Integrated fischer-tropsch process

Abstract

The present disclosure generally relates to a process for performing an integrated Fischer-Tropsch process, the process comprising: providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst with the first feed stream at a first temperature in the range of 200-900 DEG C and at a first pressure for a reverse water gas shift reaction to provide a first product stream comprising CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream; the Fischer-Tropsch catalyst is contacted with a second feed stream comprising H2 and at least a portion of CO of the first product stream at a second temperature and at a second pressure to provide a second product stream comprising C5 + hydrocarbons.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority benefit of international patent application No. PCT / CN2022 / 102724 filed on June 30, 2022, which is hereby incorporated by reference in its entirety.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] 1. Field

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

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

[0007]

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

[0009]

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

[0011]

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

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

[0014]

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

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

[0017]

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

[0019] Given the multiple reactions at play and the competing thermodynamics, there remains a need in the art for new integrations with the Fischer-Tropsch process. SUMMARY OF THE INVENTION

[0021] In one aspect, the present disclosure provides a method of performing an integrated Fischer-Tropsch process, the method comprising:

[0022] Providing a first feed stream comprising H2 and CO2;

[0023] contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream;

[0024] contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a product comprising C 5+ A second product stream of hydrocarbons.

[0025] BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0027] Figure 2 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0028] Figure 3 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0029] Figure 4 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0030] Figure 5 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein.

[0031] Figure 6 is a schematic diagram of a method for performing an integrated Fischer-Tropsch process as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0033] As described above, the reverse water gas shift reaction reacts carbon dioxide with hydrogen to form carbon monoxide and water, and can be used to provide a feedstock containing carbon monoxide and hydrogen - commonly referred to as "syngas" - for use in processes such as the Fischer-Tropsch process. However, the Sabatier reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction. The Sabatier reaction and CO methanation are exothermic and are dominant at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and are dominant at higher temperatures. Therefore, there is still a need to integrate the reverse water gas shift process with the Fischer-Tropsch process.

[0034] In one aspect, the present disclosure provides a method for performing an integrated Fischer-Tropsch process, the method comprising providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst with the first feed stream at a first temperature in the range of 200-900°C and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H2, wherein the first product stream has a lower concentration of CO2 and a higher concentration of CO than the first feed stream; contacting the Fischer-Tropsch catalyst with a second feed stream comprising H2 and at least a portion of the CO of the first product stream at a second temperature and at a second pressure to provide a product stream comprising C 5+ A second product stream of hydrocarbons.

[0035] The method as described herein comprises contacting a reverse water gas shift catalyst with a first feed stream as described herein.The reverse water gas shift catalyst is not particularly limited and one of ordinary skill in the art will be able to select an appropriate catalyst. For example, a person skilled in the art or ordinary skill will be able to select a catalyst 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." RSC Adv., 2016, 6, 49675-49691, Zhu et al., "Catalytic Reduction of CO2to COvia Reverse Water Gas Shift Reaction: Recent Advances in the Design of Activeand 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 theReverse Water-Gas Shift Reaction." Front. Chem., 2020, 8, 709. 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 a combination thereof.

[0036] Reverse water gas shift catalysts suitable for use in the methods described herein can be in various forms and are not particularly limited. For example, the reverse water gas shift catalyst can be a supported or unsupported catalyst. Although the form of the catalyst is not particularly limited, in various desirable embodiments, the reverse water gas shift catalyst is a supported catalyst, wherein the carrier includes at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide, and zinc oxide. For example, in various embodiments, the carrier includes at least one of titanium oxide, zirconium oxide, cerium oxide, and aluminum oxide. In some embodiments of the present disclosure as described herein, the carrier is a titanium dioxide carrier. In some embodiments of the present disclosure as described herein, the carrier is a zirconium dioxide carrier. In some embodiments of the present disclosure as described herein, the carrier is a ceria carrier. In some embodiments of the present disclosure as described herein, the carrier is an aluminum dioxide carrier.

[0037] Those of ordinary skill in the art will appreciate that the reverse water gas shift catalysts of the present disclosure may be provided in many forms, particularly depending on the particular form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The carrier of the reverse water gas shift catalyst may itself be provided as a discrete body of material, for example as a porous particle, pellet, or shaped extrudate, with a metal disposed thereon to provide the reverse water gas shift catalyst. However, in other embodiments, the reverse water gas shift catalyst of the present disclosure may itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or a metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths. Those of ordinary skill in the art will select an appropriate Fischer-Tropsch catalyst for a particular reactor system.

[0038] The method includes providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst as described herein with the first feed stream at a first temperature in the range of 200-900°C and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H2, the first product stream having a lower concentration of CO2 and a higher concentration of CO than the first feed stream. Figure 1 An example of such a method is shown schematically in Figure 1 In the method 100 herein, the method 100 includes performing a reverse water gas shift reaction by providing a first feed stream 111 comprising H2 and CO2 to a first reaction zone, such as a reactor 110. As described herein, a reverse water gas shift catalyst 113 is contacted with the feed stream 111 at a first temperature in the range of 200-900°C and at a first pressure to provide a first product stream 112 comprising CO and H2. The first product stream has a lower concentration of CO2 and a higher concentration of CO than the first feed stream. The method of this aspect of the present disclosure also includes contacting the Fischer-Tropsch catalyst with a second feed stream comprising H2 and at least a portion of the CO of the first product stream at a second temperature and at a second pressure to provide a first product stream 112 comprising CO and H2. 5+ A second product stream of hydrocarbons. Figure 1 In the process 100, at least a portion of the CO of the first product stream 112 is contained in the second feed stream 121, where the second feed stream 121 is contacted with the Fischer-Tropsch catalyst 123 in the second reaction zone (e.g., reactor 120). This provides a catalyst containing C 5+ A second product stream 122 of hydrocarbons.

[0039] As used herein, "feed stream" is used to refer to the total material input to a process step, such as the reverse water gas shift or Fischer-Tropsch reaction, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single inlet or through multiple inlets. For example, the H2 and CO of the first feed stream can be provided to the reverse water gas shift catalyst in a single physical stream (e.g., in a single conduit to the reactor 110) or in multiple physical streams (e.g., separate inlets for CO and H2, or one inlet for fresh CO and H2 and another inlet for recycled CO and / or H2). Similarly, "product stream" is used to refer to the total material output from a process step, such as the reverse water gas shift or Fischer-Tropsch reaction, whether provided in a single physical stream or in multiple physical streams, and whether provided through a single outlet or through multiple outlets.

[0040] 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 described elsewhere 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, does not exceed 75:1 or does not exceed 50:1. In some embodiments, the molar ratio of H2 to CO2 in the first feed stream does not exceed 20:1, for example, does not exceed 15:1 or does not exceed 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, one of ordinary skill in the art will provide a desired ratio of H2:CO2 in the first feed stream that provides a desired conversion and selectivity; if consistent with the desired conversion and selectivity, an excess of H2 can be provided to flow through the system, and a first product stream having a desired H2 to CO ratio can be provided for a downstream process (e.g., a Fischer-Tropsch process).

[0041] Other gases may also be included in the first feed stream. For example, in some embodiments, the first feed stream further comprises CO. In some embodiments of the present disclosure as otherwise 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.

[0042] The method as described herein includes contacting the rWGS catalyst with the first feed stream to carry out the rWGS reaction. It is noteworthy that the inventors have determined that the rWGS catalyst described herein can provide a desirably high CO selectivity. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO selectivity of at least 70%, such as at least 80%. In various embodiments, the reverse water gas shift reaction has a CO selectivity of at least 85%, such as or at least 90%. In various embodiments, the reverse water gas shift reaction has a CO selectivity of at least 95%, such as or at least 96%. The "selectivity" of a given reaction product as used herein is the mole fraction of the relevant component of the feed (here CO2) 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 operating at lower temperatures than many conventional reverse water gas shift catalysts, despite the competitive potential of the Sabatier reaction and CO methanation. For example, in some embodiments as otherwise described herein, the reverse water gas shift reaction has a CO selectivity of at least 98%, eg, or at least 99%.

[0043] It is noteworthy that the rWGS catalysts described herein can be operated to provide carbon monoxide even over a wide range of temperatures, such as temperatures in the range of 200-900°C, with only a minimal degree of methane formation. For example, in various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a methane selectivity of no more than 5%, such as no more than 4%. For example, in some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 2%, such as no more than 1%. In some embodiments, the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, such as no more than 0.2%.

[0044] The inventors have determined that the rWGS catalysts described herein can provide desirable high CO selectivity and desirable low methane selectivity at commercially relevant conversions. "Conversion" as used herein is the mole fraction of the relevant component feeds of the reaction (whether the reaction is a desirable product or an undesirable species). In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO2 conversion of at least 5%, such as at least 10%, or at least 20%. For example, in some embodiments, the reverse water gas shift reaction has a CO2 conversion of at least 30%, such as at least 40%, or at least 50%, or at least 60%. In various embodiments of the present disclosure as described herein, the reverse water gas shift reaction has a CO2 conversion of no more than 90%, such as no more than 80% or no more than 70%. For example, in some embodiments, the reverse water gas shift reaction has a CO2 conversion of no more than 65%, such as no more than 60%. For example, in various embodiments as described separately herein, CO conversion rate is 10-90%, for example 10-80%, or 10-70%, or 10-60%, or 10-65%, or 20-90%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30-90%, or 30-80%, or 30-70%, or 30-60%, or 30-65%, or 40-90%, or 40-80%, or 40-70%, or 40-60%, or 40-65% scope. Based on the disclosure herein, those of ordinary skill in the art will operate under the degree of conversion that provides the desired product. Of course, in other embodiments, for example when in a stacked bed or mixed bed system, effective CO conversion rate can be even higher than the conversion rate described herein.

