Fischer-Tropsch production of hydrocarbons from carbon dioxide via methanol

Abstract

The present disclosure generally relates to a process for integrated Fischer-Tropsch synthesis of hydrocarbons using methanol. In particular, the disclosure relates to a method comprising: providing a first feed stream comprising H and CO; contacting the first feed stream with a hydrogenation catalyst to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol from the first product stream; contacting the second feed stream with a methanol cracking catalyst to form a second product stream comprising CO and H; providing a third feed stream comprising H and at least a portion of the CO from the second product stream; and contacting the third feed stream with an iron-containing Fischer-Tropsch catalyst to provide a third product stream comprising C hydrocarbons and CO.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from European Patent Application No. 22190318.0, filed August 12, 2022, which is incorporated herein by reference in its entirety. [Technical Field]

[0002] The present disclosure relates to an integrated process for the Fischer-Tropsch synthesis of hydrocarbons from carbon dioxide. [Background technology]

[0003] The conversion of synthesis gas (i.e., a mixture of carbon monoxide and hydrogen, also known as syngas) to hydrocarbons via the Fischer-Tropsch process has been known for decades, but historically has lagged in performance compared to other hydrocarbon synthesis technologies. With the growing importance of alternative energy sources, the Fischer-Tropsch (FT) process has attracted renewed interest because it enables a direct and environmentally acceptable route to high-quality fuels and feedstock chemicals.

[0004] The FT process is known to produce linear hydrocarbons for use in fuels, as well as oxygenates that can be useful in fuels and also serve as valuable feedstock chemicals. Hydrocarbon fuels derived from the FT process can better meet increasingly stringent environmental regulations compared to fuels produced in conventional refineries because FT-derived fuels typically contain lower amounts of sulfur, nitrogen, and aromatic compounds, which contribute to the emission of potent pollutants such as SO2, NOx, and particulates. Products derived from the FT process often have higher octane numbers than hydrocarbons and therefore burn more completely, thereby reducing the environmental impact of such fuels. The resulting alcohols, olefins, and other oxygenates can also be used as reagents in other processes, such as the synthesis of lubricants.

[0005] Syngas is traditionally produced from fossil fuel sources, primarily by coal gasification, but it has the disadvantage of being difficult to handle because it must be transported in its low-density gas phase or liquefied under high pressure.

[0006] Therefore, there is a need to develop improved protocols for the production and handling of syngas, as well as the subsequent use of syngas in Fischer-Tropsch synthesis reactions. Summary of the Invention

[0007] The present inventors have identified a method for efficiently converting CO2 to hydrocarbons via the intermediation of methanol (MeOH) and synthesis gas. Advantageously, this method can proceed at lower temperatures compared to traditional synthesis routes and does not require the reverse water-gas shift (rWGS) process.

[0008] Thus, in one aspect, the present disclosure provides a method for conducting an integrated Fischer-Tropsch synthesis, the method comprising: Providing the first supply logistics including H2 and CO2, contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H; providing a third feed stream comprising H and at least a portion of the CO of the second product stream; contacting the third feed stream with an iron-containing Fischer-Tropsch catalyst to perform a Fischer-Tropsch synthesis to provide a third product stream comprising C5+ hydrocarbons and CO2.

[0009] Other aspects of the present disclosure will be apparent to those skilled in the art in view of the following description. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram of a method according to an exemplary embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram of a method according to an exemplary embodiment of the present disclosure. [Figure 3] FIG. 3 is a schematic diagram of a method according to an exemplary embodiment of the present disclosure. [Figure 4] FIG. 4 is a schematic diagram of a method according to an exemplary embodiment of the present disclosure. [Figure 5] FIG. 5 is a schematic diagram of a method according to an exemplary embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] This disclosure relates to technologies for preparing hydrocarbons from carbon dioxide. Carbon dioxide is a widely available gas (currently present at approximately 400 ppm in the atmosphere) that is inert to many transformations. Furthermore, due to its tendency to absorb infrared radiation, carbon dioxide has been designated as a greenhouse gas. Therefore, there is a need to develop economical methods to utilize carbon dioxide, especially waste carbon dioxide, which would otherwise add to the ever-increasing concentration of carbon dioxide in the atmosphere. Carbon dioxide is produced by many industries and can be captured as a point source to be used as a feedstock, for example, from facilities involved in steelmaking, fossil fuel power generation, cement production, fermentation processes, or fertilizer production. Carbon dioxide may also be sourced from direct air capture projects. Advantageously, hydrocarbon synthesis processes that use waste carbon dioxide as a feedstock have the potential to be low-carbon, carbon-neutral, or even have a negative carbon footprint. One way to achieve this is to convert carbon dioxide and hydrogen to methanol. Methanol, which is a liquid at ambient temperature and pressure, can optionally be transported through low-pressure pipelines, ships, or trucks, thus generally allowing for increased transportation efficiency as a liquid. The methanol can then be subjected to a methanol cracking process to produce H2 and CO in a 2:1 ratio. This mixture of H2 and CO is commonly referred to as "syngas" and finds widespread utility. At least the CO from the methanol cracking product can then be utilized in a Fischer-Tropsch synthesis reaction to produce hydrocarbons, and the H2 from the methanol cracking is also desirably used in the Fischer-Tropsch synthesis. For example, some Fischer-Tropsch processes operate at H2:CO ratios of 2:1 or greater, e.g., 2.2:1 or 3:1. In such cases, the H2 and CO mixture from the methanol cracking may be supplemented with a hydrogen source, such as a recycle stream or green hydrogen generated from renewable energy, to form the Fischer-Tropsch reaction mixture. In other Fischer-Tropsch processes, lower H2:CO ratios are desirable, e.g., in the range of 1:1 to 2:1. Thus, in such embodiments, excess H2 can be diverted from the methanol cracking feed stream to other processes.

[0012] Iron-based Fischer-Tropsch processes are desirable due to iron's low cost, low toxicity, and widespread abundance. However, the inventors have noted that iron-based Fischer-Tropsch catalysts often have high selectivity for CO2 as a byproduct. During conventional operation, this represents a significant waste of carbon, resulting in lower yields, increased operating costs, and increased emissions from the process. Furthermore, the conventional means for recycling CO2, i.e., the reverse water-gas shift reaction, operates at undesirably high temperatures and can be difficult to integrate with the Fischer-Tropsch process. The inventors have developed an integrated method for the production of hydrocarbons that utilizes carbon dioxide as a starting material, avoiding the use of the reverse water-gas shift reaction. In various embodiments, the methods described herein can operate at similar temperatures, allowing the processes to be integrated in an efficient manner. Therefore, integrating this process with an iron-based Fischer-Tropsch process allows for the easy recycling of generated CO2. This reduces wasted carbon input and also reduces CO2 emissions from the process.

[0013] Thus, in one aspect, the present disclosure provides a method for conducting an integrated Fischer-Tropsch synthesis, the method comprising: Providing the first supply logistics including H2 and CO2, contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H; providing a third feed stream comprising H and at least a portion of the CO of the second product stream; contacting the third feed stream with an iron-containing Fischer-Tropsch catalyst to perform a Fischer-Tropsch synthesis to provide a third product stream comprising C5+ hydrocarbons and CO2.

[0014] As used herein, "feed stream" refers to all materials input to a process step, e.g., CO2 hydrogenation, methanolysis, or a Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams and through a single inlet or multiple inlets. For example, the H2 and CO2 of a first feed stream may be provided to a hydrogenation reactor in a single physical stream (e.g., a single pipe to the reactor) or in multiple physical streams (e.g., separate inlets for CO2 and H2, or one inlet for fresh CO2 and H2 and another inlet for recycled CO2 and / or H2). Similarly, "product stream" refers to all materials output from a process step, e.g., carbon dioxide hydrogenation, methanolysis, or a Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams and through a single reactor outlet or multiple reactor outlets.

[0015] Advantageously, the integrated processes described herein can be substantially asymmetric in nature: methanol can be synthesized from carbon species that are primarily CO, which can then be decomposed into a stream having CO as the predominant carbon species. This is in contrast to symmetric processes, in which the streams entering methanol synthesis and exiting methanol decomposition have similar carbon compositions. Because most of the reactions described herein are equilibrium processes, they naturally lend themselves to being symmetrically integrated. However, the inventors have discovered that asymmetric processes such as those disclosed herein allow for improved control over the composition of the streams and increased process efficiency.

[0016] The first feed stream comprises H and CO for subsequent contact with a hydrogenation catalyst to produce methanol. Thus, in various embodiments described elsewhere herein, the first feed stream comprises at least 10 mol% H. For example, in various embodiments, the first feed stream comprises at least 20 mol% H, e.g., at least 30 mol% H. In various embodiments described elsewhere herein, the first feed stream comprises at least 5 mol% CO. For example, in various embodiments, the first feed stream comprises at least 10 mol% CO, e.g., at least 15 mol% CO.

[0017] Generally, CO hydrogenation to produce methanol proceeds according to the reaction: CO + 3H → CHOH + HO. Thus, in various embodiments described elsewhere herein, the H:CO ratio of the first feed stream is at least 1:1, e.g., at least 1.5:1, on a molar basis. For example, in various embodiments described elsewhere herein, the H:CO ratio of the first feed stream is at least 2:1, e.g., at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 8:1. In certain embodiments, the H:CO ratio of the first feed stream is 25:1 or less, e.g., 20:1 or less, or 15:1 or less, or 12:1 or less.

[0018] In some embodiments, the first feed stream includes other gases in addition to CO and H. For example, in various embodiments, the first feed stream further includes one or more of CO, CH, and N. For example, in certain embodiments, the first feed stream includes, in addition to CO and H, other gases (e.g., one or more of CO, CH, and N) in an amount of up to 70 mol%. In various embodiments, the first feed stream includes 1% or less O, e.g., 0.1% or less O, or 0.01% or less O, or is substantially free of O. In various embodiments, the first feed stream includes 20 mol% or less CO, e.g., 15 mol% or less CO, or 10 mol% or less CO, or even 5 mol% or less CO.

[0019] As described elsewhere herein, the first feed stream is contacted with a hydrogenation catalyst. The hydrogenation catalyst may be selected by one skilled in the art. Examples of suitable catalysts include Cu / ZnO catalysts supported on aluminum oxide or zirconium oxide, for example.

[0020] Advantageously, the CO hydrogenation reaction may be carried out at relatively low temperatures, resulting in increased energy efficiency and overall process integration. For example, in various embodiments described elsewhere herein, contacting the first feed stream with the hydrogenation catalyst is carried out at a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C. In various embodiments, contacting the first feed stream with the hydrogenation catalyst is carried out at a pressure of 100 bar or less, e.g., 80 bar or less, or 60 bar or less.

[0021] As described herein, the hydrogenation of CO advantageously produces methanol with high selectivity. Thus, in various embodiments described elsewhere herein, the hydrogenation of CO is carried out with a selectivity to methanol of at least 50%, e.g., at least 55%, or at least 60%. For example, in certain embodiments, the hydrogenation of CO is carried out with a selectivity to methanol of at least 65% (e.g., at least 70%, or at least 75%, or at least 80% to methanol). Advantageously, the hydrogenation of CO can be carried out with a low selectivity to methane. In various embodiments described elsewhere herein, the hydrogenation of CO is carried out with a selectivity to methane of 20% or less, e.g., 10% or less, or 5% or less to methane. As one of ordinary skill in the art will understand, "selectivity" for a given species is the fraction of the reacted carbon-containing reactant that is converted to that species, i.e., not counting unreacted material.

