Fischer-Tropsch production of hydrocarbons from methanol

Abstract

The present disclosure generally relates to a method for performing integrated Fischer-Tropsch synthesis of hydrocarbons using methanol. In particular, the disclosure relates to a method including providing a first feed stream comprising methanol, contacting the first feed stream with a methanol cracking catalyst to form a first product stream comprising CO and H, providing a second feed stream comprising H and at least a portion of the CO of the first product stream, and contacting the second feed stream with a Fischer-Tropsch catalyst to provide a second product stream comprising C hydrocarbons.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from European Patent Application No. 22190315.6, 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 methanol. [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 methanol to hydrocarbons through the production of synthesis gas from methanol decomposition. 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 a first feed stream comprising methanol; contacting the first 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 first product stream comprising CO and H; providing a second feed stream comprising H and at least a portion of the CO of the first product stream; contacting the second feed stream with a Fischer-Tropsch catalyst to perform a Fischer-Tropsch synthesis to provide a second product stream comprising C5+ hydrocarbons.

[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. DETAILED DESCRIPTION OF THE INVENTION

[0011] This disclosure relates to techniques for preparing hydrocarbons from methanol. Fischer-Tropsch production of hydrocarbons from synthesis gas is well known in the art. However, synthesis gas (a mixture of H2 and CO) can be difficult to store and transport at efficient densities. Furthermore, environmentally friendly modes of CO2 production, such as from carbon dioxide via the reverse water-gas shift reaction, require high operating temperatures. In contrast, methanol is a common and inexpensive commodity chemical that can be produced from numerous sources, including fermentation, biomass pyrolysis, catalytic reactions of synthesis gas, and CO2 hydrogenation. Methanol, which is a liquid at ambient temperature and pressure, may optionally be transported through low-pressure pipelines, ships, or trucks, thus generally allowing for increased transportation efficiency as a liquid. Methanol can then be subjected to a methanol cracking process to produce H2 and CO2 in a 2:1 ratio. At least the CO2 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 process is also desirably used in Fischer-Tropsch synthesis. For example, some Fischer-Tropsch processes are operated with H2:CO ratios of 2:1 or higher, e.g., 2.2:1 or 3:1. In such cases, the H2 and CO mixture from methanol decomposition may be supplemented with a hydrogen source, such as from a recycle stream or renewable energy-generated green hydrogen, to form the Fischer-Tropsch reaction mixture.

[0012] Thus, in one aspect, the present disclosure provides a method for conducting an integrated Fischer-Tropsch synthesis, the method comprising: providing a first feed stream comprising methanol; contacting the first 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 first product stream comprising CO and H; providing a second feed stream comprising H and at least a portion of the CO of the first product stream; contacting the second feed stream with a Fischer-Tropsch catalyst to perform a Fischer-Tropsch synthesis to provide a second product stream comprising C5+ hydrocarbons.

[0013] As used herein, "feed stream" is used to mean all materials input to a process step, e.g., methanol cracking or a Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams and whether through a single inlet or multiple inlets. Similarly, "product stream" is used to mean all materials output from a process step, e.g., methanol cracking or a Fischer-Tropsch reaction, whether provided in a single physical stream or multiple physical streams and whether through a single reactor outlet or multiple reactor outlets.

[0014] Methanol is a hygroscopic compound that is highly miscible with water. Therefore, many commercial methanol sources and methanol preparation methods may contain significant amounts of water or may acquire significant water content during storage or transportation. In some embodiments, entrained water 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. Therefore, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the water from the first feed 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 feed stream. In various embodiments described elsewhere herein, the first 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.

[0015] In embodiments in which water is separated from the first feed stream, 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.

[0016] The first 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.

[0017] 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 processes disclosed herein, a dedicated water-gas shift or reverse water-gas shift reactor is not used (however, 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).

[0018] As described herein, methanol decomposition is utilized to form a product stream comprising CO and H. Accordingly, in various embodiments described elsewhere herein, the first feed stream comprises at least 5 mol% methanol. For example, in certain embodiments, the first 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.

