

13. The method according to any one of claims 1-12, wherein the second temperature is in the range of 200-350°C, and wherein the first temperature is at least 100°C higher than the second temperature.

14. The method according to any one of claims 1-13, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with a C content of at least 30%. 5+ Alkanes are selectively processed.

15. The method according to any one of claims 1-14, further comprising recycling at least a portion of the H2 and / or at least a portion of the CO of the second product stream to the second feed stream or to the first feed stream, and / or further comprising recycling at least a portion of the CO2 of the second product stream to the first feed stream.

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