[0045] Advantageously, the rWGS methods described herein can be carried out at temperatures lower than those used in many conventional reverse water gas shift methods. As described above, the various methods of performing the rWGS reaction of the present disclosure can be carried out at a first temperature in the range of 200-900°C. For example, in some embodiments, the reverse water gas shift reaction is carried out at a first temperature in the range of 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 the present disclosure as described herein, the method for performing the reverse water gas shift reaction is carried out in the range of 250-900°C, for example, at a first temperature 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. In some embodiments of the disclosure as described herein, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 300-900° C., for example, in the range of 300-850° C., or 300-800° C., or 300-750° C., or 300-700° C., or 300-650° C., or 300-600° C. In some embodiments of the disclosure as described herein, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 350-900° C., for example, in the range of 350-850° C., or 350-800° C., or 350-750° C., or 350-700° C., or 350-650° C., or 350-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 400-900° C., such as in the range of 400-850° C., or 400-800° C., or 400-750° C., or 400-700° C., or 400-650° C., or 400-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 450-900° C., such as in the range of 450-850° C., or 450-800° C., or 450-750° C., or 450-700° C., or 450-650° C., or 450-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 500-900° C., such as in the range of 500-850° C., or 500-800° C., or 500-750° C., or 500-700° C., or 500-650° C., or 500-600° C. In some embodiments, the method for performing the reverse water gas shift reaction is carried out at a first temperature in the range of 550-900° C., such as 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.

[0046] In some embodiments, the reverse water gas shift reaction is carried out at a first temperature in the range of 200-500° C., e.g., 200-450° C., or 200-400° C., or 200-350° C., or 250-500° C., or 250-450° C., or 250-400° C., or 250-350° C. The inventors have noted that operation at these temperatures can provide lower energy requirements, as well as facilitate integration with subsequent Fischer-Tropsch steps.

[0047] In addition, as will be appreciated by those of ordinary skill in the art, the rWGS method described herein can be carried out at various pressures. In various embodiments of the present disclosure, the method for carrying out the reverse water gas shift reaction is carried out at a first pressure in the range of 1 to 100 bar. For example, the rWGS method is carried out at a first pressure in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 70 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar.

[0048] As will be appreciated by one of ordinary skill in the art, the rWGS methods described herein can be performed at various GHSVs (gas hourly space velocities). Thus, the GHSV for performing the reverse water gas shift reaction is not particularly limited. For example, in some embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is performed at 1,000 to 2,000,000 h -1 In various embodiments, the method for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the method for performing the reverse water gas shift reaction is carried out at a GHSV of 1,000 to 50,000 h -1, or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1 , or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h -1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

[0049] It will generally be desirable to activate the rWGS catalyst, for example, before contacting with the first feed stream. Thus, in some embodiments of the present disclosure as described herein, the method includes activating the rWGS catalyst before contacting the catalyst with the feed stream. For example, in some embodiments, activating the catalyst includes contacting the catalyst with a reducing stream comprising a reducing gas (e.g., hydrogen). In various embodiments of the present disclosure, the reducing stream comprises hydrogen in an amount of at least 25 mol%, such as at least 50 mol%, or 75 mol%, or 90 mol%. One of ordinary skill in the art will determine conditions suitable for reducing and activating the rWGS catalyst. Therefore, one of ordinary skill in the art will be able to select appropriate temperature, pressure, and time to activate the rWGS catalyst. For example, in various embodiments, the activation rWGS catalyst is carried out at a temperature in the range of 200°C to 800°C. For example, in various embodiments, activating the rWGS catalyst is carried out at a temperature in the range of 250° C. to 800° C., or 300° C. to 800° C., or 200° C. to 700° C., or 250° C. to 800° C., or 300° C. to 700° C. In some embodiments of the disclosure as described herein, activating the rWGS catalyst provides an at least 10% reduced (e.g., at least 25%, or at least 50% reduced) rWGS catalyst.

[0050] The inventors have found that contacting the rWGS catalyst as described herein with the first feed stream can provide a first product stream having advantageously high CO selectivity and low methane selectivity. As described above, the amount of CO in the first product stream can be further controlled by the rWGS reaction conditions. However, in general, the method for performing the rWGS reaction as described herein provides 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, which is consistent with the degree of conversion and selectivity described herein. For example, in various embodiments, the first product stream comprises no more than 95 mol % of CO2, or no more than 90 mol % of CO2. In some embodiments, the first product stream comprises no more than 85 mol % of CO2, or no more than 80 mol % of CO2. In other examples, the first product stream comprises no more than 75 mol % or no more than 70 mol % of CO2.

[0051] However, as described above, the inventors have determined that it may be desirable to conduct the process at an intermediate degree of conversion to provide a desirably high CO selectivity and a desirably low methane selectivity. In addition, the inventors have noted that it may be advantageous to conduct the downstream Fischer-Tropsch process with relatively high levels of inerts, and thus contemplate that it may be beneficial to feed a significant amount of CO2 to the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the first product stream comprises an amount of CO2 as well as CO. In various embodiments, the first product stream contains CO2 in the range of 5-95 mol%, for example, 5-90 mol%, or 5-85 mol%, or 5-80 mol%, or 5-75 mol%, or 5-70 mol%, or 10-95 mol%, or 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% CO2.

[0052] Other gases may also be included in the first product stream. In some embodiments of the present disclosure as described elsewhere herein, the first product stream further comprises one or more inert gases. These inert gases may be included in the first feed stream or provided from a source other than the first feed stream. For example, in some embodiments, the first product stream further comprises nitrogen and / or methane.

[0053] The first product stream may comprise H2 in various ratios combined with CO, depending on, among other things, the degree of conversion, CO selectivity, the relative amounts of H2 and CO2 in the first feed stream, and the reaction conditions. For example, in some embodiments, the ratio of H2:CO 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).

[0054] One of ordinary skill in the art will appreciate that, based on the process as described herein, the first product stream may contain H2, CO, and CO2 as well as various amounts of other components. The components of the first product stream may be separated and used for various purposes in the integrated process.

[0055] For example, in various embodiments of the present disclosure as described herein, the method further includes separating the first product stream so as to recycle at least a portion of one or more components of the first product stream (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the first feed stream. For example, when the first product stream contains CO2, the method may include recycling at least a portion of the CO2 of the first product stream (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the first feed stream. The first product stream may also contain H2; in some embodiments, the method further includes recycling at least a portion of the H2 of the first product stream (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the first feed stream.

[0056] This type of recirculation is shown in Figure 1 Here, method 100 includes separating at least a portion of CO2 (stream 114) from first product stream 112 for recycling to first feed stream 111. Similarly, method 100 includes separating at least a portion of H2 (stream 115) from first product stream 112 for recycling to first product stream 111. Although stream 115 is depicted as entering reactor 110 through a different inlet than the rest of first feed stream 111, it is considered part of the first feed stream because it is part of the material input to the process step.

[0057] In addition, as described below, the Fischer-Tropsch catalyst generally requires activation by a reducing gas. As will be appreciated by those skilled in the art, different Fischer-Tropsch catalysts require different activation conditions (e.g., gas composition, temperature, pressure, time). For example, an iron-based Fischer-Tropsch catalyst requires activation with H2 and CO, while a cobalt-based Fischer-Tropsch catalyst requires only H2 activation. Therefore, H2 and CO or only H2 from the first product stream can be used to perform the activation. Therefore, in various embodiments as described elsewhere herein, the method includes separating at least a portion of the H2 and CO from the first product stream (desirably in a ratio of at least 1:1 or at least 3:1) and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. In various other embodiments as described elsewhere herein, the method includes separating at least a portion of the H2 from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. For example, in Figure 1 In the process, stream 125 separates H2 or H2 from CO and directs it to reactor 120. This separation need not be continuous; rather, it only needs to be performed for a period of time required to provide a reducing gas to the Fischer-Tropsch catalyst for activation. Of course, as will be appreciated by those skilled in the art, other sources of H2 or CO may be used to provide a reducing gas to the Fischer-Tropsch catalyst for activation.

[0058] As indicated above, water is a product of the reverse water gas shift reaction. Thus, the first product stream will typically contain water. In many cases, it may be desirable to reduce the amount of water provided to the Fischer-Tropsch step. Thus, in various embodiments as otherwise described herein, the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream. Figure 1 In the embodiment of the present invention, the water removal zone 116 is used to remove water and provide an aqueous stream 117. It will be understood by those of ordinary skill in the art that various methods can be used to remove water from the first product stream. For example, the first product stream can be contacted with a water removal agent to remove water therefrom. For example, a molecular sieve guard bed can be used to remove water from the first product stream; water can be recovered from the molecular sieves of the guard bed, for example, by heating and vacuum. In other embodiments, a separator (knockout vessel) can be used. However, the use of a separator can in some cases sufficiently cool the first product stream so that it is desirable to reheat it for introduction into the Fischer-Tropsch process step. The water removed from the first product stream can be used as, for example, feed water for the electrolysis process described herein.

[0059] As mentioned above, one of the competing reactions in the reverse water gas shift reaction is the Sabatier reaction, which manufactures methane. Although in various embodiments, the reverse water gas shift method described herein can be carried out without forming a large amount of methane, in some embodiments, some methane may be formed. Therefore, in various embodiments of the method as described herein, the 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 a combination thereof. As will be appreciated by those of ordinary skill in the art, it may be desirable to operate the reverse water gas shift reaction so as to provide a higher amount of light hydrocarbons in the first product feed. For example, such light hydrocarbons may be inert in the further processing of the first product stream, and therefore may be acceptable at higher amounts. Those of ordinary skill in the art will be able to select appropriate reaction conditions (e.g., temperature, pressure, first feed stream composition) to provide a first product stream comprising methane in a desired amount. For example, in various embodiments as described separately herein, the first product stream comprises no more than 20 mol %, or no more than 15 mol % of methane. As described above, when a lower amount of methane is desired in the first product stream, the rWGS catalyst of the present disclosure can provide very low methane selectivity. Therefore, in various embodiments as described separately herein, the first product stream comprises no more than 10 mol % of methane. For example, in various embodiments, the first product stream comprises 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 described separately herein, the product stream comprises 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).