[0019] Optionally, the first feed stream may include one or more additional gases, which may be inert or reactive. In such embodiments, the first feed stream may further include one or more of H2, CO, CH4, CO2, and N2. In certain embodiments, the first 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 first feed stream to regulate the cracking reaction and / or to provide a desired first product stream for use in a Fischer-Tropsch process. In such embodiments, the first 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 first feed stream in an amount ranging from up to 50 mol%, e.g., up to 40 mol%, or up to 30 mol%.

[0020] In various embodiments, the first 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 first 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.

[0021] The first feed stream may be provided at an elevated temperature. For example, in various embodiments described elsewhere herein, the first 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.

[0022] The first 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 may include one or more transition metals, 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 may include an intermetallic compound or alloy. For example, the catalyst may further include one or more of Sc, Y, Ti, Zr, Ce, B, Al, Ga, In, Si, Ge, Sn, or Sb. The decomposition catalyst may 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.

[0023] 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.

[0024] Contacting the first 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 first 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.

[0025] 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%.

[0026] As described herein, the decomposition of methanol produces CO and H. Thus, in various embodiments described elsewhere herein, the first 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%. 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 first product stream has a molar ratio of hydrogen to carbon monoxide ranging from 0.5:1 to 5:1, e.g., from 1:1 to 3:1, or from 1.5:1 to 2.5:1, or from 1.5:1 to 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 first feed stream.

[0027] In various embodiments, the first product 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, excluding CO not derived from methanol decomposition (e.g., excluding any CO present in the first feed stream).

[0028] Advantageously, a portion of the methanol is consumed during the methanolysis reaction. Thus, in various embodiments described elsewhere herein, the first 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.

[0029] In some embodiments, further removal of methanol from the first 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 first 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 first product stream. Advantageously, at least a portion of the methanol of the first product stream, e.g., the methanol separated from the first 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 first product stream to the first feed stream.

[0030] 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. And, specifically, hydrogen may be present in the first feed stream, further increasing the ratio in the first product stream. Accordingly, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the H2 from the first product stream. The separated H2 is suitable for various processes. Additionally or alternatively, in various embodiments described elsewhere herein, the method further includes using at least a portion of the H2 separated from the first product stream to activate a methanol decomposition catalyst or a Fischer-Tropsch catalyst.

[0031] As described herein, the second feed stream includes at least a portion of the CO of the first product stream. Thus, in various embodiments described elsewhere herein, at least 50% of the CO of the first product stream is provided to the second 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 first product stream is provided to the second feed stream. In various embodiments, substantially all of the CO of the first product stream is provided to the second feed stream. Additionally or alternatively, in various embodiments as described elsewhere herein, the CO of the second feed stream may be partially supplied from a CO source other than the first product stream.

[0032] As described above, the second feed stream comprises H and CO, and the first product stream comprises H. In various embodiments described elsewhere herein, at least a portion of the H of the first product stream is provided to the second 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 first product stream is provided to the second feed stream. In various embodiments, substantially all of the H of the first product stream is provided to the second feed stream. Additionally or alternatively, in various embodiments as described elsewhere herein, the H of the second feed stream may be at least partially supplied from a hydrogen source other than the first product stream.

[0033] In various embodiments as described elsewhere herein, the second 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 first product stream and carried to the second feed stream. However, in other embodiments, one or more other gases (e.g., one or more of CO, CH, N) are provided to the second feed stream from a source other than the first product stream.

[0034] Advantageously, the portion of the first product stream included in the second feed stream can be tailored as desired for the process of the second feed stream. For example, in various embodiments described elsewhere herein, the portion of the first product stream included in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, e.g., in the range of 1:1 to 2.5:1.