[0022] Importantly, the CO hydrogenation reaction described herein is not a reverse water gas shift reaction. As known in the art, the reverse water gas shift reaction converts CO and H to CO and HO. Thus, in various embodiments described elsewhere herein, the hydrogenation of CO is carried out at a selectivity to CO of 20% or less, e.g., 10% or less to CO, or 5% or less. In certain embodiments, the hydrogenation of CO is carried out at a selectivity to CO of 2% or less, or 1% or less to CO.

[0023] During the CO hydrogenation reaction, at least a portion of the CO is hydrogenated to MeOH and HO. Advantageously, the process can be carried out at a relatively high conversion of CO. Thus, in various embodiments described elsewhere herein, the hydrogenation of CO is carried out at a conversion of at least 25%, e.g., at least 35%, e.g., at least 45% or at least 50% of CO.

[0024] Those skilled in the art will be familiar with catalytic methods for hydrogenating carbon dioxide to methanol.Various examples of catalysts and catalytic processes are described in R. Guil-Lopez et al., Materials, 12, 3902 (2019); Xiao et al., In; Aresta et al. (eds.), "An Economy Based on Carbon Dioxide and Water" (2019); Marlin et al., Front. Chem. (2018); Rodriguez et al., ACS Cat. 5(11), 6696 (2015); J. Choundhury, Chem. Cat. Chem. 4(5), 609 (2012), each of which is incorporated herein by reference in its entirety.

[0025] CO hydrogenation produces a first product stream. In various embodiments described elsewhere herein, the first product stream comprises at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol. As described herein, CO hydrogenation also advantageously has low selectivity to other products, such as methane and / or carbon monoxide. Accordingly, in various embodiments described elsewhere herein, the first product stream comprises 10 mol% or less methane, e.g., 5 mol% or less methane, or 2 mol% or less methane. In various embodiments described elsewhere herein, the first product stream comprises 10 mol% or less CO, e.g., 5 mol% or less CO, or 2 mol% or less CO. Of course, in some embodiments, more methane and / or CO may be present, e.g., when provided as part of the first feed stream, e.g., as a recycle from the Fischer-Tropsch product. As will be understood by one of skill in the art, the composition of the first product stream disclosed herein is calculated excluding inert gases or unreacted CO and / or H.

[0026] As described herein, the CO hydrogenation step produces both methanol and water. In some embodiments, the water formed can be harmful to subsequent processes. For example, excess water present in a methanol decomposition process step can undesirably convert CO back to CO via the water-gas shift reaction. Furthermore, extraneous water can react with methanol in a methanol steam reforming reaction to form CO and hydrogen, reducing process efficiency. Accordingly, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the water from the first product stream. For example, in certain embodiments, the method further includes separating at least 50%, or at least 75%, or at least 90%, or at least 95%, or at least 99%, or at least 99.5% of the water in the first product stream. In various embodiments described elsewhere herein, the portion of the first product stream included in the second feed stream has a water content of 10 mol% or less, e.g., 2 mol% or less, or 1 mol% or less, or 0.5 mol% or less.

[0027] In embodiments in which water is separated from the CO hydrogenation process, the water may be disposed of as waste or recycled to other processes. For example, in various embodiments, the separated water is sent to an electrolysis reactor for the formation of H gas, for example, for use in this or other processes. In certain embodiments, the separated water is subjected to a purification step before being introduced into the electrolysis reactor.

[0028] In various embodiments described elsewhere herein, not all H gas input to CO hydrogenation is reacted. Accordingly, in such embodiments, the method may further include separating at least a portion of the H from the first product stream. For example, in certain embodiments described elsewhere herein, the method further includes separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H in the first product stream. The separated H may optionally be purified and then optionally recycled. In various embodiments, at least a portion of the separated H may be recycled to the first feed stream and / or directed to another reactor. For example, in various embodiments, at least a portion of the separated H is directed to a Fischer-Tropsch reactor feed stream (e.g., at least a portion of the H separated from the first product stream is provided to a third feed stream). In certain embodiments, the method further includes activating a Fischer-Tropsch catalyst using at least a portion of the H separated from the first product stream. Additionally or alternatively, at least a portion of the H2 separated from the first product stream can be used to activate a methanol decomposition catalyst.

[0029] Advantageously, some processes described herein may be integrated to increase efficiency. For example, in various embodiments described elsewhere herein, contacting the second feed stream with a methanol cracking catalyst and contacting the first feed stream with a hydrogenation catalyst occur in the same plant. As will be understood by those skilled in the art, "same plant" means that the two processes occur within a small geographic area or region, such that it is economical to directly connect the two without significant intervening transportation steps. For example, in certain embodiments described elsewhere herein, at least a portion of the methanol of the first product stream may be provided directly to the second feed stream.

[0030] As described herein, there are many uses for hydrogen from the first product stream. Any or all of them may be utilized in certain real-world processes. In particular, the inventors recognize that the presence of hydrogen in the second feed stream may work against the conversion of methanol to carbon monoxide (i.e., because hydrogen is a by-product in that reaction, the presence of hydrogen in the second feed stream would force the equilibrium in an undesirable reverse direction). Thus, in various embodiments, the portion of the first product stream provided to the second feed stream comprises no more than 50% of the hydrogen in the first product stream, e.g., no more than 25%, no more than 10%, or no more than 5% of the hydrogen in the first product stream.

[0031] The portion of the first product stream provided to the second feed stream may advantageously be at elevated temperature and / or pressure. This can reduce capital costs by alleviating the need to heat and / or pressurize the second feed stream. Thus, in various embodiments described elsewhere herein, the portion of the first product stream provided to the second feed stream has a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C. In certain embodiments, the portion of the first product stream provided to the second feed stream is at a pressure of 0-50 barg, e.g., 1-50 barg.

[0032] Compared to gaseous compositions, compositions that are liquid at ambient temperature and pressure generally require lower capital expenditures for handling due to their increased density and reduced need for high pressure and / or low temperature. The inventors have noted that the methanol product of CO2 hydrogenation can be easily stored and / or transported. Accordingly, in various embodiments described elsewhere herein, contacting the second feed stream with the methanol cracking catalyst and contacting the first feed stream with the dehydrogenation catalyst occur in different plants. As used herein, a different "plant" is not simply a different catalyst bed or a different vessel, but rather a different facility from the facility where carbon dioxide hydrogenation occurs. In such embodiments, the plant may be, for example, at least 1 km away from the facility where hydrogenation occurs. In various such embodiments, the methanol from the first product stream may be stored and / or transported before being provided to the second feed stream.

[0033] In various embodiments described elsewhere herein, at least a portion of the methanol of the first product stream is stored (e.g., in one or more tanks) before being provided to the second feed stream. The storage can be for any suitable time. In various embodiments, the stored portion of the methanol of the first product stream is stored for at least 1 day, e.g., at least 2 days, or at least 3 days, or at least 1 week. In certain embodiments, the stored portion of the methanol is transported at least 1 km, e.g., at least 2 km, or at least 10 km, during storage. In some embodiments, the methanol may be transported via a pipeline.

[0034] The second feed stream introduces methanol for decomposition into CO and H. Methanol decomposition is a different process than methanol reforming, which reacts methanol with water to produce CO and H. Thus, in various embodiments as described elsewhere herein, methanol reforming is not utilized. For example, in certain embodiments, 10% or less (e.g., 5% or less, or 1% or less) of the H is derived from methanol reforming.

[0035] The water-gas shift reaction is another method for producing H by reacting carbon monoxide with water. The reaction is reversible; carbon dioxide can also react with hydrogen to form carbon monoxide and water. Both of these reactions are conventionally used in the art. Advantageously, the disclosed method avoids the use of both the water-gas shift reaction and the reverse water-gas shift reaction. Thus, in various embodiments described elsewhere herein, less than 10% (e.g., less than 5%, or less than 2%) of each of the H, CO, and CO of the process is produced by the water-gas shift reaction or the reverse water-gas shift reaction, as appropriate. In various methods disclosed herein, a dedicated water-gas shift or reverse water-gas shift reactor is not used (although, as will be understood by those skilled in the art, the water-gas shift or reverse water-gas shift reaction may act to a small extent as a side reaction during certain processes).

[0036] As described herein, methanol decomposition is utilized to form a product stream comprising CO and H. Accordingly, in various embodiments described elsewhere herein, the second feed stream comprises at least 5 mol% methanol. For example, in certain embodiments, the second feed stream comprises at least 7.5% methanol, e.g., at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0037] Optionally, the second feed stream may include one or more additional gases, which may be inert or reactive. In such embodiments, the second feed stream may further include one or more of H2, CO, CH4, CO2, and N2. In certain embodiments, the second feed stream includes an inert carrier gas, which includes one or more of CH4, CO2, and N2. Additionally or alternatively, H2 and / or CO may be added to the second feed stream to regulate the cracking reaction and / or to provide a desired second product stream for use in the Fischer-Tropsch process. In such embodiments, the second feed stream further includes H2 and / or CO. In various embodiments described elsewhere herein, one or more of H2, CO, CH4, CO2, and N2 are present in the second feed stream in an amount ranging from up to 50 mol%, e.g., up to 40 mol%, or up to 30 mol%.

[0038] In various embodiments, the second feed stream has a low water content. Water present can react with CO and be at least partially converted to CO and H through the water-gas shift reaction, and water can also react with methanol via reforming to provide H and CO. According to the reaction equilibrium of methanol decomposition, the produced H is antithetical to the decomposition of methanol to CO and H. Thus, in various embodiments described elsewhere herein, the second feed stream has a water concentration of 5 mol% or less, e.g., 2 mol% or less, or 1 mol% or less, or 0.5 mol% or less, or 0.3 mol% or less, or 0.2 mol% or less, or 0.1 mol% or less.

[0039] The second feed stream may be provided at an elevated temperature. For example, in various embodiments described elsewhere herein, the second feed stream has a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0040] The second feed stream is contacted with a methanol decomposition catalyst. Any suitable decomposition catalyst can be used, and a variety are known in the art. For example, the decomposition catalyst can include a transition metal, such as one or more transition metals selected from Groups 7-11 of the periodic table. In certain embodiments, the methanol decomposition catalyst includes one or more of Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ir, or Pt, or mixtures thereof. In some embodiments, the decomposition catalyst can include an intermetallic compound or alloy. For example, the catalyst can further include one or more of Sc, Y, Ti, Zr, Ce, B, Al, Ga, In, Si, Ge, Sn, or Sb. The decomposition catalyst can be a supported catalyst, where the support is a refractory oxide such as diamond oxide, silica, zirconia, ceria, titania, alumina, lanthanum oxide, or magnesia. In some embodiments, the methanol decomposition catalyst is, for example, a copper / zinc oxide catalyst on alumina.

[0041] Those skilled in the art will be familiar with catalytic methods for decomposing methanol into CO and H. Various examples of catalysts and catalytic processes are described in U.S. Pat. Nos. 6,541,142, 9,833,773, 4,716,859, and Usami et al., "Catalytic methanol decomposition at low temperatures over palladium supported on metal oxides," Appl. Cat. A 171(1): 123-130 (1998), each of which is incorporated herein by reference in its entirety.