[0060] 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. Figure 1 In the method 100, at least a portion of one or more light hydrocarbons are separated from the first product stream 112 to provide a light hydrocarbon stream 118. The light hydrocarbon stream can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be combusted to provide heat or other energy (e.g., electricity for electrolysis) for integrated processes or other processes.

[0061] Of course, as will be appreciated by one of ordinary skill in the art, the light hydrocarbon stream may also be used in other processes. For example, as will be appreciated by one of ordinary skill in the art, some rWGS catalysts may have reforming capabilities. Without being bound by theory, the inventors hypothesize that one explanation for the low methane production observed using the rWGS catalysts as described herein is that methane is formed but then immediately reformed to CO and H2. Therefore, in some embodiments as described herein, the light hydrocarbons of the process stream are recycled to the feed stream for the rWGS reaction.

[0062] As described above, the reverse water gas shift process can be provided at a variety of temperatures. In some cases, these temperatures can be relatively close to the temperature of the subsequent Fischer-Tropsch step (typically 150-400°C, such as 200-350°C, or other temperatures as described below). In other cases, the reverse water gas shift process can be carried out at a temperature significantly higher than the temperature of the Fischer-Tropsch step. The inventors have noted that it may be desirable to provide heat exchange with a relatively hot first product stream in order to cool the first product stream to a temperature more suitable for the Fischer-Tropsch step and to provide heat to the integrated process elsewhere. For example, in various embodiments of the method as otherwise described herein, the method further includes exchanging heat between at least a portion of the first product stream and at least a portion of the first feed stream, thereby cooling at least a portion of the first product stream and heating at least a portion of the first feed stream. In Figure 2 An example of such a method is shown schematically in Figure 2 In the process 200, the first reactor 210, the first feed stream 211, the first product stream 212, the reverse water gas shift catalyst 213, the second reactor 220, the second feed stream 221, the second product stream 222 and the Fischer-Tropsch catalyst 223 are generally as described above. Here, the process 200 includes exchanging heat between at least a portion of the first product stream 212 and at least a portion of the first feed stream 211 in the first heat exchange zone 230, thereby cooling at least a portion of the first product stream 212 and heating at least a portion of the first feed stream 211. It will be appreciated by those of ordinary skill in the art that a variety of heat exchangers may be used for this purpose.

[0063] Of course, any excess heat in the first product stream can additionally or alternatively be used for other purposes. For example, in various embodiments, the method further includes exchanging heat between at least a portion of the first product stream and the steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone. This is shown in FIG. Figure 2Here, after heat exchange with the first feed stream 211, the first product stream 212 is directed to the steam generating zone 232 to cool the first product stream 212 and provide heat to the steam generating zone 232. Steam can be generated from the provided heat, and electricity can be generated from the steam. For example, in Figure 2 In the embodiment of the present invention, the electric current 264 is provided by generating electricity using the steam generated in the steam generating area 232. Of course, as will be appreciated by one of ordinary skill in the art, the steam generated in the steam generating area can be used for other processes. In various embodiments, the steam can be used to heat the first feed stream. For example, in Figure 2 In the embodiment of the present invention, the steam stream 266 generated in the steam generating zone 232 is directed to the heat exchange zone 290 to heat the first feed stream 211.

[0064] As described above, at least a portion of the CO of the first product stream is included in the second feed stream for reaction in the Fischer-Tropsch process. For example, in various embodiments as described elsewhere herein, at least 25% of the CO of the first product stream, for example, at least 50% of the CO of the first product stream, at least 75% of the CO, or at least 90% of the CO is included in the second feed stream. Of course, as described above, a portion of the CO of the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0065] In some embodiments, substantially all of the CO in the second feed stream is from the first product stream. However, in other embodiments, the CO can be provided to the second feed stream from other sources (fossil-derived or other). For example, in various embodiments, CO is provided to the second feed stream from a CO source other than the first product stream. Figure 2 In the embodiment of the present invention, a CO stream 226a from some other source is included in the second feed stream 221. It will be appreciated by those skilled in the art that CO can be provided from a variety of sources, such as gasification, reforming, or electrochemical CO2 reduction. In addition, as described in more detail below, CO can be recycled from the second product stream to the second feed stream; and / or can be provided by reaction of a light hydrocarbon stream, such as by partial oxidation or reforming (e.g., steam reforming and / or autothermal reforming).

[0066] As described above, the second feed stream includes H2. It is worth noting that the first product stream will generally include H2, such as unreacted H2 from the first feed stream. In various embodiments, the first product stream includes H2, wherein the second feed stream includes at least a portion of the H2 of the first product stream. For example, in various embodiments as described elsewhere herein, at least 25% of the H2 of the first product stream, such as at least 50% of the H2 of the first product stream, at least 75% of the H2, or at least 90% of the H2 is included in the second feed stream. Of course, as described above, a portion of the H2 of the first product stream can be used for other purposes, such as catalyst activation as described herein.

[0067] In some embodiments, substantially all of the H2 in the second feed stream comes from the first product stream. In fact, one of ordinary skill in the art can provide more H2 in the first feed stream than is required for the reverse water gas shift reaction so as to provide excess H2 in the first product stream, which can then provide the required amount of H2 to the second feed stream for the Fischer-Tropsch step. However, in other embodiments, H2 can be provided to the second feed stream from other sources. For example, in various embodiments, H2 is provided to the second feed stream from a source of H2 other than the first product stream. Figure 2 In the embodiment of the present invention, H2 stream 226b from some other source is included in the second feed stream 221. It will be appreciated by one of ordinary skill in the art that H2 can be provided from a variety of sources, such as gasification, reforming, or H2O electrolysis (including the electrolysis described herein). In addition, as described in more detail below, H2 can be recycled from the second product stream to the second feed stream.

[0068] Based on the disclosure herein, one of ordinary skill in the art can adjust the relative amounts of H2 and CO in the second feed stream to provide a desired ratio. For example, more or less of the H2 of the first feed stream and / or more or less of the H2 from electrolysis may be included in the second feed stream. Similarly, more or less of the CO of the first feed stream and more or less of the CO from other sources (e.g., partial oxidation and reforming as described below) may be included in the second feed stream.

[0069] As described above, it may be desirable to carry out the Fischer-Tropsch process step in the presence of significant levels of inerts. One such inert, CO2, may come from the reverse water-gas shift, for example via the first product stream. Therefore, in various embodiments as described elsewhere herein, the second feed stream comprises at least a portion of the CO2 of the first product stream. For example, in various embodiments, at least 10% of the CO2 of the first product stream, such as at least 25% of the CO2 of the first product stream, at least 50% of the CO2, at least 75% of the CO2, or at least 90% of the CO2 is contained in the second feed stream. Of course, in other embodiments, the second feed stream may not contain any significant amount of CO2 of the first product stream. Therefore, in various embodiments, the second feed stream does not contain a significant amount of CO2 of the first product stream. Although it may generally be desirable to recycle CO2 to the first feed stream for use in the reverse water-gas shift reaction, as described in more detail below, unreacted CO2 may be recycled from the second product stream to the first feed stream.

[0070] Additionally or alternatively, however, it may be desirable to include additional inert content in the second feed stream, whether CO2 or other inerts such as nitrogen and methane. For example, in various embodiments, one or more inerts (e.g., CO2, nitrogen, and / or methane) are provided to the second feed stream from a source other than the first product stream. Figure 2 In the second feed stream 221, an inert material stream 226c from some other source is included. It will be appreciated by those skilled in the art that inerts can be provided from a variety of sources. In addition, as described in more detail below, inerts can be recycled from the second product stream to the second feed stream.

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

[0072] As described above, other gases may also be included in the second feed stream. For example, as described above, it may be desirable to conduct the Fischer-Tropsch process step in the presence of a significant amount of inerts (i.e., components other than H2 or CO). For example, in various embodiments, the second feed stream comprises up to 80 mol% of one or more inerts, such as in the range of 3-80 mol%, or 5-80 mol%, or 10-80 mol%, or 15-80 mol%, or 30-80 mol%. In various embodiments, the second feed stream comprises up to 70 mol% inerts, up to 60 mol% inerts, or up to 50 mol% inerts, for example, 3-70 mol%, or 5-70 mol%, or 10-70 mol%, or 15-70 mol%, or 30-70 mol%, or 3-60 mol%, or 5-60 mol%, or 10-60 mol%, or 15-60 mol%, or 30-60 mol%, or 3-50 mol%, or 5-50 mol%, or 10-50 mol%, or 15-50 mol%, or 30-50 mol% inerts. In various embodiments, the second feed stream comprises up to 80% of one or more inerts selected from CO2, methane and nitrogen, for example up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%. In various embodiments, the second feed stream comprises up to 80 mol% CO2, for example up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol%.

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

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

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

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

[0077] The method described herein comprises contacting a Fischer-Tropsch catalyst with a second feed stream as described herein. There is no particular limitation on the Fischer-Tropsch catalyst used in the method as described herein, and one of ordinary skill in the art will be able to select a catalyst suitable for their desired Fischer-Tropsch product. In some embodiments, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0078] For example, in some embodiments of the present disclosure as described herein, the Fischer-Tropsch catalyst comprises cobalt, for example, in an amount in the range of 5-25 wt % calculated as Co(0). "Calculated as Co(0)" and similar terms refer to the use of the weight of the cobalt atoms / ions themselves in the calculation, rather than the total amount of any compounds or polynuclear ions in which those cobalt atoms / ions may be combined. For example, in various embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 7-25 wt %, or 10-25 wt %, or 5-20 wt %, or 7-20 wt %, or 10-20 wt %, calculated as Co(0). As will be understood by those of ordinary skill in the art, cobalt-based catalysts are typically provided to the reaction zone in the form of cobalt oxide on a support; the cobalt can be reduced and activated in situ (e.g., with H2) to provide an active catalyst species having a significant concentration of Co(0).