[0035] The second feed stream is contacted with a Fischer-Tropsch catalyst, as described elsewhere herein. Thus, in various embodiments, as described elsewhere herein, the second feed stream has an H2:CO molar ratio suitable for Fischer-Tropsch synthesis. For example, in various embodiments, the second feed stream has an 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 second feed stream has an H2:CO molar ratio of at least 1.2:1. For example, in various embodiments, the second feed stream can have an 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.

[0036] The Fischer-Tropsch catalyst may be selected by one of ordinary skill in the art. In various embodiments described elsewhere herein, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof (e.g., comprises cobalt or iron). In certain embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount ranging from 2 to 30 wt. %, e.g., from 5 to 25 wt. %, or from 8 to 20 wt. %, calculated as Co(0). In certain embodiments, the Fischer-Tropsch catalyst comprises iron in an amount ranging from 15 to 95 wt. %, e.g., from 25 to 95 wt. %, or from 30 to 90 wt. %, calculated as Fe(0). In various embodiments described elsewhere herein, the Fischer-Tropsch catalyst further comprises manganese (e.g., manganese in an amount ranging from 0.1 to 15 wt. %, or from 1 to 10 wt. %).

[0037] 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.

[0038] 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 includes cobalt, this method results in at least a portion of the cobalt being converted to cobalt metal. Desirably, the reduction results in at least 50% of the cobalt being provided as cobalt(0). Those skilled in the art can use conventional methods to reduce cobalt catalyst materials (e.g., cobalt oxide or cobalt hydroxide-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% by volume H (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 H). As noted above, H for the reduction can be obtained from the first product stream. H can also be separated and recycled from the second product stream for use in the reduction of the Fischer-Tropsch catalyst.

[0039] 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. 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 second feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20 to 40 barg.

[0040] 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.

[0041] Advantageously, in various embodiments as described elsewhere herein, contacting the second feed stream with the Fischer-Tropsch catalyst and contacting the first 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.

[0042] 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 second 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 second product stream can vary depending on the catalyst type and process conditions, as 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.

[0043] Generally, long-chain hydrocarbons are more desirable than short-chain hydrocarbons. Accordingly, in various embodiments described elsewhere herein, the second product stream comprises C1-C4 hydrocarbons, and the method further comprises separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. 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 second 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 second feed stream, as described elsewhere herein.

[0044] 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 described elsewhere herein, the method further includes including at least a portion of the light hydrocarbon stream in a second feed stream. Additionally or alternatively, at least a portion of the light hydrocarbon stream can be included in the first feed stream for passage to the second feed stream.

[0045] In various embodiments, the second product stream may contain unreacted H. In various embodiments described elsewhere herein, the method further includes separating at least a portion of the H from the second 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 second product stream is provided to a second feed stream. And, as described above, at least a portion of the H separated from the second product stream can be used to activate a Fischer-Tropsch catalyst.

[0046] In various embodiments, the second product stream can include unreacted CO. In various embodiments described elsewhere herein, the method further includes separating at least a portion of the CO from the second 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 second product stream is provided to a second feed stream.

[0047] In various embodiments, the second product stream may include CO. Accordingly, in various embodiments described elsewhere herein, the method further includes separating at least a portion of the CO from the second product stream. The separated CO may then be sent to a process requiring it.

[0048] It may be desirable to provide a C5+ hydrocarbon product stream from the second product stream, i.e., a product stream containing at least 70 wt.% C5+ hydrocarbons, e.g., at least 80 wt.% C5+ hydrocarbons, or at least 85 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.

[0049] 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 both of the first and second product streams, as described above.

[0050] 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 described elsewhere herein, one or more products are provided from at least a portion of the C5+ hydrocarbons of the second 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).

[0051] 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 16,000 hr, or from 8000 hr to 12,000 hr, or from 2000 hr to 12,000 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.

[0052] Hydrogen gas may be added to the second feed stream to increase the H:CO ratio. 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 and / or the second feed stream is from a renewable resource.

[0053] 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.

[0054] 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.