[0042] Contacting the second feed stream with the methanol decomposition catalyst is carried out at a temperature suitable for efficient methanol decomposition. In various embodiments described elsewhere herein, contacting the second feed stream with the methanol decomposition catalyst is carried out at a temperature ranging from 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C. Contacting can be carried out at various suitable pressures, e.g., ranging from 0 to 50 barg. In various embodiments described elsewhere herein, contacting with the methanol decomposition catalyst can be integrated with a Fischer-Tropsch reactor. Thus, in such embodiments, contact with the methanol decomposition catalyst may be carried out at relatively high pressures, for example up to 50 barg, such as in the range of 20 to 40 barg.

[0043] As described herein, contacting the second feed stream with the methanol decomposition catalyst may be carried out in the same plant as contacting the first feed stream with the hydrogenation catalyst. In such instances, it may be advantageous to adjust the temperatures of the methanol decomposition and hydrogenation reactions to avoid excessive heating and cooling capital and energy costs. Thus, in certain embodiments described elsewhere herein, contacting the second feed stream with the methanol decomposition catalyst is carried out at a temperature within 75° C., e.g., within 50° C., of the temperature of contacting the first feed stream with the hydrogenation catalyst.

[0044] The methanol decomposition reaction ideally produces CO and H2, with minimal other products. Thus, in various embodiments described elsewhere herein, the decomposition of methanol is carried out at a carbon product selectivity of at least 50% relative to CO, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90% relative to CO2. Advantageously, in various embodiments, the decomposition of methanol is carried out at a selectivity of 20% or less relative to CO2, e.g., 15% or less, or 10% or less, or 5% or less. In various embodiments described elsewhere herein, the decomposition of methanol is carried out at a methanol conversion of at least 30%, e.g., at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0045] As described herein, the decomposition of methanol produces CO and H. Thus, in various embodiments described elsewhere herein, the second product stream comprises at least 20 mol %, e.g., at least 35 mol %, or at least 50 mol %, or at least 65 mol % of the sum of CO and H. Without being bound by theory, methanol decomposition under these conditions is expected to produce 2 moles of H per mole of CO. Thus, in various embodiments described elsewhere herein, the second product stream has a molar ratio of hydrogen to carbon monoxide in the range of 0.5:1 to 5:1, e.g., 1:1 to 3:1, or 1.5:1 to 2.5:1, or 3.5:1. Of course, in other embodiments, this molar ratio may be different, for example, as a result of including H or CO in the second feed stream.

[0046] In various embodiments, the second product stream comprises 20 mol% or less of CO, e.g., 15 mol% or less of CO, or 10 mol% or less of CO, or 5 mol% or less of CO, excluding CO not derived from methanol decomposition (e.g., excluding any CO present in the second feed stream, such as unreacted CO from methanol synthesis).

[0047] Advantageously, a portion of the methanol is consumed during the methanolysis reaction. Thus, in various embodiments described elsewhere herein, the second product stream comprises 75 mol% or less methanol, e.g., 60 mol% or less methanol, 50 mol% or less methanol, or 25 mol% or less methanol.

[0048] In some embodiments, further removal of methanol from the second product stream is desirable. For example, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the methanol from the second product stream, e.g., separating at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream. Advantageously, at least a portion of the methanol of the second product stream, e.g., the methanol separated from the second product stream, may be transferred or recycled to other processes. For example, in various embodiments described elsewhere herein, the method further includes recycling at least a portion of the methanol separated from the second product stream to the second feed stream.

[0049] As described herein, the methanol decomposition reaction theoretically produces CO and H2 in a 2:1 molar ratio, but actual reaction output can vary. This can result in excess hydrogen for subsequent processes, depending on the desired ratio. In particular, hydrogen may be present in the second feed stream, further increasing the ratio in the second product stream. Accordingly, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the H2 from the second product stream. The separated H2 is suitable for various processes. For example, in certain embodiments, at least a portion of the H2 separated from the second product stream is provided to the first feed stream. Additionally or alternatively, in various embodiments described elsewhere herein, the method further includes activating a methanol decomposition catalyst or a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the second product stream.

[0050] As described herein, the third feed stream includes at least a portion of the CO of the second product stream. Thus, in various embodiments described elsewhere herein, at least 50% of the CO of the second product stream is provided to the third feed stream. For example, in certain embodiments, at least 75%, e.g., at least 90%, or at least 95%, or at least 99% of the CO of the second product stream is provided to the third feed stream. In various embodiments, substantially all of the CO of the second product stream is provided to the third feed stream. Additionally or alternatively, in various embodiments as described elsewhere herein, the CO of the third feed stream may be partially supplied from a CO source other than the second product stream.

[0051] As described above, the third feed stream comprises H and CO, and the second product stream comprises H. In various embodiments described elsewhere herein, at least a portion of the H of the second product stream is provided to the third feed stream. For example, in certain embodiments, at least 50%, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99% of the H of the second product stream is provided to the third feed stream. In various embodiments, substantially all of the H of the second product stream is provided to the third feed stream. Additionally or alternatively, in various embodiments as described elsewhere herein, the H of the third feed stream may be at least partially supplied from a hydrogen source other than the second product stream.

[0052] In various embodiments as described elsewhere herein, the third feed stream may include other gases, such as CO, CH, or N. In embodiments where other gases are included, they may be contained in the second product stream and carried to the third feed stream. However, in other embodiments, one or more other gases (e.g., one or more of CO, CH, N) are provided to the third feed stream from a source other than the second product stream.

[0053] Advantageously, the portion of the second product stream included in the third feed stream may be adjusted as desired for the process of the third feed stream. For example, in various embodiments described elsewhere herein, the portion of the second product stream included in the third feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, e.g., in the range of 1:1 to 2.5:1.

[0054] As described elsewhere herein, the third feed stream is contacted with a Fischer-Tropsch catalyst. Thus, in various embodiments, as described elsewhere herein, the third feed stream has a H2:CO molar ratio suitable for Fischer-Tropsch synthesis. For example, in various embodiments, the third feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1, e.g., in the range of 1:1 to 2.5:1. In certain embodiments, the third feed stream has a H2:CO molar ratio of at least 1.2:1. For example, in various embodiments, the third feed stream can have a H2:CO molar ratio in the range of 1.2:1 to 2.5:1, or in the range of 1.4:1 to 2.5:1, or in the range of 1.6:1 to 2.2:1. In other embodiments, the third feed stream may have a H2:CO molar ratio in the range of 1:1 to 2:1, for example, 1:1 to 1.8:1, or 1:1 to 1.6:1, or 1:1 to 1.4:1.

[0055] As described herein, the methods disclosed herein can advantageously utilize an iron-containing Fischer-Tropsch catalyst. In certain embodiments, the Fischer-Tropsch catalyst comprises an amount of iron, calculated as Fe(0), ranging from 15 to 95 wt. %, e.g., 25 to 95 wt. %, or 30 to 90 wt. %. The iron-containing Fischer-Tropsch catalyst may comprise additional elements to tailor reactivity and product distribution. For example, in various embodiments described elsewhere herein, the iron-containing Fischer-Tropsch catalyst further comprises sodium, potassium, magnesium, calcium, ruthenium, palladium, platinum, rhodium, rhenium, manganese, chromium, nickel, iron, zinc, copper, molybdenum, tungsten, zirconium, gallium, thorium, lanthanum, cerium, or a combination thereof. For example, in certain embodiments, the iron-containing Fischer-Tropsch catalyst further comprises at least one of copper, zinc, and manganese. In various embodiments described elsewhere herein, the Fischer-Tropsch catalyst further comprises manganese (e.g., in an amount of 0.1 to 15 wt. %, or 1 to 10 wt. %).

[0056] In various embodiments described elsewhere herein, the Fischer-Tropsch catalyst is a supported catalyst, and the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, silicon oxide, magnesium oxide, and zinc oxide (e.g., at least one of titanium oxide, aluminum oxide, and silicon oxide). For example, in certain embodiments, the support is a titanium dioxide support, an alumina support, or a silica support. In various embodiments, the support is a shaped particle, e.g., an extrudate. The catalyst can be prepared using methods conventional in the art.

[0057] Prior to use, certain catalysts require activation. In various embodiments described elsewhere herein, the Fischer-Tropsch catalyst is activated in a reducing atmosphere. In various embodiments, the catalyst is subsequently reduced to produce a reduced catalyst material for use in catalyzing a Fischer-Tropsch reaction. In embodiments in which the Fischer-Tropsch catalyst contains iron, this method results in at least a portion of the iron being converted to iron metal. Desirably, the reduction results in at least 50% of the iron being provided as iron(0). Those skilled in the art can use conventional methods to reduce iron catalyst materials (e.g., iron oxide-based materials) to the metallic form. In various embodiments described elsewhere herein, the first reducing agent is hydrogen gas, H2. Hydrogen gas may be mixed with other gases, such as inert carrier gases. Examples of such inert carrier gases include nitrogen, carbon dioxide, argon, or helium. Hydrogen gas may be mixed with carbon monoxide, with or without one or more additional carrier gases. In various embodiments, the reduction is carried out by contacting the first catalyst material with a first reducing gas, the first reducing gas comprising a first reducing agent, the first reducing gas comprising at least 50% H by volume (e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or essentially 100% H by volume). In various embodiments, the contacting is carried out at an elevated temperature, e.g., in the range of 300°C to 550°C. As noted above, the H for the reduction can be provided from the first product stream or the second product stream. H can also be separated and recycled from the third product stream for use in the reduction of the Fischer-Tropsch catalyst.

[0058] Carburization can be used for certain catalysts to increase their reactivity and / or selectivity. During carburization, the catalyst is contacted with a carbon-containing gas, often at elevated temperatures. Accordingly, in various embodiments described elsewhere herein, the Fischer-Tropsch catalyst is carburized. For example, in certain embodiments, the method further includes contacting the Fischer-Tropsch catalyst with a carburizing gas at a temperature ranging from 200°C to 400°C. In certain embodiments, the carburizing gas contains CO in an amount of at least 1% by volume (e.g., at least 22% by volume, or at least 3% by volume, or at least 5% by volume, or at least 10% by volume, or at least 15% by volume, or at least 20% by volume). For example, the carburizing gas may contain at least 50% by volume CO (e.g., at least 60% by volume, or at least 70% by volume, or at least 80% by volume, or at least 90% by volume, or at least 95% by volume, or essentially 100% by volume CO). In various embodiments, the carburizing gas further includes H2 and / or N2. For example, in certain embodiments, the carburizing gas includes H2 in the range of 1% to 99% by volume. In such embodiments, the carburizing gas may further include N2 in the range of 1% to 99% by volume. The carburizing gas may be mixed with an inert carrier gas. Examples of such inert carrier gases include nitrogen, methane, carbon dioxide, argon, or helium.

[0059] Activation of iron-containing Fischer-Tropsch catalysts can also proceed by direct carburization without reduction. Without being bound by theory, it is believed that iron carbide is obtained by contacting an iron oxide precursor with a carburizing gas. Accordingly, in certain embodiments described elsewhere herein, iron-containing Fischer-Tropsch catalysts are carburized without a prior reduction step. In certain embodiments described elsewhere herein, Fischer-Tropsch catalysts are activated in a reducing and / or carburizing atmosphere. Advantageously, the integrated processes described herein may contain one or more recycles to increase overall process efficiency. Accordingly, in some embodiments described elsewhere herein, the reducing and / or carburizing atmosphere includes at least a portion of the hydrogen from the second product stream and / or at least a portion of the hydrogen from the first product stream.