[0079] In some embodiments, the Fischer-Tropsch catalyst comprises iron, for example, in an amount in the range of 5-95 wt % calculated as Fe(0). For example, in various embodiments, the Fischer-Tropsch catalyst comprises iron in an amount in the range of 10-95 wt %, or 25-95 wt %, or 50-95 wt %, or 5-85 wt %, or 10-85 wt %, or 25-85 wt %, or 50-85 wt %, or 5-75 wt %, or 10-75 wt %, or 25-75 wt % calculated as Fe(0). As will be appreciated by those of ordinary skill in the art, iron-based catalysts are typically provided to the reaction zone in the form of metallic iron or iron oxide optionally on a carrier; iron can be activated (e.g., by reaction with H2 and CO) to provide an active catalyst species having a significant concentration of iron carbide.

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

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

[0082] Those of ordinary skill in the art will appreciate that the Fischer-Tropsch catalysts of the present disclosure may be provided in many forms, particularly depending on the particular form of the reactor system in which they are to be used, for example in a fixed bed or as a fluidized bed. The support for the Fischer-Tropsch catalyst may itself be provided as a discrete body of material, for example as a porous particle, pellet or shaped extrudate, wherein the metal is provided thereon to provide the Fischer-Tropsch catalyst. However, in other embodiments, the Fischer-Tropsch catalyst of the present disclosure may itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths. Those of ordinary skill in the art will select an appropriate Fischer-Tropsch catalyst for a particular reactor system.

[0083] As with rWGS catalysts, Fischer-Tropsch catalysts are typically activated prior to use, for example to provide cobalt(0) species on cobalt-based catalysts, or iron carbide species on iron-based catalysts. Such activation may be performed prior to contacting the Fischer-Tropsch catalyst with the second feed stream.

[0084] For example, in some embodiments, the Fischer-Tropsch catalyst is activated by contact with a reducing gas. For example, hydrogen can be a gas that is particularly suitable for activating a Fischer-Tropsch catalyst, such as when the activation is a reduction to a metal (0) species, such as for many cobalt-based catalysts. In various embodiments of the present disclosure as described elsewhere herein, the reducing gas comprises at least a portion of the H2 from the first product stream. For example, in some embodiments, the method further includes separating at least a portion of the H2 from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst. Figure 1 In the method 100 schematically shown in , at least a portion of the hydrogen stream 125 is separated from the first product stream 112 and contacted with the Fischer-Tropsch catalyst 123 to activate it. In other embodiments, H2 present in the second feed stream can be used to activate the catalyst. As will be understood by those of ordinary skill in the art, the activation temperature may vary depending on the Fischer-Tropsch catalyst used. Therefore, those of ordinary skill in the art will be able to select an appropriate temperature for activating the catalyst, for example in the range of 200-400°C.

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

[0086] As described above, the method includes contacting the Fischer-Tropsch catalyst with the second feed stream at a second temperature and a second pressure. One of ordinary skill in the art will select appropriate reaction conditions in conjunction with the specific feed and catalyst for providing the desired Fischer-Tropsch process. In some embodiments of the present disclosure as described herein, the second temperature is in the range of 150-400°C. For example, in various embodiments, the second temperature is in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C. In some specific embodiments, the second temperature is in the range of 200-350°C.

[0087] It is noteworthy that in many embodiments, the first temperature and the second temperature can be relatively close to each other. The inventors have noted that the reverse water gas shift catalyst described herein can provide suitable activity and CO selectivity even at relatively low temperatures. Therefore, the first product stream can be provided with a temperature suitable for or at least close to that suitable for the Fischer-Tropsch reaction step. This can desirably provide improved process integration. For example, in various embodiments, the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

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

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

[0090] As will be appreciated by those of ordinary skill in the art, the Fischer-Tropsch process described herein can be performed at various GHSV (gas hourly space velocity) values. Thus, there is no particular limitation on the GHSV at which the Fischer-Tropsch reaction is performed. For example, in some embodiments of the present disclosure, the process of performing the Fischer-Tropsch reaction is performed at 1,000 to 2,000,000 h -1 In various embodiments, the process for performing the reverse water gas shift reaction is carried out at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 In various embodiments of the present disclosure, the process of carrying out the Fischer-Tropsch reaction is carried out at a GHSV of 1,000 to 50,000 h. - 1 , or 2,000 to 50,000h -1 , or 5,000 to 50,000h -1 , or 10,000 to 50,000h -1 , or 1,000 to 40,000h -1 , or 2,000 to 40,000h-1 , or 5,000 to 40,000h -1 , or 10,000 to 40,000h -1 , or 1,000 to 30,000h -1 , or 2,000 to 30,000h -1 , or 5,000 to 30,000h -1 , or 10,000 to 30,000h -1 The results are carried out under a range of GHSV.

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

[0092] Additional components may be present in the second product stream. For example, in some embodiments, the second product stream comprises water, which is another product of the Fischer-Tropsch reaction. One or more light hydrocarbons (i.e., C1-C4) may also be present as byproducts. CO and / or H2 may be present, such as unreacted CO and / or H2 from the second feed stream. CO2 or other inerts described herein may also be present. Such components of the second product stream may be separated and / or recycled in various ways.

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

[0094] Light hydrocarbons, while generally not a desired portion of a Fischer-Tropsch product for use as a fuel or lubricant, can themselves be used for many purposes. Thus, in various embodiments, the method further comprises separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. The light hydrocarbon stream can, for example, be recycled to the first feed stream or the second feed stream. For example, in Figure 2 In the method 200, the light hydrocarbons can be provided as part of the recycle stream 236, which becomes part of the second feed stream 221. Figure 3 In the method 300, the light hydrocarbons can be provided as part of the recycle stream 336, which becomes part of the first feed stream 311. Figure 4 In the method 400 , light hydrocarbons are recycled to the first feed stream 411 via the recycle stream 442 .

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

[0096] Other methods can be used to provide CO and / or CO2 from a light hydrocarbon stream. For example, reforming technologies such as steam reforming and autothermal reforming can be used to provide CO through the reaction of hydrocarbons with water. Therefore, in various embodiments, the method further includes reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon stream to provide a reforming stream containing CO and / or CO2, and including at least a portion of the reforming stream in the first feed stream and / or the second feed stream. The water separated from the first and / or second product stream can be provided as part of the feed to the reforming described herein.

[0097] In addition, the light hydrocarbon stream can be burned to provide thermal energy, which can be used to heat various process streams, or to generate electricity. Thus, in various embodiments, the method includes burning at least a portion of the light hydrocarbon stream to provide energy, such as thermal energy or electrical energy. For example, in Figure 4 In the method 400, a portion of the light hydrocarbon stream 450 is combusted in a power generation area (here, in a generator 470) to generate electricity 472. In various embodiments, the thermal energy can be used to provide the required heat load for the reverse water gas shift process. For example, in Figure 4 In the method 400 of , a portion of the light hydrocarbon stream 450 is burned in the power generation zone (here, in the heat generator 480) to produce a heat stream 482. The heat stream 482 is directed to the heat exchange zone 490 to heat the first feed stream 411. Thermal energy can be similarly provided to the Fischer-Tropsch reaction. And as will be understood by those of ordinary skill in the art, other treatments of the light hydrocarbon stream (e.g., partial oxidation) can also provide energy, which can be used, for example, as described herein.

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

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

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

[0101] In some cases, for example, when H2 is provided to the second feed stream from a source of H2 other than the first product stream, the H2 from the second product stream may constitute a majority of the H2 of the first feed stream, for example at least 90%, at least 95%, or at least 98% of the H2 of the first feed stream. This is shown, for example, in Figure 4 Here, the primary H2 input to the process is through stream 440, which becomes part of the second feed stream 421. The H2 of the second product stream is contained in recycle stream 442, which becomes part of the first feed stream 411.

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

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

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

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

[0106] In some cases, for example, when CO2 is provided to the second feed stream from a CO2 source other than the first product stream, the CO2 from the second product stream may constitute a majority of the CO2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 of the first feed stream. This is shown, for example, in Figure 4 Here, the primary CO2 input to the process is through stream 440, which becomes part of the second feed stream 421. The CO2 of the second product stream is contained in a recycle stream 442, which becomes part of the first feed stream 411.

[0107] As described above, the Fischer-Tropsch process provides a 5+ A second product stream of hydrocarbons (e.g., unsubstituted hydrocarbons such as alkanes and olefins, and / or oxygenated hydrocarbons such as alcohols). Thus, in various embodiments, the second product stream is composed of C 5+ At least a portion of the hydrocarbons provides one or more products. 5+ Hydrocarbons can be used as the basis for various fuels, such as gasoline, diesel, and aviation fuel. Other products, such as waxes and lubricants, can also be made. And olefins and oxygenates can be used as feedstocks in various other processes.

[0108] A person skilled in the art will use conventional post-processing techniques to remove the C 5+ The product of the hydrocarbon is converted into a desirable product such as a desirable fuel. For example, in various embodiments, the method further comprises hydrotreating the C 5+ At least a portion of the hydrocarbons. As will be understood by one of ordinary skill in the art, hydroprocessing is the treatment of a hydrocarbon stream with hydrogen in the presence of a suitable catalyst. A variety of hydroprocessing techniques are known and one of ordinary skill in the art will apply them herein. For example, in Figure 3 In the method 300, the second product stream 322 is hydrotreated in the hydrotreating reactor 350 to provide a hydrotreated product stream 352.

[0109] As noted above, CO2 and H2 are substantial inputs to the claimed process. Advantageously, the inventors have recognized that each of these inputs can be derived from renewable or otherwise environmentally responsible sources.