[0055] 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 produced 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 authority. Thus, in various embodiments described elsewhere herein, at least a portion of the H2 in the second 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 to the second feed stream by electrolysis of water. In various embodiments, the water electrolysis is carried out using electricity obtained, at least in part, from a renewable resource.

[0056] 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 second product stream.

[0057] 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., from the second product stream) to provide a pOX stream. In such embodiments, the oxidation may be carried out using O. Thus, in certain embodiments, at least a portion of the O produced by water electrolysis is fed to a partial oxidation reactor.

[0058] Blue hydrogen is defined as hydrogen gas produced in a process that relies somewhat on fossil fuels for production but 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 processes 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. WO 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 second feed stream is blue hydrogen.

[0059] 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 as described elsewhere herein, at least a portion of the H in the second feed stream is grey hydrogen.

[0060] 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 second feed stream is black hydrogen and / or brown hydrogen.

[0061] Pink hydrogen is produced by the electrolysis of water, and the energy required for the electrolysis is generated by nuclear power. In various embodiments described elsewhere herein, at least a portion of the H2 in the second feed stream is pink hydrogen. Pink hydrogen is also known as purple hydrogen or red hydrogen.

[0062] Turquoise hydrogen is produced by methane pyrolysis, with the by-products being hydrogen gas and solid elemental carbon. In various embodiments described elsewhere herein, at least a portion of the H2 of the second feed stream is turquoise hydrogen.

[0063] 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 of the second feed stream is white hydrogen.

[0064] As described herein, the disclosed methods, in various embodiments, include 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, such that feedstocks cannot be transferred between them without intervening transportation and storage steps. Thus, in various embodiments described elsewhere herein, the first reaction zone includes a first reactor containing a methanol decomposition catalyst, and the second reaction zone includes a second reactor containing a Fischer-Tropsch catalyst. In various embodiments described elsewhere herein, the first reaction zone includes a first catalyst bed containing a methanol decomposition catalyst, and the second reaction zone includes a second catalyst bed containing a Fischer-Tropsch catalyst. For example, in certain embodiments, the first catalyst bed and the second catalyst bed are located within the same reactor, eg, in a catalyst stack or catalyst bed section.

[0065] 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, the first and second catalyst beds are immiscible. Catalyst intermixing occurs when catalysts for different processes share the same catalyst bed. As used herein, two different catalyst beds within one reactor are immiscible. In certain embodiments as described elsewhere herein, the first and second catalyst beds are located in separate reactors.

[0066] 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.

[0067] An exemplary embodiment is illustrated in the schematic diagram of FIG. 1, which shows a process 100 contained within a single plant 141 .

[0068] In the embodiment of FIG. 1 , crude methanol stream 111 is subjected to an optional water removal step, whereby water is sent to electrolysis reactor 160 via dehydration stream 112. First feed stream 121 is sent to methanol decomposition reaction zone 120 (here, methanol decomposition reactor), where it contacts methanol decomposition catalyst 123 to decompose at least a portion of the methanol and form first product stream 122 comprising CO and H. First feed stream 121 can also be augmented by introducing other gases, such as CO and / or H, through an augmentation feed (not shown). In the embodiment of FIG. 1 , from first reaction zone 120, first product stream 122 is directed to second feed stream 131. Second feed stream 131 comprises H (e.g., from the first product stream) and at least a portion of the CO of the first product stream. Second feed stream 131 can also be augmented by introducing other gases, such as CO and / or H, through an augmentation feed (not shown). The second feed stream 131 is delivered to a Fischer-Tropsch reaction zone 130 (here, a Fischer-Tropsch reactor) in which a Fischer-Tropsch catalyst 133 is disposed. The second feed stream 131 contacts the Fischer-Tropsch catalyst 133 to provide a second product stream 132 comprising C5+ hydrocarbons. In the embodiment of FIG. 1, the second product stream 132 is directed from the second reaction zone 130. Here, a light hydrocarbon stream 136 is separated from the second product stream 132 and directed to a power generator 170. Additionally or alternatively, a light hydrocarbon stream 137, optionally comprising vapor phase products, is separated from the second product stream 132 and recycled to the second feed stream 131. Examples of vapor phase products for recycle include CO, H2, CH4, CO2, C2H4, C3H6, C3H8, C3H7OH, and HO. The generator 170 uses the light hydrocarbon stream to generate electricity 172 (e.g., by combusting the light hydrocarbon stream to form steam, which can then 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 FIG. 1 , at least a portion of the water can be separated from the second product stream 132, which can be directed to the electrolysis reactor 160 via water stream 138. The electrolysis reactor uses power derived at least in part from the light hydrocarbon stream (although other power sources, including renewable sources, can be used) to electrolyze the water (here, separated from the crude methanol stream and / or the second product stream) to provide hydrogen gas.