[0060] The temperature of the Fischer-Tropsch synthesis may suitably be in the range of 200 to 400° C., for example, 200 to 300° C., or 210 to 400° C., or 210 to 300° C., or 220 to 400° C., or 220 to 300° C. In various embodiments described elsewhere herein, the temperature of the Fischer-Tropsch synthesis is in the range of 200 to 250° C., for example, or 200 to 240° C., or 200 to 230° C., or 200 to 220° C., or 210 to 250° C., or 210 to 240° C., or 210 to 230° C., or 220 to 250° C., or 220 to 240° C., or 230 to 250° C. For example, in certain embodiments, contacting the third feed stream with the Fischer-Tropsch catalyst is conducted at a temperature in the range of 150-400°C, e.g., 150-350°C, or 150-300°C, or 150-250°C, or 150-220°C, or 220-400°C, or 220-350°C, or 220-300°C, or 220-280°C, or 240-400°C, or 240-350°C, or 240-300°C, or 300-400°C. The reaction pressure may suitably be in the range of 10 to 50 barg, for example, 20 to 50 barg, or 25 to 50 barg, or 10 to 40 barg, or 20 to 40 barg, or 25 to 40 barg, or 10 to 35 barg, or 20 to 35 barg, or 25 to 35 barg. In certain embodiments, contacting the third feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20 to 40 barg.

[0061] Subject to the limitations set forth herein, one skilled in the art can adapt conventional Fischer-Tropsch catalysts and methods to arrive at the methods of the present disclosure. Suitable techniques for catalyst preparation and hydrocarbon synthesis, particularly the synthesis of C5+ hydrocarbons and / or oxygenates, are well known in the art and are described, for example, in International Patent Application Publication No. WO 2019 / 154885, the entire contents of which are incorporated herein by reference.

[0062] Advantageously, in various embodiments as described elsewhere herein, contacting the third feed stream with the Fischer-Tropsch catalyst and contacting the second feed stream with the methanol cracking catalyst may be carried out in the same plant. This may be, for example, in different beds within the same reactor or in different reactors. In such embodiments, the two processes may be integrated together to provide efficient conversion of methanol to hydrocarbons.

[0063] The Fischer-Tropsch process is typically used to produce C5+ hydrocarbons, such as unsubstituted C5+ hydrocarbons (e.g., alkanes and alkenes) and oxygenated C5+ hydrocarbons (e.g., C5+ alcohols, aldehydes, ketones, carboxylic acids). It is desirable for the Fischer-Tropsch reactions described herein to be operated with high selectivity to hydrocarbons. For example, in various embodiments described elsewhere herein, contacting the Fischer-Tropsch catalyst with the third feed stream is carried out with a C5+ selectivity of at least 30%, e.g., at least 50%, or at least 70%. The hydrocarbon composition of the third product stream can vary depending on the catalyst type and process conditions known in the art. In various embodiments, the hydrocarbon composition comprises hydrocarbons (e.g., linear hydrocarbons, branched hydrocarbons, saturated or unsaturated hydrocarbons) and their oxygenated derivatives. In various embodiments described elsewhere herein, the hydrocarbon composition comprises at least one of an alkane, an alkene, and an alcohol.

[0064] As discussed above, the inventors have noted that iron-containing Fischer-Tropsch catalysts often produce large amounts of CO. Because CO is a common waste product, in conventional processes, this CO production is undesirable and represents a significant obstacle to economical Fischer-Tropsch production of hydrocarbons. However, as described elsewhere herein, CO produced in the third product stream can, in some embodiments, be advantageously recycled back into the first feed stream. Thus, the present methods realize the benefits of iron-containing Fischer-Tropsch catalysts while mitigating their drawbacks. Thus, in certain embodiments described elsewhere herein, contacting the third feed stream with the Fischer-Tropsch catalyst produces CO with a selectivity of at least 2%. For example, in certain embodiments, contacting produces CO with a selectivity of at least 5%, or at least 10%, or at least 12%, or at least 15%, or at least 20%. In various embodiments, the selectivity to CO does not exceed 50%.

[0065] Generally, long-chain hydrocarbons are more desirable than short-chain hydrocarbons. Accordingly, in various embodiments described elsewhere herein, the third product stream comprises C1-C4 hydrocarbons, and the method further comprises separating at least a portion of the C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream. In certain embodiments, the method further comprises oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream and / or the third feed stream. For example, catalytic partial oxidation of hydrocarbon feedstocks is described in EP 0 303 438 A1, the entire contents of which are incorporated herein by reference. Additionally or alternatively, in certain embodiments, at least a portion of the light hydrocarbon stream may be sent to an autothermal reforming unit, such as a steam reforming unit and / or an electrically heated steam reforming unit. The resulting hydrogen and / or carbon oxides may then be at least partially included in the first steam feed and / or the third feed stream, as described elsewhere herein.

[0066] The light hydrocarbon stream contains multiple components, including short-chain (e.g., C1-C4) saturated hydrocarbons, short-chain olefins, and short-chain oxygenates. In particular, olefins (e.g., ethene, propene, butene) and alcohols can also be recycled to the Fischer-Tropsch reactor to produce additional C5+ hydrocarbons. Accordingly, in various embodiments as described elsewhere herein, the method further includes including at least a portion of the light hydrocarbon stream in a third feed stream. Additionally or alternatively, at least a portion of the light hydrocarbon stream may be included in the first feed stream and / or the second feed stream and sent to the third feed stream.

[0067] In various embodiments, the third product stream may contain unreacted H. In various embodiments, as described elsewhere herein, the method further includes separating at least a portion of the H from the third product stream. The separated H may then be sent to a process requiring it. For example, in certain embodiments, at least a portion of the H separated from the third product stream is provided to the first feed stream and / or the third feed stream. And, as described above, at least a portion of the H separated from the third product stream can be used to activate a Fischer-Tropsch catalyst.

[0068] In various embodiments, the third product stream can include unreacted CO. In various embodiments as described elsewhere herein, the method further includes separating at least a portion of the CO from the third product stream. The separated CO may then be sent to a process requiring it. For example, in certain embodiments, at least a portion of the CO separated from the third product stream is provided to a third feed stream.

[0069] As discussed above, the use of an iron-containing Fischer-Tropsch catalyst can produce relatively large amounts of CO2. In various embodiments, the third product stream can include CO2. For example, in certain embodiments, the third product stream can include at least 1% CO2, e.g., at least 2% CO2, or at least 3% CO2, or at least 4% CO2, or at least 5% CO2, or at least 7.5% CO2, or at least 10% CO2. Accordingly, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the CO2 from the third product stream. The separated CO2 may then be sent to a process requiring it. For example, in certain embodiments, at least a portion of the CO2 separated from the third product stream is provided to the first feed stream. Thus, in such embodiments, the first feed stream includes CO2, and at least a portion of the CO2 is recycled from the third product stream.

[0070] It may be desirable to provide a C5+ hydrocarbon product stream from the third product stream, i.e., a product stream containing at least 50 wt% C5+ hydrocarbons, e.g., at least 60 wt% C5+ hydrocarbons, or at least 70 wt% C5+ hydrocarbons. As one skilled in the art will appreciate, this can be accomplished, for example, by separating at least a portion of the C1-C4 hydrocarbons, CO, CO2, and other components such as H2, as described above.

[0071] Additionally, in some cases, it may be desirable to perform further conversions on the C5+ hydrocarbon product stream. Hydrotreating, i.e., contacting the C5+ hydrocarbon product stream with hydrogen and a hydrotreating catalyst, can be used for this purpose. Thus, in various embodiments, the methods described elsewhere herein include hydrotreating the C5+ hydrocarbon product stream by contacting the C5+ hydrocarbon product stream with hydrogen and a hydrotreating catalyst. Various hydrotreating process steps can be used. For example, hydrocracking can be used to provide products having lower molecular weights, e.g., to convert higher molecular weight waxes to lower molecular weight products for use as fuels such as aviation fuel, diesel fuel, or gasoline. Hydrodeoxygenation can be used to convert oxygenates to non-oxygenated hydrocarbons. Hydrotreating can also be used to convert olefins to alkanes. Hydroisomerization can be used to change the mixture of hydrocarbon isomers. At least a portion of the H2 used for hydrotreating can be H2 separated from one or more of the first, second, and third product streams, as described above.

[0072] As will be appreciated by those skilled in the art, the Fischer-Tropsch process described herein can be used to provide a variety of end products. For example, in various embodiments as described elsewhere herein, one or more products are provided from at least a portion of the C5+ hydrocarbons of the third product stream. The one or more products can be, for example, one or more of a fuel (e.g., diesel fuel, gasoline, or aviation fuel), a wax, or an oil (e.g., for use in lubrication or metalworking).

[0073] The methods described herein can be performed at high throughput. For example, in various embodiments described elsewhere herein, CO hydrogenation, MeOH decomposition, and / or Fischer-Tropsch synthesis are performed at GHSVs ranging from 2000 hr to 20,000 hr. For example, in various such embodiments, the contacting is carried out at a GHSV ranging from 4000 hr to 18,000 hr, or from 6000 hr to 14,000 hr, or from 8000 hr to 12,000 hr, or from 2000 hr to 10,000 hr, or from 4000 hr to 10,000 hr, or from 6000 hr to 10,000 hr, or from 2000 hr to 8,000 hr, or from 4000 hr to 8,000 hr, or from 2000 hr to 6000 hr. Of course, higher and lower space velocities can also be used, depending on the system.

[0074] The inventors have noted that carbon dioxide is the primary carbon input to the processes described herein, and that the carbon dioxide can be advantageously provided by a variety of sources. Importantly, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the carbon dioxide in the first feed stream can be derived from renewable sources.

[0075] Carbon dioxide is a common waste product, and it is often desirable to remove it from waste streams rather than release it into the atmosphere. Such capture of carbon dioxide is important to the implementation of many renewable initiatives, as it helps lower the carbon dioxide footprint of the associated processes. Advantageously, the carbon dioxide utilized in the methods described herein can be carbon dioxide collected from the atmosphere or carbon dioxide that would otherwise be released into the atmosphere, for example, from combustion or other industrial processes. Carbon dioxide may be captured when it is recovered or absorbed after being released from an industrial process, or it may be taken directly from the atmosphere. Methods of carbon dioxide capture are known to those skilled in the art. In various embodiments, at least a portion of the CO2 of the first feed stream is from direct air capture. Additionally, or alternatively, carbon dioxide is often scrubbed from industrial wastewater, particularly from processes that produce large amounts of carbon dioxide as a by-product. Accordingly, in various embodiments described elsewhere herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the CO2 of the first feed stream is captured from a manufacturing plant, such as a bioethanol plant, steel mill, or cement plant.

[0076] As mentioned above, renewable sources can be used to provide CO2 for the claimed methods. For example, biomass is an attractive source of renewable carbon dioxide for use in the methods described herein. One source of biomass is agricultural products in the form of dedicated energy crops such as switchgrass, miscanthus, bamboo, sorghum, tall fescue, kochia, wheatgrass, poplar, willow, silver maple, eastern cottonwood, green ash (ash), black walnut, sweetgum (gum), and sycamore. Another source of biomass is agricultural waste or agricultural crop residues. Conventional agricultural activities, including the production of food, feed, fiber, and forest products, generate large amounts of waste plant material. Examples of such materials include corn stover, wheat straw, oat straw, barley straw, sorghum stubble, and rice straw. A third source of biomass comes from forestry residues left after timber operations. Biomass can also be in the form of commercial waste, industrial waste, sewage sludge, and municipal waste, including commercial and residential trash, including yard trimmings, paper and paperboard, plastics, rubber, leather, textiles, and food waste. Accordingly, in various embodiments described elsewhere herein, at least a portion of the CO2 of the first feed stream is derived from renewable resources. For example, in certain embodiments, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the CO2 of the first feed stream is derived from biomass, e.g., agricultural biomass or municipal waste biomass. Additional sources of agricultural biomass will be apparent to those skilled in the art, as determined by local availability, economics, and process suitability.