[0110] CO2 can be captured from the environment in general, or more directly from the process of forming CO2 (especially in areas where it is difficult to reduce emissions). This can make the final hydrocarbon product essentially carbon neutral or have a lower carbon intensity. Therefore, in some embodiments of the present disclosure as described herein, at least a portion of the CO2 of the first feed stream and / or the second feed stream comes from a renewable source. In some embodiments, at least a portion of the CO2 of the first feed stream and / or the second feed stream (e.g., at least 25%, at least 50%, or at least 75%) comes from direct air capture. In some embodiments, at least a portion of the CO2 of the first feed stream and / or the second feed stream (e.g., at least 25%, at least 50%, or at least 75%) comes from a manufacturing plant such as a bioethanol plant (e.g., CO2 produced by fermentation), a steel plant, or a cement plant. Therefore, the rWGS-Fischer-Tropsch integrated process of the present disclosure as described herein can not only be carbon neutral, but can also be a net consumer of carbon dioxide in some cases. These benefits make the integrated approach particularly attractive for decarbonizing transportation fuels (for the automotive and aviation sectors), since the carbon monoxide produced in the rWGS reaction can be readily used to synthesize liquid hydrocarbon fuels via the Fischer-Tropsch process using established techniques.

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

[0112] The inventors have noted that electrolysis of water is a desirable way to provide hydrogen to the claimed method. Thus, in some embodiments, the method includes providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water. In some embodiments, the electrolysis of water is performed at least in part using electricity from a renewable source, for example to provide so-called "green hydrogen." However, the inventors have noted that electricity can be generated as part of the claimed method, for example using heat exchange from the first or second product stream, or by burning light hydrocarbons as described above. In some embodiments, the electrolysis of water is performed at least in part using electricity generated according to the method as described herein. For example, in Figure 2 In method 200, water 262 separated from the first product stream is electrolyzed in electrolyzer 260 using electricity 264 generated from steam produced by heat exchange from the first product stream in steam generating zone 232. H2 generated in the electrolysis is provided to the first feed stream via stream 265. In some embodiments, at least a portion of the O2 generated in the electrolysis is provided to a first feed stream as described herein and as described herein. Figure 6 The partial oxidation reaction zone shown in the embodiment of FIG. 4 is a partial oxidation reaction zone shown in FIG. 4. The hydrogen from the electrolysis can also be burned to provide thermal energy, for example, which can be used to heat the first feed stream.

[0113] The methods described herein can be operated in a variety of reactor systems. In some embodiments, the first reaction zone (i.e., where the reverse water gas shift process step is performed) includes a first reactor in which a reverse water gas shift catalyst is disposed, and the second reaction zone (i.e., where the Fischer-Tropsch process step is performed) includes a second reactor in which a Fischer-Tropsch catalyst is disposed. Examples of such methods are schematically shown in Figure 1 , 2 and 4. In these embodiments, the method (100, 200, 400) is carried out in a reactor system comprising a first reactor (110, 210, 410) in which a reverse water gas shift catalyst (113, 213, 413) is disposed and a second reactor (120, 220, 420) in which a Fischer-Tropsch catalyst (123, 223, 423) is disposed. The reactor used in the integrated process of the present disclosure as described herein is not particularly limited, and a person of ordinary skill in the art will be able to select an appropriate reactor.

[0114] However, other embodiments are possible. For example, in some embodiments, the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein the second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed. In some embodiments, the first reactor bed and the second reactor bed are disposed in the same reactor. Figure 3, where the reverse water gas shift catalyst 313 is disposed in a first catalyst bed 314 and the Fischer-Tropsch catalyst 323 is disposed in a second catalyst bed 324. Here, the catalyst beds 314 and 324 are in the same reactor 305 with the process gas flowing between them. Such a configuration may be particularly desirable when the first temperature and the second temperature are relatively close to each other.

[0115] In various embodiments, the method is carried out in a reactor system comprising a first catalyst container in which one or more reverse water gas shift catalysts are disposed, and wherein the second reaction zone comprises a second catalyst container in which one or more Fischer-Tropsch catalysts are disposed. These may be provided in the same reactor, as described above for the catalyst bed.

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

[0117] In the embodiments specifically described above, separate rWGS and Fischer-Tropsch catalysts are used in admixture, for example, in separate reactors, in separate zones of the same reactor, or even in the same zone of a reactor.

[0118] However, the inventors have also noted that there are certain commonalities between the rWGS catalysts described herein and certain Fischer-Tropsch catalysts. For example, as will be appreciated by one of ordinary skill in the art, manganese is a common modifier used in Fischer-Tropsch catalysts, particularly those based on cobalt. The inventors have also noted that similar supports can be used for each catalyst.

[0119] Therefore, in addition to the above-mentioned configuration, the inventors have contemplated providing a single bifunctional catalyst having reverse water gas shift activity and Fischer-Tropsch activity. This bifunctional catalyst comprises rWGS active catalyst metal and Fischer-Tropsch active catalyst metal in the same body. It will be understood by those skilled in the art that both rWGS catalyst and Fischer-Tropsch catalyst are supported catalysts, such as metal oxide supported catalysts. Therefore, in various embodiments of the present disclosure, rWGS active catalyst metal and Fischer-Tropsch active catalyst metal can be disposed together on the same carrier to provide a bifunctional catalyst. For example, in some embodiments, the carrier of the bifunctional catalyst itself is provided as a discrete body of material, such as a porous particle, pellet or shaped extrudate, wherein the rWGS active catalyst metal and the FT active catalyst metal are disposed thereon to provide a bifunctional catalyst. The rWGS active catalyst metal and the FT active catalyst metal can be uniformly distributed throughout the carrier, or can be distributed in discrete regions throughout the carrier. However, in other embodiments, the bifunctional catalyst of the present disclosure itself can be formed as a layer on the substrate below. For example, in some embodiments, the bifunctional catalyst is formed by a rWGS active catalyst metal layer and a FT active catalyst metal layer on the substrate below. The rWGS-active catalyst metal and the FT-active catalyst metal may be uniformly distributed on the underlying substrate. In other embodiments, the rWGS-active catalyst metal and the FT-active catalyst metal may be in discrete regions on the underlying substrate. The underlying substrate is not particularly limited. It may be formed, for example, of a metal or metal oxide, and may itself be provided in a variety of forms, such as particles, pellets, shaped extrudates or monoliths.

[0120] The bifunctional catalyst comprises a support material, a 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 that is a metal oxide support that includes at least one of titanium oxide, zirconium oxide, cerium oxide, or aluminum oxide. The rWGS active catalyst metal and the Fischer-Tropsch active catalyst metal are not particularly limited, and one of ordinary skill in the art will be able to select the appropriate metal. For example, a person skilled in the art or ordinary skill will be able to select an appropriate rWGS active metal as 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." 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 a combination thereof. Similarly, one of ordinary skill in the art will be able to select an appropriate Fischer-Tropsch active metal as described herein. For example, the Fischer-Tropsch active metal may be selected from cobalt, iron, rhodium, ruthenium, manganese or a combination thereof.

[0121] The ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is not particularly limited, and one of ordinary skill in the art will be able to select an appropriate ratio. For example, in some embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.1: 1. In various embodiments, the ratio of rWGS active catalyst metal to FT active catalyst metal in the bifunctional catalyst is at least 0.2: 1, or 0.5, or 1: 1.

[0122] Such catalysts can be used for Figure 5 In those embodiments described, one of ordinary skill in the art will select reaction conditions that provide an appropriate balance of reverse water gas shift activity and Fischer-Tropsch activity.

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

[0124] Additional aspects of the disclosure are provided by the embodiments listed below, which may be combined in any number and in any combination that is not logically or technically inconsistent.

[0125] Embodiment 1. A method for performing an integrated Fischer-Tropsch process, the method comprising:

[0126] Providing a first feed stream comprising H2 and CO2;

[0127] contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream;

[0128] contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a product comprising C 5+ A second product stream of hydrocarbons.

[0129] Embodiment 2. The method of Embodiment 1, 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.

[0130] Embodiment 3. The method of Embodiment 1 or Embodiment 2, wherein the molar ratio of H2 to CO2 in the first feed stream is at least 0.9:1, eg, at least 1:1 or at least 1.5:1.

[0131] Embodiment 4. The method of any one of Embodiments 1-3, 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.

[0132] Embodiment 5. The method of any one of Embodiments 1-4, wherein the molar ratio of H2 to CO2 in the first feed stream is no more than 100:1, for example no more than 75:1, or 50:1.

[0133] Embodiment 6. The method of any one of Embodiments 1-4, wherein the molar ratio of H2 to CO2 in the first feed stream is no more than 20:1, for example no more than 15:1, or 10:1.

[0134] Embodiment 7. The method of any one of Embodiments 1-6, wherein the molar ratio of H2 to CO2 in the first feed stream is in the range of 0.5:1 to 10:1.

[0135] Embodiment 8. A method according to any one of Embodiments 1-7, wherein the first feed stream further comprises CO.

[0136] Embodiment 9. A method according to any one of Embodiments 1-8, wherein the first feed stream further comprises one or more inert gases (e.g., nitrogen and / or methane).

[0137] Embodiment 10. The method of any one of Embodiments 1-9, wherein the reverse water gas shift reaction has a CO selectivity of at least 70%, such as at least 80%.

[0138] Embodiment 11. The method of any one of Embodiments 1-9, wherein the reverse water gas shift reaction has a CO selectivity of at least 85%, such as at least 90%.

[0139] Embodiment 12. The method of any one of Embodiments 1-11, wherein the reverse water gas shift reaction has a CO selectivity of at least 95%, such as at least 96%.

[0140] Embodiment 13. The method of any one of Embodiments 1-11, wherein the reverse water gas shift reaction has a CO selectivity of at least 98%, for example or at least 99%.

[0141] Embodiment 14. The method of any one of Embodiments 1-13, wherein the reverse water gas shift reaction has a methane selectivity of no more than 5%, such as no more than 4%.