[0069] As described above, methanol can be formed 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. For example, in the embodiment of FIG. 2 , methanol is loaded into a storage tank 217 and then transported to a second plant 243, here by truck 218. A first feed stream 221 is delivered to a methanol cracking reaction zone 220, where it contacts a methanol cracking catalyst 223 to produce a first product stream 222 comprising CO and H. Here, at least a portion of the first product stream 222 is provided to a second feed stream 231. The second feed stream 231 is delivered to a Fischer-Tropsch reaction zone 230, where it contacts a Fischer-Tropsch catalyst 233 to produce a second product stream 232 comprising C5+ hydrocarbons.

[0070] Another illustrative embodiment is shown in the schematic diagram of Figure 3. Here, in process 300, an additional gas stream 324 is added to crude methanol stream 312, with optional dehydration (not shown), and the resulting mixture is provided as first feed stream 321. First feed stream 321 is directed to a methanol decomposition reaction zone 320, where it provides a first product stream 322 along with a methanol decomposition catalyst 323. Here, first product stream 322 is directed from the methanol decomposition reaction zone, and unreacted methanol is substantially separated from the first product stream (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) and recycled to first feed stream 321 via methanol recycle 325. At least a portion of the H2 in first product stream 322 can also or alternatively be fed to second reaction zone 330 to activate Fischer-Tropsch catalyst 333 via H2 stream 327. The remainder of first product stream 322 is provided as part of second feed stream 331 and directed to Fischer-Tropsch reaction zone 330. Also, a portion of second feed stream 331 is additional gas stream 335, which supplies additional H and / or CO to the Fischer-Tropsch reaction zone through another inlet. The second feed stream contacts Fischer-Tropsch catalyst 333 in the Fischer-Tropsch reaction zone to provide second product stream 332 comprising C hydrocarbons. Second product stream 332 is directed from the Fischer-Tropsch reaction zone, and a light hydrocarbon stream 336 is separated therefrom and directed to partial oxidation unit 350. As will be appreciated by those skilled in the art, partial oxidation units oxidize light hydrocarbons to provide CO and CO, and at least a portion of the CO produced from partial oxidation unit 350 is included in second feed stream 331 via CO stream 351.

[0071] 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, a first feed stream 421 is fed to a stacked-bed reactor 425 comprising a methanol decomposition reaction zone 420 (here, a first bed of the stacked-bed reactor comprising a methanol decomposition catalyst 423) and a Fischer-Tropsch reaction zone 430 (here, a second bed of the stacked-bed reactor comprising a Fischer-Tropsch catalyst 433). The first feed stream 421 contacts the methanol decomposition catalyst 423 to provide a first product stream 422 comprising CO and H. The first product stream is fed to the Fischer-Tropsch reaction zone as a second feed stream 431, which contacts the Fischer-Tropsch catalyst 433 to provide a second product stream 432 comprising C5+ hydrocarbons. Here, at least a portion of the C5+ hydrocarbons of the second product stream are sent to a hydrotreating unit 460, where they are hydrotreated to provide a final product stream 465. H2 may also be provided to the hydrotreating unit in a portion of the second product stream directed to the hydrotreating unit.