[0077] To produce carbon dioxide from carbon-containing materials such as biomass, the material is typically subjected to gasification. Gasification involves heating the material under controlled conditions to produce a gaseous stream of carbon monoxide, hydrogen, and carbon dioxide. Controlled amounts of other reactants, such as oxygen and / or steam, can be used to adjust the process. Gasification conditions are adjusted according to the carbon-containing material being gasified to efficiently produce gaseous products. In various embodiments, the carbon dioxide in the first feed stream comprises carbon dioxide from the gasification of biomass, e.g., at least 50%, at least 75%, at least 90%, or at least 95% of the carbon dioxide is from the gasification of biomass. The biomass can be from any source, as described above, or can be combined from multiple sources.

[0078] Conventional H gas is most commonly obtained from natural gas, often through methane steam reforming, partial oxidation of hydrocarbons, and / or coal gasification. However, each of these processes, as conventionally practiced, releases significant amounts of CO into the atmosphere and relies on fossil fuels as starting materials and / or energy sources. In contrast, other H sources are known that are preferable from an environmental standpoint. Accordingly, in various embodiments described elsewhere herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the H in the first feed stream, the second feed stream, and / or the third feed stream is from a renewable resource.

[0079] As is known in the art, hydrogen can be named based on its color depending on its source. Example types of hydrogen include green hydrogen, blue hydrogen, gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0080] One potential source of green hydrogen is through the electrolysis of water. Numerous electrolysis methods are known in the art. For example, electrolysis may be performed on pure water to produce hydrogen gas and oxygen gas, or on other solutions, such as saline solution, to produce hydrogen gas and another product (e.g., chlorine gas). In certain embodiments, hydrogen is formed through the electrolysis of saline solution. Water electrolysis is further described in U.S. Pat. No. 4,312,720, U.S. Pat. No. 4,021,323, and U.S. Pat. No. 4,094,751, each of which is incorporated by reference in its entirety.

[0081] To qualify as green hydrogen, the electricity used in the electrolysis of water must come from a renewable source, i.e., a source that does not rely on the combustion of fossil fuels. Examples of renewable electricity sources include solar power via photovoltaic capture or solar thermal technology, wind power, geothermal energy capture, hydroelectric energy, or other renewable sources. Hydrogen generated using solar energy for water electrolysis is sometimes referred to as yellow hydrogen. Suitable renewable energy sources are known to those skilled in the art and may be optionally selected through certification by an appropriate institution. Thus, in various embodiments described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is green hydrogen and / or yellow hydrogen. For example, in certain embodiments, the method further includes providing at least a portion of the H2 in the first feed stream and / or the third feed stream by water electrolysis. In various embodiments, the water electrolysis is performed using electricity obtained at least in part from a renewable resource.

[0082] Certain recycle streams may also be adapted to provide power for water electrolysis, if desired. For example, in various embodiments as described elsewhere herein, water electrolysis is carried out using electricity generated at least in part from steam created by combustion of a light hydrocarbon stream that is provided at least in part from the third product stream.

[0083] Water electrolysis conventionally produces both H and O gases. As described elsewhere herein, in some embodiments, the method further includes oxidizing at least a portion of a light hydrocarbon stream (e.g., obtained from the third product stream) to provide a pOX stream. In such embodiments, the oxidation may be performed using O. Thus, in certain embodiments, at least a portion of the O produced by water electrolysis is fed to a partial oxidation reactor.

[0084] Blue hydrogen is defined as hydrogen gas that relies somewhat on fossil fuels for production but is produced in a manner that is entirely carbon-neutral (i.e., does not result in any net introduction of carbon dioxide into the atmosphere). In various embodiments described elsewhere herein, the hydrogen utilized in the methods described elsewhere herein includes blue hydrogen. An example of blue hydrogen is hydrogen gas produced from fossil-fuel-derived hydrocarbons, such as methane gas, with the resulting carbon product captured or otherwise utilized. For example, steam reforming of methane can be performed to produce three moles of hydrogen gas and one mole of carbon monoxide per mole of methane. Methane steam reforming is highly endothermic and requires a significant energy input. Of course, the energy required to carry out these methods must come from renewable sources or sources with appropriate carbon capture technology. Thus, in various embodiments as described elsewhere herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the hydrogen is formed by steam reforming of methane. Steam reforming of methane to produce hydrogen is described in International Patent Application Publication No. 2004 / 022480, which is incorporated herein by reference in its entirety. Thus, in various embodiments as described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is blue hydrogen.

[0085] Grey hydrogen is the most common source of H. Grey hydrogen is produced from natural gas / methane by steam reforming, but in contrast to blue hydrogen, the resulting greenhouse gases (e.g., CO) are not captured. In various embodiments described elsewhere herein, at least a portion of the H in the first feed stream and / or the third feed stream is grey hydrogen.

[0086] Black hydrogen and brown hydrogen are produced from black or lignite coal, respectively, often by its gasification without carbon capture. In various embodiments as described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is black hydrogen and / or brown hydrogen.

[0087] Pink hydrogen is produced by the electrolysis of water, and the energy required for the electrolysis is generated by nuclear power. Pink hydrogen is sometimes referred to as purple hydrogen or red hydrogen. In various embodiments described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is pink hydrogen. Pink hydrogen is also known as purple hydrogen or red hydrogen.

[0088] Turquoise hydrogen is produced by methane pyrolysis, with by-products being hydrogen gas and solid elemental carbon. In various embodiments described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is turquoise hydrogen.

[0089] White hydrogen is naturally occurring hydrogen that can be released by fracking. In various embodiments as described elsewhere herein, at least a portion of the H2 in the first feed stream and / or the third feed stream is white hydrogen.

[0090] As described herein, the disclosed methods, in various embodiments, involve three central reactions: CO hydrogenation, methanol decomposition, and Fischer-Tropsch synthesis. As described herein, these reactions can be advantageously carried out in different spatial configurations relative to one another. As known in the art, a reaction zone consists of one or more catalyst beds, and one or more reaction zones may be located within the same plant. Different plants are typically geographically separated, so that feedstocks cannot be transferred between them without intervening transportation and storage steps. Thus, in various embodiments described elsewhere herein, the first reaction zone comprises a first reactor in which a hydrogenation catalyst is disposed, the second reaction zone comprises a second reactor in which a methanol decomposition catalyst is disposed, and the third reaction zone comprises a third reactor in which a Fischer-Tropsch catalyst is disposed. In various embodiments described elsewhere herein, the first reaction zone includes a first catalyst bed containing a hydrogenation catalyst, the second reaction zone includes a second catalyst bed containing a methanol cracking catalyst, and the third reaction zone includes a third catalyst bed containing a Fischer-Tropsch catalyst. For example, in certain embodiments, the first, second, and third catalyst beds are located within the same reactor, e.g., a catalyst stack or catalyst bed section. In some embodiments, the second and third reactor beds are located within the same reactor, and the first catalyst bed is located within a different reactor than the second and third catalyst beds. For example, in certain embodiments, the first reactor is located in a first plant, and the second and third reactors are located in a second plant.

[0091] As described herein, in some embodiments, various catalyst beds may be located in different reactors. Placing catalyst beds in separate reactors can have various process advantages. For example, such separation allows individual units to experience reactor downtime (e.g., for maintenance) independently of one another. Furthermore, reactors can be maintained at different temperatures to maximize individual process selectivity and efficiency. Exothermic and endothermic chemical reactions require temperature control to maintain stable operating temperatures. Because different catalysts change activity at different rates over time, separate processes performed in separate reactors simplify temperature control. Thus, in certain embodiments as described elsewhere herein, none of the first, second, and third catalyst beds are intermixed. Catalyst intermixing occurs when catalysts for different processes share the same catalyst bed. As used herein, two different catalyst beds within one reactor are not intermixed. In certain embodiments as described elsewhere herein, the first, second, and third catalyst beds are located in separate reactors.

[0092] In some embodiments, similar catalysts may be used for some reactions. For example, in some embodiments, the methanol cracking catalyst and the Fischer-Tropsch synthesis catalyst have the same composition. In particular embodiments, the methanol cracking catalyst and the Fischer-Tropsch synthesis catalyst are the same catalyst.

[0093] An exemplary embodiment is shown in the schematic diagram of FIG. 1, which depicts a process 100 contained within a single plant 141. A first feed stream 111 comprising H and CO is sent to a hydrogenation reaction zone 110 (here, a hydrogenation reactor) where it is contacted with a hydrogenation catalyst 113 under conditions suitable to produce a first product stream 112 comprising methanol. The first product stream typically contains other materials as well. For example, in the embodiment of FIG. 1, the first product stream comprises CO, and at least a portion of the CO is separated from the first product stream and recycled to the first feed stream 111 via CO recycle 114. Similarly, the first product stream may include H (e.g., unreacted H) and / or CO (e.g., from a recycle stream from the third product stream). Here, at least a portion of the H and / or CO is separated from the first product stream and recycled to the first feed stream 111 via H and / or CO recycle stream 115. In the embodiment of FIG. 1 , H2 bypass 124 removes at least a portion of the H2 from first product stream 112 and introduces it into third feed stream 131 for use as a Fischer-Tropsch reactant. H2 activation stream 134 removes at least a portion of the H2 from first product stream 112 and introduces it into the third reaction zone for optional activation of Fischer-Tropsch catalyst 133. The embodiment of FIG. 1 illustrates three different uses for the hydrogen separated from first product stream 112; those skilled in the art will understand that many real-world processes include none, one, two, or all three of these. Any water present can be removed from first product stream 112 by water separation stream 116 to provide a primarily dry second feed stream (121); optionally, water feed stream 116 can be fed to electrolysis reactor 160.

[0094] In the embodiment of FIG. 1 , the remaining portion of first product stream 112 (i.e., after the separations described above) is provided to second feed stream 121. Second feed stream 121 comprises at least a portion of the methanol from the first product stream and is sent to a methanol decomposition reaction zone 120 (here, a methanol decomposition reactor) where it contacts a methanol decomposition catalyst 123 to decompose at least a portion of the methanol and form a second product stream 122 comprising CO and H. In the embodiment of FIG. 1 , from second reaction zone 120, second product stream 122 is directed to a third feed stream 131. Third feed stream 131 comprises H (e.g., from the second product stream) and at least a portion of the CO from the second product stream. Third feed stream 131 is sent to a Fischer-Tropsch reaction zone 130 (here, a Fischer-Tropsch reactor) in which a Fischer-Tropsch catalyst 133 is located. The third feed stream 131 contacts a Fischer-Tropsch catalyst 133 to provide a third product stream 132 comprising C5+ hydrocarbons. In the embodiment of FIG. 1, the third product stream 132 is directed from the third reaction zone 130. Here, a light hydrocarbon stream 136 is separated from the third product stream 132 and sent to a power generator 170. Additionally or alternatively, a light hydrocarbon stream 137, optionally comprising vapor-phase products, is separated from the third product stream 132 and recycled to the third feed stream 131. Examples of vapor-phase products for recycling include CO, H2, CH4, CO2, C2H4, C3H6, C3H8, C3H7OH, and HO. A CO2 recycle stream 138 can be used to recycle CO2 from the third product stream 132 to the first feed stream 111. A generator 170 uses the light hydrocarbon stream to generate electricity 172 (e.g., by combusting the light hydrocarbon stream to form steam, which in turn can drive a turbine), which is supplied to the electrolysis reactor 160. As one skilled in the art will appreciate, the Fischer-Tropsch reaction produces water as a by-product, and as shown in Figure 1, at least a portion of the water can be separated from the third product stream 132, which can be directed to the electrolysis reactor 160 via water stream 138.The electrolysis reactor electrolyzes water (now separated from the first product stream and / or the third product stream) to provide hydrogen gas, using power derived at least in part from the light hydrocarbon stream (although other power sources, including renewable sources, can be used). H gas from the electrolysis reactor 160 is returned to the first feed stream via electrolysis H stream 117.