[0142] Embodiment 15. The method of any one of Embodiments 1-13, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%, such as no more than 1%.

[0143] Embodiment 16. The method of any one of Embodiments 1-13, wherein the reverse water gas shift reaction has a methane selectivity of no more than 0.5%, such as no more than 0.2%.

[0144] Embodiment 17. The method of any one of Embodiments 1-16, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 5%, such as at least 10%, or 20%.

[0145] Embodiment 18. The method of any one of Embodiments 1-16, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 30%, such as at least 40%.

[0146] Embodiment 19. The method of any one of Embodiments 1-18, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 90%, such as no more than 80%, or no more than 70%.

[0147] Embodiment 20. The method of any one of Embodiments 1-18, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 65%, for example no more than 60%.

[0148] Embodiment 21. The method of any one of Embodiments 1-20, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 200-850°C, for example, in the range of 200-800°C, 200-750°C, 200-700°C, or 200-650°C, or 200-600°C.

[0149] Embodiment 22. The method described in any one of Embodiments 1-20, 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.

[0150] Embodiment 23. The method described in any one of Embodiments 1-20, 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 200-850°C, or 200-800°C, or 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.

[0151] Embodiment 24. The method described in any one of Embodiments 1-20, 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.

[0152] Embodiment 25. The method described in any one of Embodiments 1-20, 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.

[0153] Embodiment 26. The method described in any one of Embodiments 1-20, 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.

[0154] Embodiment 27. The method described in any one of Embodiments 1-20, 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.

[0155] Embodiment 28. The method described in any one of Embodiments 1-20, 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.

[0156] Embodiment 29. The method of any one of Embodiments 1-20, 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.

[0157] Embodiment 30. The method of any one of embodiments 1-29, wherein the reverse water gas shift reaction is carried out at a pressure in the range of 1 to 100 bar (for example, in the range of 1 to 70 bar, or 1 to 50 bar, or 1 to 40 bar, or 1 to 35 bar, or 5 to 80 bar, or 5 to 50 bar, or 5 to 40 bar, or 5 to 35 bar, or 10 to 70 bar, 10 to 50 bar, or 10 to 40 bar, or 10 to 35 bar, or 20 to 70 bar, 20 to 50 bar, or 20 to 40 bar, or 20 to 35 bar, or 25 to 70 bar, 25 to 50 bar, or 25 to 40 bar, or 25 to 35 bar).

[0158] Embodiment 31. The method of any one of embodiments 1-30, wherein the reverse water gas shift reaction is carried out at 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0159] Embodiment 32. The method of any one of Embodiments 1-46, wherein the method comprises activating the reverse water gas shift catalyst, for example, before contacting the reverse water gas shift catalyst with the first feed stream.

[0160] Embodiment 33. The method of Embodiment 32, wherein activating the rWGS catalyst comprises contacting the rWGS catalyst with a reducing feed stream comprising a reducing gas (eg, hydrogen).

[0161] Embodiment 34. The method of Embodiment 32 or Embodiment 33, wherein the reducing feed stream comprises hydrogen in an amount of at least 25 mol % (e.g., at least 50 mol %, or 75 mol %, or 90 mol %).

[0162] Embodiment 35. The method of any one of Embodiments 32-34, wherein activation of the rWGS catalyst is carried out at a temperature in the range of 200°C to 800°C (e.g., in the range of 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C).

[0163] Embodiment 36. The method of any one of Embodiments 32-35, wherein activation of the rWGS catalyst provides a catalyst that is at least 10% reduced (eg, at least 25%, or 50% reduced).

[0164] Embodiment 37. The method of any one of Embodiments 1-36, wherein the first product stream contains no more than 95 mol % CO2 (e.g., no more than 90 mol % CO2).

[0165] Embodiment 38. The method of any one of Embodiments 1-36, wherein the first product stream contains no more than 85 mol % CO2 (e.g., no more than 80 mol % CO2).

[0166] Embodiment 39. The method of any one of Embodiments 1-36, wherein the first product stream contains no more than 75 mol % CO2 (e.g., no more than 70 mol % CO2).

[0167] Embodiment 40. The method of any one of Embodiments 1-36, wherein the first product feed stream contains CO2 in the range of 5-95 mol%, for example, 5-90 mol%, or 5-85 mol%, or 5-80 mol%, or 5-75 mol%, or 5-70 mol%, or 10-95 mol%, or 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% CO2.

[0168] Embodiment 41. The method of any one of Embodiments 1-40, wherein the first product stream comprises no more than 20 mol% methane, eg, no more than 15 mol% methane.

[0169] Embodiment 42. The method of any one of Embodiments 1-40, wherein the first product feed stream contains no more than 10 mol% methane, for example, no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol% methane.

[0170] Embodiment 43. The method of any one of Embodiments 1-42, wherein the ratio of H2:CO in the first product stream is at most 100:1, e.g., at most 50:1, or at most 25:1, or at most 10:1.

[0171] Embodiment 44. The method of any one of Embodiments 1-42, wherein the ratio of H2:CO in the first product feed stream is in the range of 0.1:1 to 100:1 (for example, in the range of 0.1:1 to 50:1, or 0.1:1 to 25:1, or 0.1:1 to 10:1, or 0.1:1 to 5:1, or 1:1 to 100:1, or 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 10:1, or 1:1 to 5:1).

[0172] Embodiment 45. The method of any one of Embodiments 1-44, wherein the method further comprises separating the first product stream so as to recycle at least a portion of one or more components of the first product stream to the first feed stream.

[0173] Embodiment 46. The method of any one of Embodiments 1-45, wherein the method further comprises separating the first product stream so as to recycle at least a portion of the CO2 of the first product stream (e.g., at least 5 mole%, at least 10 mole%, at least 25 mole%, at least 50 mole%, at least 75 mole%, or at least 90 mole%) to the first feed stream.

[0174] Embodiment 47. The method of any one of Embodiments 1-46, wherein the method further comprises separating the first product stream so as to recycle at least a portion of the H2 (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the first feed stream.

[0175] Embodiment 48. The method of any one of Embodiments 1-47, wherein the method comprises separating at least a portion of H2 and / or CO from the first product stream and contacting it with a Fischer-Tropsch catalyst to activate the Fischer-Tropsch catalyst.

[0176] Embodiment 49. The method of any one of Embodiments 1-48, wherein the method further comprises removing at least a portion (e.g., at least 25%, at least 50%, or at least 75%) of the water from the first product stream.

[0177] Embodiment 50. The method of any one of Embodiments 1-49, wherein the first product stream comprises one or more light hydrocarbons (e.g., methane, ethane, propane).

[0178] Embodiment 51. The method of Embodiment 50 further comprises separating at least a portion of one or more light hydrocarbons from the first product stream to provide a light hydrocarbon stream.

[0179] Embodiment 52. The method of any one of Embodiments 1-51, 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.

[0180] Embodiment 53. The method of any one of Embodiments 1-52, wherein the method further comprises exchanging heat between at least a portion of the first product stream and a steam generating zone, thereby cooling at least a portion of the first product stream and providing heat to the steam generating zone.

[0181] Embodiment 54. The method of Embodiment 53, further comprising generating steam from the heat provided to the steam generating zone, and generating electricity from the steam.

[0182] Embodiment 55. The method of Embodiment 53 or 54, wherein the steam is used to heat the first feed stream and / or the second feed stream.

[0183] Embodiment 56. A method as described in any one of Embodiments 1-55, wherein at least 25% of the CO of the first product stream, for example, at least 50% of the CO, at least 75% of the CO, or at least 90% of the CO of the first product stream is contained in the second feed stream.

[0184] Embodiment 57. The method of any one of Embodiments 1-56, wherein CO is provided to the second feed stream from a CO source other than the first product stream.

[0185] Embodiment 58. The method of any one of Embodiments 1-57, 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.

[0186] Embodiment 59. The method of any one of Embodiments 1-58, wherein at least 25% of the H2 of the first product stream, for example, at least 50% of the H2 of the first product stream, at least 75% of the H2, or at least 90% of the H2 of the first product stream is contained in the second feed stream.

[0187] Embodiment 60. The method of any one of Embodiments 1-59, wherein H2 is provided to the second feed stream from a hydrogen source other than the first product stream.

[0188] Embodiment 61. The method of any one of Embodiments 1-60, wherein the second feed stream comprises at least a portion of the CO2 of the first product stream.

[0189] Embodiment 62. A method as described in any one of Embodiments 1-61, wherein at least 10% of the CO2 of the first product stream, for example, at least 25% of the CO2 of the first product stream, at least 50% of the CO2, at least 75% of the CO2, or at least 90% of the CO2 of the first product stream is contained in the second feed stream.

[0190] Embodiment 63. The method of any one of Embodiments 1-61, wherein the second feed stream does not contain a significant amount of CO2 of the first product stream.

[0191] Embodiment 64. The method of any one of Embodiments 1-63, wherein the portion of the first product stream contained in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 10:1, for example, in the range of 1:1 to 3:1.

[0192] Embodiment 65. The method of any one of Embodiments 1-64, wherein the portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, for example, or no more than 2 mol%, or no more than 0.5 mol%.

[0193] Embodiment 66. The method of any one of Embodiments 1-65, wherein the portion of the first product stream contained in the second feed stream has a CO2 content in the range of 10-95 mol% CO2, for example, 10-90 mol%, or 10-85 mol%, or 10-80 mol%, or 10-75 mol%, or 10-70 mol%, or 20-95 mol%, or 20-90 mol%, or 20-85 mol%, or 20-80 mol%, or 20-75 mol%, or 20-70 mol%, or 30-95 mol%, or 30-90 mol%, or 30-85 mol%, or 30-80 mol%, or 30-75 mol%, or 30-70 mol% CO2.

[0194] Embodiment 67. The method of any one of Embodiments 1-66, wherein the second feed stream has a H2:CO ratio in the range of 0.5:1 to 6:1.