[0072] 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.

[0073] Embodiment 1: A method for conducting an integrated Fischer-Tropsch synthesis, comprising: providing a first feed stream comprising methanol; contacting the first 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 first product stream comprising CO and H; providing a second feed stream comprising H and at least a portion of the CO of the first product stream; The method includes contacting the second feed stream with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a second product stream comprising C5+ hydrocarbons.

[0074] Embodiment 2: The method of embodiment 1, further comprising separating at least a portion of the water from the first feed stream (e.g., at least 50%, at least 75%, or at least 90% of the water in the first feed stream).

[0075] Embodiment 3: The method of embodiment 1 or 2, wherein the first feed stream has a water content of 10 mol% or less, such as, or 2 mol% or less, or 0.5 mol% or less.

[0076] Embodiment 4: The method of any of embodiments 1-3, wherein the first 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.

[0077] Embodiment 5: The method of any of embodiments 1-4, wherein the first 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.

[0078] Embodiment 6: The method of any of embodiments 1-5, wherein the first feed stream further comprises one or more of H2, CO, CH4, CO2, and N2.

[0079] Embodiment 7: The method of any of embodiments 1-6, wherein the first feed stream has a water concentration of 5 mol% or less, e.g., 2 mol% or less, or 1 mol% or less.

[0080] Embodiment 8: The method of any of embodiments 1-7, wherein the first 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.

[0081] Embodiment 9: The method of any one of embodiments 1-8, wherein the methanol decomposition catalyst is, for example, a copper / zinc oxide on alumina catalyst.

[0082] Embodiment 10: The method of any of embodiments 1-9, wherein contacting the first feed stream with the methanol decomposition catalyst is conducted 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.

[0083] Embodiment 11: The method of any of embodiments 1-10, 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%.

[0084] Embodiment 12: The method of any one of embodiments 1 to 11, wherein the decomposition of methanol is carried out at a selectivity for CO of 20% or less, e.g., 15% or less, 10% or less, or 5% or less.

[0085] Embodiment 13: The method of any of embodiments 1 to 12, 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%.

[0086] Embodiment 14: The method of any of embodiments 1-13, wherein the first 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 %.

[0087] Embodiment 15: The method of any of embodiments 1-13, wherein the first 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.

[0088] Embodiment 16: The method of any one of embodiments 1 to 15, wherein the first 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, such as 1.5:1 to 2.5:1.

[0089] Embodiment 17: The method of any one of embodiments 1-16, wherein the first 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.

[0090] Embodiment 18: The method of any of Embodiments 1-17, further comprising separating at least a portion of the methanol from the first product stream (e.g., at least 50%, at least 75%, or at least 90% of the methanol in the first product stream).

[0091] Embodiment 19: The method of embodiment 18, further comprising recycling at least a portion of the methanol separated from the first product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the first product stream, to the first feed stream.

[0092] Embodiment 20: The method of any one of embodiments 1-19, further comprising separating at least a portion of the H2 from the first product stream.

[0093] Embodiment 21: The method of embodiment 19 or 20, further comprising activating a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream.

[0094] Embodiment 22: The method of any of embodiments 1-21, 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 first product stream is provided to the second feed stream.

[0095] Embodiment 23: The method of any of embodiments 1-22, wherein at least a portion of the H2 of the first product stream is provided to the second feed stream.

[0096] Embodiment 24: The method of any of embodiments 1 to 23, 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 first product stream is provided to the second feed stream.

[0097] Embodiment 25: The method of any one of embodiments 1-24, wherein H2 is provided to the second feed stream from a hydrogen source other than the first product stream.

[0098] Embodiment 26: The method of any of embodiments 1-25, wherein CO is provided to the second feed stream from a CO source other than the first product stream.

[0099] Embodiment 27: The method of any of embodiments 1-26, wherein one or more of CO2, CH4, and N2 is provided to the second feed stream from a source other than the first product stream.