[0095] As described above, methanol can be formed via the hydrogenation of carbon dioxide in a first plant and then transported (e.g., via vehicle or pipeline) to a second plant, where the methanol is cracked and the resulting carbon monoxide can be used in a Fischer-Tropsch reaction to provide hydrocarbons. An example of such an embodiment is shown in the schematic diagram of FIG. 2. Here, the carbon dioxide hydrogenation step of process 200 occurs in first plant 241. A first feed stream 211 comprising carbon dioxide and hydrogen is directed to a hydrogenation reaction zone 210 (here, a hydrogenation reactor) containing a CO2 hydrogenation catalyst 213. The first feed stream 211 contacts the CO2 hydrogenation catalyst 213 to hydrogenate at least a portion of the CO2 to produce a first product stream 212 comprising methanol. The first product stream 212 can be subjected to various separations (not shown) as described herein, and the methanol from the first product stream can then be stored for later use and / or transported to another plant. 1 , at least a portion of first product stream 212, the portion comprising methanol, is charged to storage tank 217 and then transported thereto by truck 218 to second plant 243. A portion of the first product stream is provided to second feed stream 221, which is directed to methanol cracking reaction zone 220, where it contacts methanol cracking catalyst 223 to produce second product stream 222 comprising CO and H. Here, at least a portion of second product stream 222 is provided to third feed stream 231. Third feed stream 231 is sent to Fischer-Tropsch reaction zone 230, where it contacts Fischer-Tropsch catalyst 233 to result in third product stream 232 comprising C5+ hydrocarbons.

[0096] Another illustrative embodiment is shown in the schematic diagram of Figure 3, where in process 301, a first feed stream 311 is delivered to a first reaction zone 310 and contacted with a CO2 hydrogenation catalyst 313 to hydrogenate at least a portion of the CO2 in the first feed stream to form a first product stream 312 comprising methanol. The first product stream 312 is directed from the first reaction zone 310, an additional gas stream 324 is added, and the resulting mixture is provided as a second feed stream 321. The second feed stream 321 is directed to a methanol decomposition reaction zone 320, where it is coupled with a methanol decomposition catalyst 323 to provide a second product stream 322. Here, the second product stream 322 is directed from the methanol decomposition reaction zone, and unreacted methanol is substantially separated from the second product stream (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) and recycled to the second feed stream 321 via a methanol recycle 325. In particular, at least a portion of the H2 in second product stream 322 can be separated and recycled to first feed stream 311 via H2 recycle 326. At least a portion of the H2 in second product stream 322 can also or alternatively be provided to third reaction zone 330 to activate Fischer-Tropsch catalyst 333 via H2 stream 327. The remainder of second product stream 322 is provided as part of third feed stream 331 and directed to Fischer-Tropsch reaction zone 330. Also, part of third feed stream 331 is additional gas stream 335, which supplies additional H2 and / or CO to the Fischer-Tropsch reaction zone through a separate inlet. The third feed stream contacts Fischer-Tropsch catalyst 333 in the Fischer-Tropsch reaction zone to provide third product stream 332 comprising C5+ hydrocarbons. A third product stream 332 is conducted from the Fischer-Tropsch reaction zone, and a light hydrocarbon stream 336 is separated therefrom and conducted to a partial oxidation unit 350. The partial oxidation unit oxidizes light hydrocarbons to provide CO and CO, as will be understood by those skilled in the art, and at least a portion of the CO produced from partial oxidation unit 350 is included in third feed stream 331 via CO stream 351.At least a portion of the CO 2 generated from partial oxidation unit 350 is included in first feed stream 311 via CO 2 stream 352 .

[0097] As noted above, various catalysts can be fed together in the same reactor. An example of such an embodiment is shown in the schematic diagram of FIG. 4. Here, in process 400, CO hydrogenation occurs in one reactor, while both methanol decomposition and Fischer-Tropsch synthesis occur in separate reactions. A first feed stream 411 containing CO and H is sent to a first reaction zone 410 (here, a hydrogenation reactor) and contacts a hydrogenation catalyst 413 to provide a first product stream containing methanol. The first product stream 412 is fed as a second feed stream 421 to a stacked-bed reactor 425 containing a methanol decomposition reaction zone 420 (here, a first bed of a stacked-bed reactor containing a methanol decomposition catalyst 423) and a Fischer-Tropsch reaction zone 430 (here, a second bed of a stacked-bed reactor containing a Fischer-Tropsch catalyst 433). The second feed stream 421 contacts a methanol decomposition catalyst 423 to provide a second product stream 422 containing CO and H. The second product stream is fed to a Fischer-Tropsch reaction zone as third feed stream 431, which contacts a Fischer-Tropsch catalyst 433 to provide a third product stream 432 comprising C5+ hydrocarbons, wherein at least a portion of the C5+ hydrocarbons of the third product stream are sent to a hydrotreating unit 460, where they are hydrotreated to provide a final product stream 465. wherein at least a portion of the H2 of the first product stream is separated and directed to the hydrotreating unit 460 via stream 462. H2 may also be provided to the hydrotreating unit in the portion of the third product stream that is directed to the hydrotreating unit.

[0098] In some embodiments, the conversion of CO to hydrocarbons via a methanol intermediate may be carried out in a single reactor, for example, with various catalysts arranged in series. In the embodiment of FIG. 5, process 500 utilizes a syngas source stream 512 entering reactor 525 as a first feed stream 521 in zone 520. First feed stream 521 contacts a hydrogenation catalyst 513, then passes directly to a methanol cracking catalyst 523, and finally to a Fischer-Tropsch catalyst 533. The resulting gas mixture is removed from zone 530 as a third product stream 532. Recycle stream 513 extracts CO gas, in any mixture with light hydrocarbons and other gases, and recycles it to source CO stream 512.

[0099] The invention will now be further described, by way of example only, with reference to the following examples. In the examples, CO conversion is defined as moles of CO used / moles of CO fed x 100, and carbon selectivity is defined as moles of CO attributable to a particular product / moles of CO converted x 100. Unless otherwise specified, temperatures referred to in the examples are applied temperatures, not catalyst / bed temperatures. Unless otherwise specified, pressures referred to in the examples are absolute pressures. [Example]

[0100] Example 1: Fischer-Tropsch production of hydrocarbons using an iron-containing Fischer-Tropsch catalyst

[0101] Two catalysts were evaluated for selectivity to hydrocarbons and CO2, as shown in Table 1 below. Prior to testing, each was activated at 400°C in 100% H2 and then carburized for 4 hours at 400°C in 3% CO, 92% H2, and 5% N2. Fischer-Tropsch synthesis was then performed using a 1:1 H2 / CO feed flow at a GHSV of 2000 hr-1, 30 barg, and 20% N2. Catalyst 1 had a composition of 50Fe2O3 / 4.4SiO2 / 2.6CuO / 0.5K2O, and catalyst 2 had a composition of ZnO / ZnFe2O4, 34.7 wt% Fe. [Table 1]

[0102] Advantageously, in certain embodiments, the methods disclosed herein allow for efficient recycling of the CO2 product back into the first feed stream, where it can be converted to MeOH and subsequently converted to synthesis gas. Therefore, the production of CO2, traditionally considered highly detrimental, has a much smaller impact on process efficiency, theoretically having zero impact on carbon utilization efficiency. Therefore, we can calculate the C5+ selectivity without counting CO2 as a waste product (Table 1, far right column), revealing excellent C5+ selectivities of approximately 85% for each of the catalysts tested. Therefore, the methods disclosed herein have the surprising effect of increasing the effective long-chain hydrocarbon selectivity in processes incorporating iron-containing Fischer-Tropsch catalysts.

[0103] Various exemplary embodiments of the present disclosure include, but are not limited to, the enumerated embodiments listed below, which can be combined in any number and in any combination that is not technically or logically consistent.

[0104] Embodiment 1: A method for conducting an integrated Fischer-Tropsch synthesis, comprising: Providing the first supply logistics including H2 and CO2, contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H; providing a third feed stream comprising H and at least a portion of the CO of the second product stream; The method includes contacting the third feed stream with an iron-containing Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a third product stream comprising C5+ hydrocarbons and CO2.

[0105] Embodiment 2: The method of embodiment 1, wherein the first feed stream comprises at least 10 mol% H2, e.g., at least 20 mol% H2, or at least 30 mol% H2.

[0106] Embodiment 3: The method of embodiment 1 or embodiment 2, wherein the first feed stream comprises at least 5 mol% CO2, e.g., at least 10 mol% CO2, or at least 15 mol% CO2.

[0107] Embodiment 4: The method of any of embodiments 1-3, wherein the H2:CO2 ratio of the first feed stream is at least 1:1, e.g., at least 1.5:1, at least 2:1, at least 2.5:1, at least 3:1, or at least 4:1.

[0108] Embodiment 5: The method of any of embodiments 1-4, wherein the first feed stream further comprises one or more of CO, CH4, and N2.

[0109] Embodiment 6: The method of any one of embodiments 1-5, wherein the first feed stream comprises 20 mol% or less CO, e.g., 15 mol% or less CO, or 10 mol% or less CO, or 5 mol% or less CO.

[0110] Embodiment 7: The method of any one of embodiments 1-6, wherein the hydrogenation catalyst is a copper / zinc oxide catalyst, for example, supported on aluminum oxide or zirconium oxide.

[0111] Embodiment 8: The method of any of embodiments 1 to 7, wherein the contacting of the first feed stream with the hydrogenation catalyst is carried out at a temperature in the range of 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C.

[0112] Embodiment 9: The method of any of embodiments 1-8, wherein the hydrogenation of CO2 is carried out with a selectivity to methanol of at least 50%, e.g., at least 65% or at least 80%.

[0113] Embodiment 10: The method of any one of embodiments 1-9, wherein the hydrogenation of CO2 is carried out at a selectivity to methane of 20% or less, such as 10% or less, or 5% or less.

[0114] Embodiment 11: The method of any one of embodiments 1 to 10, wherein the hydrogenation of CO2 is carried out at a selectivity to CO of 20% or less, such as 10% or less, or 5% or less.

[0115] Embodiment 12: The method of any of embodiments 1 to 11, wherein the hydrogenation of CO2 is carried out at a conversion of CO2 of at least 25%, such as at least 35%, such as at least 45% or at least 50%.

[0116] Embodiment 13: The method of any of embodiments 1-12, wherein the first product stream comprises at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol.

[0117] Embodiment 14: The method of any one of embodiments 1-13, wherein the first product stream comprises 10 mol% or less methane, e.g., 5 mol% or less methane, or 2 mol% or less methane.

[0118] Embodiment 15: The method of any one of embodiments 1-14, wherein the first product stream comprises 10 mol% or less CO, e.g., 5 mol% or less CO, or 2 mol% or less CO.