[0195] Embodiment 68. The method of any one of Embodiments 1-66, wherein the second feed stream has a H2:CO ratio in a range of 1:1 to 3:1, for example, 1:1 to 2.5:1.

[0196] Embodiment 69. The method of any one of Embodiments 1-66, wherein the second feed stream has a H2:CO ratio of at least 1.4:1, e.g., in a range of 1.4:1 to 3:1, or 1.4:1 to 2.5:1.

[0197] Embodiment 70. The method of any one of Embodiments 1-69, wherein the second feed stream comprises up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% of one or more inerts.

[0198] Embodiment 71. The method of any one of Embodiments 1-69, wherein the second feed stream contains up to 80%, e.g., up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% of one or more inerts selected from CO2, methane and nitrogen.

[0199] Embodiment 72. The method of any one of Embodiments 1-71, wherein the second feed stream contains up to 80%, for example up to 70 mol%, up to 60 mol%, or up to 50 mol%, or 15-70 mol%, or 30-70 mol%, or 15-60 mol%, or 30-60 mol%, or 15-50 mol%, or 30-50 mol% CO2.

[0200] Embodiment 73. The method of any one of Embodiments 1-72, wherein the second feed stream has a water content of no more than 10 mol%, eg, or no more than 2 mol%, or no more than 0.5 mol%.

[0201] Embodiment 74. The method of any one of Embodiments 1-73, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0202] Embodiment 75. The method of any one of Embodiments 1-73, wherein the Fischer-Tropsch catalyst contains cobalt in an amount in the range of 5-25 wt%, calculated as Co(0), for example 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt%.

[0203] Embodiment 76. The method of any one of Embodiments 1-74, wherein the Fischer-Tropsch catalyst contains iron in an amount in the range of 5-95 wt.%, calculated as Fe(0), for example 10-95 wt.%, or 25-95 wt.%, or 50-95 wt.%, or 5-85 wt.%, or 10-85 wt.%, or 25-85 wt.%, or 50-85 wt.%, or 5-75 wt.%, or 10-75 wt.%, or 25-75 wt.%.

[0204] Embodiment 77. The method of any one of Embodiments 74-76, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0205] Embodiment 78. The method of Embodiment 77, wherein manganese is present in an amount of up to 15 wt%, calculated as Mn(0), for example up to 12 wt%, or up to 10 wt%, or up to 7 wt%, or in the range of 0.1-15 wt%, for example 0.1-10 wt%, or 0.1-5 wt%, 0.5-15 wt%, or 0.5-10 wt%, or 0.5-5 wt%.

[0206] Embodiment 79. The method of any one of Embodiments 1-78, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide, and zinc oxide.

[0207] Embodiment 80. The method of any one of Embodiments 1-78, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0208] Embodiment 81. The method of any one of Embodiments 1-78, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titanium dioxide support.

[0209] Embodiment 82. The method of any one of Embodiments 1-81, wherein the Fischer-Tropsch catalyst is activated by contact with a reducing gas, such as hydrogen.

[0210] Embodiment 83. The method of Embodiment 80, wherein the reducing gas comprises at least a portion of the hydrogen from the first product stream.

[0211] Embodiment 84. The method of any one of Embodiments 1-81, wherein the Fischer-Tropsch catalyst is activated by contact with H2 and CO.

[0212] Embodiment 85. The method of Embodiment 84, wherein the reducing gas comprises at least a portion of H2 and CO from the first product stream.

[0213] Embodiment 86. The method of any one of Embodiments 82-84, wherein the activation is performed at a temperature in the range of 200-400°C.

[0214] Embodiment 87. The method of any one of Embodiments 1-86, wherein the second temperature is in the range of 150-400°C (for example in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0215] Embodiment 88. The method of any one of Embodiments 1-87, wherein the second temperature is in the range of 200-350°C.

[0216] Embodiment 89. The method of any one of Embodiments 1-88, wherein the first temperature is within 100°C of the second temperature, such as within 50°C of the second temperature, or within 25°C of the second temperature.

[0217] Embodiment 90. The method of any one of Embodiments 1-89, wherein the first temperature is at least 100°C higher than the second temperature, for example at least 150°C higher than the second temperature, or at least 200°C higher than the second temperature.

[0218] Embodiment 91. The method of any one of Embodiments 1-90, wherein the second pressure is in the range of 10-50 bar (e.g., 20-50 bar, or 25-50 bar, or 10-40 bar, or 20-40 bar, or 25-40 bar, or 10-35 bar, or 20-35 bar, or 25-35 bar).

[0219] Embodiment 92. The method of any one of Embodiments 1-91, wherein the second pressure is in the range of 20-50 bar.

[0220] Embodiment 93. The method of any one of Embodiments 1-92, wherein the Fischer-Tropsch reaction is carried out at a temperature of 1,000 to 2,000,000 h. -1 range (e.g. 1,000 to 1,200,000h -1 , or 1,000 to 500,000h -1 , or 1,000 to 100,000h -1 , or 5,000 to 1,200,000h -1 , or 5,000 to 500,000h -1 , or 5,000 to 100,000h -1 , or 10,000 to 1,200,000h -1 , or 10,000 to 500,000h -1 , or 10,000 to 100,000h -1 The results were carried out under GHSV of 2.5 GHz and 1.5 GHz.

[0221] Embodiment 94. The method of any one of Embodiments 1-93, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% C 5+ Selective.

[0222] Embodiment 95. The method of any one of Embodiments 1-94, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ The selectivity of alkanes is carried out.

[0223] Embodiment 96. The method of any one of Embodiments 1-95, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide the second product stream with at least 30%, such as at least 50%, or at least 70% of the C 5+ Alkanes and C 5+ The selectivity of alcohol is carried out.

[0224] Embodiment 97. The method of any one of Embodiments 1-96, further comprising separating at least a portion of the water from the second product stream.

[0225] Embodiment 98. The method of any one of Embodiments 1-97, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0226] Embodiment 99. The method described in Embodiment 98 further comprises including at least a portion of a light hydrocarbon stream in the first feed stream and / or the second feed stream.

[0227] Embodiment 100. The method of Embodiment 98 or Embodiment 99 further comprises oxidizing at least a portion of the light hydrocarbon stream to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream and / or the second feed stream.

[0228] Embodiment 101. The method described in any one of Embodiments 98-100 further includes reforming (e.g., steam reforming and / or autothermal reforming) at least a portion of the light hydrocarbon stream to provide a reforming stream containing CO and / or CO2, and including at least a portion of the reforming stream in the first feed stream and / or the second feed stream.

[0229] Embodiment 102. The method of Embodiment 100 or Embodiment 101, wherein the oxidation or reforming provides energy, thermal energy or electrical energy.

[0230] Embodiment 103. The method of any one of Embodiments 98-102 further comprises combusting at least a portion of the light hydrocarbon stream to provide energy, such as heat or electricity.

[0231] Embodiment 104. The method of Embodiment 102 or Embodiment 103, wherein thermal energy is provided and the thermal energy is used to heat the first feed stream.

[0232] Embodiment 105. The method of any one of Embodiments 1-104, wherein the method further comprises exchanging heat between at least a portion of the second product stream and a steam generating zone, thereby cooling at least a portion of the first feed stream and providing heat to the steam generating zone.

[0233] Embodiment 106. The method of Embodiment 105 further comprises generating steam from heat provided to the steam generating zone, and generating electricity from the steam.

[0234] Embodiment 107. The method of Embodiment 105 or 106, wherein steam is used to heat the first feed stream and / or the second feed stream.

[0235] Embodiment 108. The method of any one of Embodiments 1-107, 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.

[0236] Embodiment 109. The method of any one of Embodiments 1-108, further comprising recycling at least a portion of the H2 of the second product stream to the second feed stream.

[0237] Embodiment 110. The method of any one of Embodiments 1-109 further comprises recycling at least a portion of the H2 of the second product stream to the first feed stream.

[0238] Embodiment 111. The method of Embodiment 110 further comprises providing H2 to the second feed stream from a H2 source other than the first product stream.

[0239] Embodiment 112. The method of Embodiment 111, wherein the H2 from the second product stream constitutes a majority of the H2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the H2 of the first feed stream.

[0240] Embodiment 113. The method of any one of Embodiments 1-112 further comprises recycling at least a portion of the CO of the second product stream to the second feed stream.

[0241] Embodiment 114. The method of any one of Embodiments 1-113 further comprises recycling at least a portion of the CO of the second product stream to the first feed stream.

[0242] Embodiment 115. The method of any one of Embodiments 1-114, further comprising recycling at least a portion of the inerts of the second product stream to the second feed stream.

[0243] Embodiment 116. The method of any one of Embodiments 1-115, further comprising recycling at least a portion of the inerts of the second product stream to the first feed stream.

[0244] Embodiment 117. The method of any one of Embodiments 1-116 further comprises recycling at least a portion of the CO2 of the second product stream to the first feed stream.

[0245] Embodiment 118. The method of Embodiment 117 further comprises providing CO2 to the second feed stream from a CO2 source other than the first product stream.

[0246] Embodiment 119. The method of Embodiment 118, wherein the CO2 from the second product stream constitutes a majority of the CO2 of the first feed stream, for example, at least 90%, at least 95%, or at least 98% of the CO2 of the first feed stream.

[0247] Embodiment 120. The method of any one of Embodiments 1-119, wherein the C of the second product stream 5+ At least a portion of the hydrocarbons provides one or more products.

[0248] Embodiment 121. The method of Embodiment 120, wherein the one or more products include fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants, and waxes.

[0249] Embodiment 122. The method of any one of Embodiments 1-121, further comprising hydrotreating the C of the second product stream. 5+ at least a portion of a hydrocarbon.

[0250] Embodiment 123. The method of any one of Embodiments 1-122, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream is from a renewable source.

[0251] Embodiment 124. The method of any one of Embodiments 1-123, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream comes from direct air capture.