[0119] Embodiment 16: The method of any of embodiments 1-15, further comprising separating at least a portion of the water from the first product stream (e.g., at least 50%, at least 75%, or at least 90% of the water in the first product stream).

[0120] Embodiment 17: The method of any one of embodiments 1-16, wherein the portion of the first product stream included in the second feed stream has a water content of 10 mol % or less, e.g., or 2 mol % or less, or 0.5 mol % or less.

[0121] Embodiment 18: The method of any one of embodiments 1-17, further comprising separating at least a portion of the H2 (e.g., at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 in the first product stream) from the first product stream.

[0122] Embodiment 19: The method of embodiment 18, further comprising recycling at least a portion of the H2 separated from the first product stream to the first feed stream.

[0123] Embodiment 20: The method of embodiment 18 or embodiment 19, further comprising providing at least a portion of the H2 separated from the first product stream to a third feed stream.

[0124] Embodiment 21: The method of any of embodiments 18-20, further comprising activating a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream.

[0125] Embodiment 22: The method of any of embodiments 18-21, further comprising activating a methanol decomposition catalyst using at least a portion of the H2 separated from the first product stream.

[0126] Embodiment 23: The method of any one of embodiments 1-22, wherein the portion of the first product stream provided to the second feed stream comprises no more than 50% of the hydrogen in the first product stream, e.g., no more than 25%, no more than 10%, or no more than 5% of the hydrogen in the first product stream.

[0127] Embodiment 24: The process of any one of embodiments 1 to 23, wherein the contacting of the second feed stream with the methanolic decomposition catalyst and the contacting of the first feed stream with the hydrogenation catalyst occur in the same plant.

[0128] Embodiment 25: The method of any one of Embodiments 1-24, wherein at least a portion of the methanol of the first product stream is fed directly to the second feed stream.

[0129] Embodiment 26: The method of embodiment 25, wherein the portion of the first product stream that is fed to the second feed stream has a temperature in the range of 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C.

[0130] Embodiment 27: The process of any one of embodiments 1 to 26, wherein the contacting of the second feed stream with the methanolic decomposition catalyst and the contacting of the first feed stream with the dehydrogenation catalyst occur in different plants.

[0131] Embodiment 28: The method of any of embodiments 1-27, wherein at least a portion of the methanol of the first product stream is stored (e.g., in one or more tanks) before being fed to the second feed stream.

[0132] Embodiment 29: The method of embodiment 28, wherein the stored portion of the methanol of the first product stream is stored for at least 1 day, such as at least 2 days or at least 1 week.

[0133] Embodiment 30: The method of embodiment 28 or embodiment 29, wherein the stored portion of methanol is transported at least 1 km, e.g., at least 2 km or at least 10 km, during storage.

[0134] Embodiment 31: The method of any of embodiments 1-30, wherein the second feed stream comprises at least 5 mol% methanol, e.g., at least 7.5% methanol, or at least 10 mol% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0135] Embodiment 32: The method of any one of embodiments 1-31, wherein the second feed stream further comprises one or more of H2, CO, CH4, CO2, and N2.

[0136] Embodiment 33: The method of any one of embodiments 1 to 32, wherein the second feed stream has a water concentration of 5 mol% or less, e.g., 2 mol% or less, or 1 mol% or less.

[0137] Embodiment 34: The method of any of embodiments 1 to 33, wherein the second feed stream has a temperature in the range of 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C.

[0138] Embodiment 35: The method of any one of embodiments 1 to 34, wherein the methanol decomposition catalyst is, for example, a copper / zinc oxide on alumina catalyst.

[0139] Embodiment 36: The process of any of embodiments 1-35, wherein contacting the second feed stream with the methanol decomposition catalyst is conducted at a temperature in the range of 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C.

[0140] Embodiment 37: The process of any one of embodiments 1 to 36, wherein contacting the second feed stream with the methanolic decomposition catalyst is conducted at a temperature within 75°C, e.g., within 50°C, of ​​the temperature of contacting the first feed stream with the hydrogenation catalyst.

[0141] Embodiment 38: The method of any of embodiments 1 to 37, wherein the decomposition of methanol is carried out at a carbon product selectivity relative to CO of at least 50%, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0142] Embodiment 39: The method of any one of embodiments 1 to 38, wherein the decomposition of methanol is carried out at a selectivity to CO of 20% or less, e.g., 15% or less, 10% or less, or 5% or less.

[0143] Embodiment 40: The method of any of embodiments 1 to 39, wherein the decomposition of methanol is carried out to a conversion of methanol of at least 30%, e.g., at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0144] Embodiment 41: The method of any of embodiments 1-40, wherein the second product stream comprises at least 20 mol % of the sum of CO and H, e.g., at least 35 mol %, or at least 50 mol %, or at least 65 mol %.

[0145] Embodiment 42: The method of any of embodiments 1-41, wherein the second product stream comprises 20 mol% or less CO2, e.g., 15 mol% or less CO2, or 10 mol% or less CO2, or 5 mol% or less CO2, excluding CO2 not derived from methanol decomposition.

[0146] Embodiment 43: The method of any one of embodiments 1 to 42, wherein the second product stream has a molar ratio of hydrogen to carbon monoxide in the range of 0.5:1 to 5:1, such as 1:1 to 3:1, 1.5:1 to 2.5:1, such as 1.5:1 to 3.5:1.

[0147] Embodiment 44: The method of any one of embodiments 1-43, wherein the second product stream comprises 75 mol% or less methanol, e.g., 60 mol% or less methanol, or 50 mol% or less methanol, or 25 mol% or less methanol.

[0148] Embodiment 45: The method of any of embodiments 1-44, further comprising separating at least a portion of the methanol from the second product stream (e.g., at least 50%, at least 75%, or at least 90% of the methanol in the second product stream).

[0149] Embodiment 46: The method of embodiment 45, further comprising recycling at least a portion of the methanol separated from the second product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream, to the second feed stream.

[0150] Embodiment 47: The method of any one of embodiments 1 to 46, further comprising separating at least a portion of the H2 from the second product stream.

[0151] Embodiment 48: The method of embodiment 47, further comprising providing H2 separated from the second product stream to the first feed stream.

[0152] Embodiment 49: The method of any of embodiments 47 or 48, further comprising activating a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the second product stream.

[0153] Embodiment 50: The method of any of embodiments 1-49, wherein at least 50%, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99% of the CO of the second product stream is provided to the third feed stream.

[0154] Embodiment 51: The method of any of embodiments 1-50, wherein at least a portion of the H2 of the second product stream is provided to the third feed stream.

[0155] Embodiment 52: The method of any of embodiments 1 to 51, wherein at least 50%, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99% of the H2 of the second product stream is provided in the third feed stream.

[0156] Embodiment 53: The method of any of embodiments 1-52, wherein H2 is provided to the third feed stream from a hydrogen source other than the second product stream.

[0157] Embodiment 54: The method of any of embodiments 1-53, wherein CO is provided to the third feed stream from a CO source other than the second product stream.

[0158] Embodiment 55: The method of any of embodiments 1-54, wherein one or more of CO2, CH4, and N2 is provided to the third feed stream from a source other than the second product stream.

[0159] Embodiment 56: The method of any one of embodiments 1 to 55, wherein the portion of the second product stream included in the third feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, e.g., 1:1 to 2.5:1, or 1.5:1 to 3.5:1.

[0160] Embodiment 57: The method of any one of embodiments 1 to 56, wherein the third feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1.

[0161] Embodiment 58: The method of any one of embodiments 1 to 57, wherein the third feed stream has a H2:CO molar ratio in the range of 1:1 to 2.5:1.

[0162] Embodiment 59: The method of any one of embodiments 1 to 58, wherein the third feed stream has a H2:CO molar ratio of at least 1.2:1, for example, in the range of 1.2:1 to 2.5:1.

[0163] Embodiment 60: The method of any one of embodiments 1 to 59, wherein the Fischer-Tropsch catalyst further comprises sodium, potassium, magnesium, calcium, ruthenium, palladium, platinum, rhodium, rhenium, manganese, chromium, nickel, iron, zinc, copper, molybdenum, tungsten, zirconium, gallium, thorium, lanthanum, cerium, or a combination thereof.

[0164] Embodiment 61: The method of any one of embodiments 1 to 60, wherein the Fischer-Tropsch catalyst comprises iron in an amount ranging from 25 to 95 wt. %, calculated as Fe(0).

[0165] Embodiment 62: The method of any one of embodiments 1 to 61, wherein the Fischer-Tropsch catalyst further comprises at least one of sodium, potassium, copper, zinc, and manganese.

[0166] Embodiment 63: The method of any one of embodiments 1 to 62, wherein the Fischer-Tropsch catalyst is a supported catalyst, and the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, magnesium oxide, silicon oxide, and zinc oxide.

[0167] Embodiment 64: The method of any one of embodiments 1 to 63, wherein the Fischer-Tropsch catalyst is a supported catalyst, and the support comprises at least one of zinc oxide, aluminum oxide, and silicon oxide.

[0168] Embodiment 65: The method of any one of embodiments 1 to 64, wherein the Fischer-Tropsch catalyst is activated in a reducing and / or carburizing atmosphere.

[0169] Embodiment 66: The method of embodiment 65, wherein the reducing atmosphere comprises at least a portion of the hydrogen from the second product stream and / or at least a portion of the hydrogen of the first product stream.

[0170] Embodiment 67: The method of any one of embodiments 1 to 66, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is conducted at a temperature in the range of 150 to 400°C (e.g., in the range of 150 to 350°C, or 150 to 300°C, or 150 to 250°C, or 150 to 220°C, or 220 to 400°C, or 220 to 350°C, or 220 to 300°C, or 220 to 280°C, or 240 to 400°C, or 240 to 350°C, or 240 to 300°C, or 300 to 400°C).

[0171] Embodiment 68: The method of any one of embodiments 1 to 67, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is conducted at a temperature in the range of 200 to 350°C.

[0172] Embodiment 69: The method of any one of embodiments 1 to 68, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is conducted at a pressure in the range of 10 to 50 barg (e.g., 20 to 50 barg, or 25 to 50 barg, or 10 to 40 barg, or 20 to 40 barg, or 25 to 40 barg, or 10 to 35 barg, or 20 to 35 barg, or 25 to 35 barg).

[0173] Embodiment 70: The method of any one of embodiments 1 to 69, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is conducted at a pressure in the range of 20 to 40 barg.

[0174] Embodiment 71: The method of any one of embodiments 1 to 70, wherein contacting the third feed stream with the Fischer-Tropsch catalyst and contacting the second feed stream with the methanol decomposition catalyst are carried out in the same plant.

[0175] Embodiment 72: The method of any one of embodiments 1 to 71, wherein contacting the Fischer-Tropsch catalyst with the third feed stream is carried out at a C5+ selectivity of at least 30%, e.g., at least 50%, or at least 70%.

[0176] Embodiment 73: The method of any one of embodiments 1 to 72, wherein the C5+ hydrocarbons of the third product stream comprise C5+ oxygenates.

[0177] Embodiment 74: The method of any one of embodiments 1 to 73, wherein contacting the third feed stream with a Fischer-Tropsch catalyst produces CO2 with a selectivity of at least 2% (e.g., at least 5%, or at least 10%, or at least 15%).

[0178] Embodiment 75: The method of any one of embodiments 1 to 74, further comprising separating at least a portion of the C1 to C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream.

[0179] Embodiment 76: The method of embodiment 75, further comprising oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream or the third feed stream.