[0252] Embodiment 125. The method of any one of Embodiments 1-124, wherein at least a portion of the CO2 of the first feed stream and / or the second feed stream is captured from a manufacturing plant such as a bioethanol plant, a steel plant, or a cement plant.

[0253] Embodiment 126. The method of any one of Embodiments 1-125, wherein at least a portion of the H2 of the first feed stream or the second feed stream is from a renewable source.

[0254] Embodiment 127. The method of any one of Embodiments 1-126, wherein at least a portion of the H2 of the first feed stream or the second feed stream is green hydrogen.

[0255] Embodiment 128. The method of any one of Embodiments 1-127, wherein at least a portion of the H2 of the first feed stream or the second feed stream is blue hydrogen.

[0256] Embodiment 129. The method of any one of Embodiments 1-128, wherein at least a portion of the H2 of the first feed stream or the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0257] Embodiment 130. The method of any one of Embodiments 1-129 further comprises providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water.

[0258] Embodiment 131. The method of Embodiment 130, wherein the electrolysis of water is performed at least in part using electricity from a renewable source.

[0259] Embodiment 132. The method of Embodiment 130 or Embodiment 131, wherein the electrolysis of water is carried out at least in part using electricity generated by steam produced by heat exchange from the first product stream and / or the second product stream or by combustion of a light hydrocarbon stream.

[0260] Embodiment 133. The method of any one of Embodiments 130-132 further comprises providing at least a portion of the O2 produced in the electrolysis to partial oxidation.

[0261] Embodiment 134. The method of any one of Embodiments 1-133, wherein the method is carried out in a reactor system comprising a first reactor in which a reverse water gas shift catalyst is disposed and a second reactor in which a Fischer-Tropsch catalyst is disposed.

[0262] Embodiment 135. The method described in any one of Embodiments 1-134, wherein the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is disposed and wherein a second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0263] Embodiment 136. The method described in Embodiment 135, wherein the first reactor bed and the second reactor bed are arranged in the same reactor.

[0264] Embodiment 137. The method of any one of Embodiments 1-133, wherein the method is performed in a reactor system comprising a first catalyst container having one or more reverse water gas shift catalysts disposed therein, and wherein a second reaction zone comprises a second catalyst container having one or more Fischer-Tropsch catalysts disposed therein.

[0265] Embodiment 138. The method of Embodiment 137, wherein the one or more first catalyst containers and the one or more second catalyst containers are disposed in the same reactor.

[0266] Embodiment 139. The method of any one of Embodiments 1-138, wherein the method is carried out in a reactor system comprising a reactor comprising a reverse water gas shift catalyst and a Fischer-Tropsch catalyst, for example, disposed therein in admixture.

[0267] The details shown herein are presented as examples only and for the purpose of illustrative discussion of the preferred embodiments of the present invention, and are presented in order to provide the most useful and easily understood descriptions of the principles and concepts of the various embodiments of the present invention. In this regard, no attempt is made to show the structural details of the present invention in more detail than is required for a basic understanding of the present invention. The description in conjunction with the drawings and / or embodiments makes it clear to those skilled in the art how several forms of the present invention can be embodied in practice. Thus, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, equipment or configurations, and therefore can certainly vary. It should also be understood that the terms used herein are only used for the purpose of describing specific aspects, and are not intended to be restrictive unless specifically defined herein.

[0268] The terms "a", "an", "the" and similar referents used in the context of describing the present invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of numerical ranges herein is intended merely to serve as a shorthand process for individually referring to each individual value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into this specification as if it were individually referenced herein. It will be further understood that the endpoints of each range are significant both relative to the other endpoint and independently of the other endpoint.

[0269] Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order of steps. The use of any and all embodiments or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the present invention, rather than to limit the scope of the present invention otherwise claimed. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the present invention.

[0270] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise", "comprising", etc. should be interpreted in an inclusive sense and not in an exclusive or exhaustive sense; that is, in the sense of "including but not limited to". Words using the singular or plural number also include the plural and singular, respectively. In addition, when used in this application, the words "herein", "above", and "below" and words of similar meaning shall refer to this application as a whole and not to any particular parts of this application.

[0271] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of the elements, steps, ingredients, or components specifically stated therein. As used herein, the transitional terms "comprise" or "comprises" are meant to include, but are not limited to, and allow for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of excludes any elements, steps, ingredients, or components that are not specified. The transitional phrase "consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiment.

[0272] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0273] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0274] The grouping of the alternative elements of the present invention disclosed herein or embodiments should not be construed as limiting. Each group member can be mentioned and claimed individually or in any combination with other members of the group or other elements found herein. For reasons of convenience and / or patentability, it is contemplated that one or more members in the group may be included in the group or deleted from the group. When any such inclusion or deletion occurs, this specification is considered to contain the group modified, thereby satisfying the written specifications of all Markush groups used in the appended claims.

[0275] Some embodiments of the present invention are described herein, including the best mode of implementing the present invention known to the inventor. Of course, after reading the foregoing description, changes in the embodiments described will become apparent to those of ordinary skill in the art. The inventor expects those skilled in the art to appropriately adopt these changes, and the inventor intends to practice the present invention in a manner different from that specifically described herein. Therefore, the present invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, the present invention encompasses any combination of the above-mentioned elements in all possible variations thereof.

[0276] Throughout this specification, numerous patents and printed publications have been cited. Each of the cited references and printed publications is individually incorporated herein by reference in its entirety.

[0277] In addition, it should be understood that the embodiments of the present invention disclosed herein illustrate the principles of the present invention. Other modifications that may be adopted are within the scope of the present invention. Therefore, by way of example and not limitation, alternative configurations of the present invention may be utilized according to the teachings herein. Therefore, the present invention is not limited to what is precisely shown and described.

Claims

1. A method for performing an integrated Fischer-Tropsch process, the method comprising: Providing a first feed stream comprising H2 and CO2; contacting a reverse water gas shift catalyst with a first feed stream at a first temperature in the range of 200-900° C. and at a first pressure to perform a reverse water gas shift reaction to provide a first product stream comprising CO and H 2 , the first product stream having a lower concentration of CO 2 and a higher concentration of CO than the first feed stream; contacting the Fischer-Tropsch catalyst at a second temperature and a second pressure with a second feed stream comprising H2 and at least a portion of the CO of the first product stream to provide a catalyst comprising C 5+ A second product stream of hydrocarbons.

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

1.

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

4. The method of claim 1, wherein the reverse water gas shift reaction has a methane selectivity of no more than 2%.

5. The method of claim 1, wherein the reverse water gas shift reaction has a CO2 conversion rate of at least 30%.

6. The method of claim 1, wherein the reverse water gas shift reaction has a CO2 conversion rate of no more than 80%.

7. The method of claim 1, wherein the reverse water gas shift reaction is carried out at a temperature in the range of 400-700°C.

8. The method of claim 1, wherein the method comprises activating the reverse water gas shift catalyst with a reducing feed stream comprising a reducing gas.

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

10. The process of claim 1, wherein the first product stream comprises no more than 5 mole percent methane.

11. The method of claim 1, wherein the method further comprises separating the first product stream to recycle at least a portion of the CO2 and at least a portion of the H2 of the first product stream to the first feed stream.

12. The method of claim 1, 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.

13. The process of claim 1, wherein at least 25% of the CO of the first product stream is contained in the second feed stream.

14. The process of claim 1, wherein the first product stream comprises H2, and wherein at least 25% of the H2 of the first product stream is contained in the second feed stream.

15. The process of claim 1, wherein at least 10% of the CO2 of the first product stream is contained in the second feed stream.

16. The process of claim 1, wherein the second feed stream does not contain a significant amount of CO2 of the first product stream.

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

1.

18. The method of claim 1, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

19. The method of claim 18, wherein the Fischer-Tropsch catalyst further comprises manganese.

20. The process of claim 1, wherein the Fischer-Tropsch catalyst is activated by contact with a reducing gas comprising at least a portion of the hydrogen from the first product stream.

21. The method of claim 1, wherein the second temperature is in the range of 200-350°C.

22. The method of claim 1, wherein the first temperature is at least 100°C higher than the second temperature.

23. The process of claim 1, wherein the Fischer-Tropsch catalyst is contacted with the second feed stream to provide a second product stream having a carbon content of at least 30%. 5+ The selectivity of alkanes is carried out.

24. The method of claim 1, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

25. The process of claim 24, further comprising including at least a portion of a light hydrocarbon stream in the first feed stream and / or the second feed stream.

26. The process of claim 24, further comprising oxidizing at least a portion of the light hydrocarbon stream to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream and / or the second stream.

27. The method of claim 24, further comprising combusting at least a portion of the light hydrocarbon stream to provide thermal energy, and wherein the thermal energy is used to heat the first feed stream.

28. The process of claim 1, wherein the process 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.

29. The method of claim 1, further comprising recycling at least a portion of the H2 of the second product stream to the second feed stream.

30. The process of claim 1, further comprising recycling at least a portion of the H2 of the second product stream to the first feed stream, wherein the H2 from the second product stream comprises at least 90% of the H2 of the first feed stream.

31. The process of claim 1, further comprising recycling at least a portion of the CO of the second product stream to the second feed stream or the first feed stream.

32. The method of claim 1, further comprising recycling at least a portion of the CO2 of the second product stream to the first feed stream, wherein the CO2 from the second product stream constitutes at least 90% of the CO2 of the first feed stream.

33. The method of claim 1, wherein the method is carried out in a reactor system comprising a first reactor in which a reverse water gas shift catalyst is disposed and a second reactor in which a Fischer-Tropsch catalyst is disposed.

34. The method of claim 1, wherein the method is carried out in a reactor system comprising a first catalyst bed in which a reverse water gas shift catalyst is arranged and a second catalyst bed in which a Fischer-Tropsch catalyst is arranged, wherein the first reactor bed and the second reactor bed are arranged in the same reactor.

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