[0180] Embodiment 77: The method of embodiment 75 or embodiment 76, further comprising including at least a portion of the light hydrocarbon stream in a third feed stream.

[0181] Embodiment 78: The method of any one of embodiments 1 to 77, further comprising separating at least a portion of the H2 of the third product stream.

[0182] Embodiment 79: The method of embodiment 78, wherein at least a portion of the H2 separated from the third product stream is provided to the first feed stream and / or the third feed stream.

[0183] Embodiment 80: The method of embodiment 78 or embodiment 79, wherein at least a portion of the H2 separated from the third product stream is used to activate the Fischer-Tropsch catalyst.

[0184] Embodiment 81: The method of any one of embodiments 1 to 80, further comprising separating at least a portion of the CO of the third product stream.

[0185] Embodiment 82: The method of embodiment 81, wherein at least a portion of the CO separated from the third product stream is provided to the third feed stream.

[0186] Embodiment 83: The method of any one of embodiments 1 to 82, further comprising separating at least a portion of the CO2 of the third product stream.

[0187] Embodiment 84: The method of embodiment 83, wherein at least a portion of the CO2 separated from the third product stream is provided to the first feed stream.

[0188] Embodiment 85: The method of any one of embodiments 1 to 84, further comprising providing a C5+ hydrocarbon product stream from the third product stream comprising at least 80 wt% C5+ hydrocarbons, e.g., at least 90 wt% C5+ hydrocarbons.

[0189] Embodiment 86: The method of any one of Embodiments 1 to 85, further comprising hydrotreating at least a portion of the third product stream of C5+ hydrocarbons by contacting the C5+ hydrocarbon product stream with hydrogen and a hydrotreating catalyst.

[0190] Embodiment 87: The method of embodiment 86, wherein at least a portion of the hydrogen used in hydroprocessing is provided from any of the first product stream, the second product stream, and the third product stream.

[0191] Embodiment 88: The method of any one of embodiments 1 to 87, wherein one or more products are provided from at least a portion of the C5+ hydrocarbons of the third product stream, and the one or more products are one or more of a fuel, a wax, or an oil.

[0192] Embodiment 89: The method of any of embodiments 1-88, wherein at least a portion of the CO2 of the first feed stream is derived from a renewable source.

[0193] Embodiment 90: The method of any of embodiments 1-89, wherein at least a portion of the CO2 of the first feed stream is from direct air capture.

[0194] Embodiment 91: The method of any of embodiments 1-90, wherein at least a portion of the CO2 of the first feed stream is captured from a manufacturing plant, such as a bioethanol plant, a steel mill, or a cement factory.

[0195] Embodiment 92: The method of any one of embodiments 1 to 91, wherein at least a portion of the H2 of the first feed stream and / or the third feed stream is from a renewable source.

[0196] Embodiment 93: The method of any one of embodiments 1 to 92, wherein at least a portion of the hydrogen in the first feed stream and / or the third feed stream is green hydrogen.

[0197] Embodiment 94: The method of any one of embodiments 1 to 93, wherein at least a portion of the hydrogen in the first feed stream and / or the third feed stream is blue hydrogen.

[0198] Embodiment 95: The method of any one of embodiments 1 to 94, wherein at least a portion of the hydrogen in the first feed stream and / or the third feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0199] Embodiment 96: The method of any one of embodiments 1 to 95, further comprising providing at least a portion of the H2 to the first feed stream and / or the third feed stream by electrolysis of water.

[0200] Embodiment 97: The method of embodiment 96, wherein the electrolysis of water is carried out using electricity derived at least in part from renewable resources.

[0201] Embodiment 98: The method of embodiment 96 or embodiment 97, wherein the electrolysis of water is performed using electricity generated at least in part from steam produced by combustion of a light hydrocarbon stream provided from the third product stream.

[0202] Embodiment 99: The method of any one of Embodiments 96 to 98, further comprising the step of Embodiment 76, wherein at least a portion of the O2 produced by water electrolysis is supplied to a partial oxidation reactor.

[0203] Embodiment 100: The method of any one of embodiments 1 to 99, wherein the first reaction zone comprises a first reactor disposed with a hydrogenation catalyst, the second reaction zone comprises a second reactor disposed with a methanol decomposition catalyst, and the third reaction zone comprises a third reactor disposed with a Fischer-Tropsch catalyst.

[0204] Embodiment 101: The method of any one of embodiments 1 to 100, wherein the first reaction zone comprises a first catalyst bed having a hydrogenation catalyst disposed therein, the second reaction zone comprises a second catalyst bed having a methanol decomposition catalyst disposed therein, and the third reaction zone comprises a third catalyst bed having a Fischer-Tropsch catalyst disposed therein.

[0205] Embodiment 102: The method of embodiment 101, wherein the first catalyst bed, the second catalyst bed, and the third catalyst bed are arranged in a catalyst stack or bed section within the same reactor.

[0206] Embodiment 103: The method of embodiment 101, wherein the second catalyst bed and the third catalyst bed are located in the same reactor, and the first catalyst bed is located in a different reactor from the second and third catalyst beds.

[0207] Embodiment 104: The method of any one of Embodiments 101-104, wherein none of the first catalyst bed, the second catalyst bed, and the third catalyst bed are mixed together.

[0208] Embodiment 105: The method of embodiment 101, wherein the first catalyst bed, the second catalyst bed, and the third catalyst bed are disposed in separate reactors.

[0209] Embodiment 106: The method of any one of embodiments 1 to 105, wherein the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition (e.g., are the same catalyst).

[0210] The details set forth herein are presented by way of example only for purposes of illustrative discussion of various embodiments of the present disclosure and to provide what is believed to be the most useful and readily understood explanation of the principles and conceptual aspects of various embodiments of the present disclosure. In this regard, no attempt is made to show details related to the methods of the present disclosure in more detail than is necessary for a fundamental understanding of the methods described herein; the description, taken together with the examples, will make clear to those skilled in the art how some forms of the methods of the present disclosure can be actually embodied. Therefore, before the disclosed methods and devices are described, it should be understood that the aspects described herein are not limited to specific embodiments, apparatus, or configurations, which may, of course, vary. It should also be understood that the terminology used herein is intended to describe particular aspects only and is not intended to be limiting unless specifically defined herein.

[0211] As used in the context of describing the methods of the present disclosure (particularly in the context of the embodiments and claims that follow), the terms "a," "an," "the," and similar referents should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0212] All methods described herein can be performed in any suitable order of steps, unless otherwise indicated herein or clearly contradicted by context. Any and all examples provided herein, or the use of exemplary language (e.g., "etc."), are intended merely to better clarify the methods of the present disclosure and do not impose limitations on the scope of the disclosure. No language in the present specification should be construed as indicating any non-claimed element essential to the practice of the methods of the present disclosure.

[0213] Unless the context clearly dictates otherwise, throughout this specification and the claims, words like "comprise," "comprising," and the like are to be construed in an inclusive sense, i.e., "including, but not limited to," rather than an exclusive or exhaustive sense. Words using the singular or plural also include the plural and singular, respectively. Furthermore, the words "herein," "above," and "below," and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of this application.

[0214] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of, or consist of its specified recited elements, steps, ingredients, or components. As used herein, the transitional phrases "comprise" or "comprises" mean including, but not limited to, and allow for the inclusion of unspecified elements, steps, ingredients, or components, even if they amount to a large amount. The transitional phrase "consisting of" excludes any unspecified element, step, ingredient, or component. 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.

[0215] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0216] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0217] Groupings of alternative elements or embodiments of the present disclosure should not be construed as limiting. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to include the modified group and thus satisfy the written description of all Markush groups used in the appended claims.

[0218] Several embodiments of various aspects of the present disclosure are described herein, including the best mode known to the inventors for carrying out the methods described herein. Of course, variations of these described embodiments will become apparent to those skilled in the art upon reading the foregoing description. Those skilled in the art will employ such variations as appropriate, and thus the methods of the present disclosure can be carried out in ways other than those specifically described herein. Accordingly, the scope of the present disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the present disclosure unless otherwise indicated herein or clearly contradicted by context.

[0219] As used herein, the phrase "at least a portion" is used to mean that at least a partial amount, up to the total possible amount, is required.

[0220] Finally, it should be understood that the various embodiments herein are illustrative of the methods of the present disclosure. Other modifications that may be employed are within the scope of the present disclosure. Thus, by way of example, and not of limitation, alternative configurations of the methods may be utilized in accordance with the teachings herein. Thus, the methods of the present disclosure are not limited to that precisely as shown and described.

Claims

1. 1. A method for conducting integrated Fischer-Tropsch synthesis, comprising: Providing the first supply logistics including H2 and CO2, contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H; providing a third feed stream comprising H and at least a portion of the CO of the second product stream; contacting the third feed stream with an iron-containing Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a third product stream comprising C5+ hydrocarbons and CO2.

2. 10. The method of claim 1, further comprising separating at least a portion of the water from the first product stream (e.g., at least 50%, at least 75%, or at least 90% of the water in the first product stream).

3. 3. The method of claim 1 or claim 2, wherein the second feed stream comprises at least 5 mol% methanol, e.g., at least 7.5% methanol, or at least 10 mol% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

4. The method of any one of claims 1 to 3, wherein the second feed stream has a water concentration of 5 mol% or less, such as 2 mol% or less, or 1 mol% or less.

5. 5. The process of any one of claims 1 to 4, wherein contacting the second feed stream with the methanol decomposition catalyst is conducted at a temperature within 75°C, e.g., within 50°C, of ​​the temperature of contacting the first feed stream with the hydrogenation catalyst.

6. 6. The method of any one of claims 1 to 5, further comprising separating at least a portion of the methanol from the second product stream (e.g., at least 50%, at least 75%, or at least 90% of the methanol in the second product stream) and recycling at least a portion of the methanol separated from the second product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream, to the second feed stream.

7. 7. The method of any one of claims 1 to 6, further comprising separating at least a portion of the H2 from the second product stream and providing the H2 separated from the second product stream to the first feed stream.

8. 8. The method of any one of claims 1 to 7, wherein the portion of the second product stream included in the third feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, e.g., 1:1 to 2.5:1 or 1.5:1 to 3.5:

1.

9. 9. The process of any one of claims 1 to 8, wherein the Fischer-Tropsch catalyst comprises iron in an amount in the range of 25 to 95 wt.%, calculated as Fe(0).

10. The method of any one of claims 1 to 9, wherein the Fischer-Tropsch catalyst further comprises at least one of sodium, potassium, copper, zinc, and manganese.

11. 11. The method of any one of claims 1 to 10, wherein the Fischer-Tropsch catalyst is a supported catalyst, and the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, magnesium oxide, silicon oxide, and zinc oxide.

12. 12. The method of any one of claims 1 to 11, wherein the Fischer-Tropsch catalyst is activated in a reducing and / or carburizing atmosphere, the reducing and / or carburizing atmosphere comprising at least a portion of the hydrogen from the second product stream and / or at least a portion of the hydrogen from the first product stream.

13. 13. The process of any one of claims 1 to 12, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst and the contacting of the second feed stream with the methanol cracking catalyst occur in the same plant.

14. 14. The method of any one of claims 1 to 13, wherein contacting the third feed stream with a Fischer-Tropsch catalyst produces CO2 with a selectivity of at least 2% (e.g., at least 5%, or at least 10%, or at least 15%).

15. 15. The method of any one of claims 1 to 14, further comprising separating at least a portion of the CO2 of the third product stream, wherein at least a portion of the CO2 separated from the third product stream is provided to the first feed stream.

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