[0100] Embodiment 28: The method of any one of embodiments 1 to 27, wherein the portion of the first product stream included in the second feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, such as in the range of 1:1 to 2.5:1.

[0101] Embodiment 29: The method of any one of embodiments 1 to 28, wherein the second feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1.

[0102] Embodiment 30: The method of any one of embodiments 1 to 29, wherein the second feed stream has a H2:CO molar ratio in the range of 1:1 to 2.5:1.

[0103] Embodiment 31: The method of any one of embodiments 1 to 30, wherein the second 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.

[0104] Embodiment 32: The method of any one of embodiments 1 to 31, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0105] Embodiment 33: The method of any one of embodiments 1 to 32, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount ranging from 5 to 25 wt.%, calculated as Co(0).

[0106] Embodiment 34: The method of any one of embodiments 1 to 32, wherein the Fischer-Tropsch catalyst comprises iron in an amount ranging from 25 to 95 wt. %, calculated as Fe(0).

[0107] Embodiment 35: The method of any one of embodiments 32-34, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0108] Embodiment 36: The method of any one of embodiments 32-35, 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.

[0109] Embodiment 37: The method of any one of embodiments 32-36, wherein the Fischer-Tropsch catalyst is a supported catalyst, and the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0110] Embodiment 38: The method of any one of embodiments 32-37, wherein the Fischer-Tropsch catalyst is a supported catalyst and the support is a titanium dioxide support.

[0111] Embodiment 39: The method of any one of embodiments 1 to 38, wherein the Fischer-Tropsch catalyst is activated in a reducing atmosphere.

[0112] Embodiment 40: The method of embodiment 39, wherein the reducing atmosphere comprises at least a portion of the hydrogen from the first product stream.

[0113] Embodiment 41: The method of any one of embodiments 1 to 40, wherein contacting the second 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 200°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 200 to 250°C, or 250 to 400°C, or 250 to 350°C, or 250 to 300°C, or 300 to 400°C).

[0114] Embodiment 42: The method of any one of embodiments 1 to 41, wherein contacting the second feed stream with the Fischer-Tropsch catalyst occurs at a temperature in the range of 200 to 350°C.

[0115] Embodiment 43: The method of any one of embodiments 1 to 42, wherein contacting the second 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).

[0116] Embodiment 44: The method of any one of embodiments 1 to 43, wherein contacting the second feed stream with the Fischer-Tropsch catalyst is conducted at a pressure in the range of 20 to 40 barg.

[0117] Embodiment 45: The method of any one of embodiments 1 to 44, wherein the contacting of the second feed stream with the Fischer-Tropsch catalyst and the contacting of the first feed stream with the methanol decomposition catalyst occur in the same plant.

[0118] Embodiment 46: The method of any one of embodiments 1 to 45, wherein contacting the Fischer-Tropsch catalyst with the second feed stream is carried out at a C5+ selectivity of at least 30%, e.g., at least 50%, or at least 70%.

[0119] Embodiment 47: The method of any one of embodiments 1 to 46, wherein the C5+ hydrocarbons of the second product stream comprise C5+ oxygenates.

[0120] Embodiment 48: The method of any one of embodiments 1 to 47, further comprising separating at least a portion of the C1 to C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0121] Embodiment 49: The method of embodiment 48, 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 second feed stream.

[0122] Embodiment 50: The method of embodiment 49 or embodiment 50, further comprising including at least a portion of the light hydrocarbon stream in the second feed stream.

[0123] Embodiment 51: The method of any one of embodiments 1 to 50, further comprising separating at least a portion of the H2 of the second product stream.

[0124] Embodiment 52: The method of embodiment 51, wherein at least a portion of the H2 separated from the second product stream is recycled to the second feed stream.

[0125] Embodiment 53: The method of embodiment 51 or embodiment 52, wherein at least a portion of the H2 separated from the second product stream is used to activate a Fischer-Tropsch catalyst.

[0126] Embodiment 54: The method of any one of embodiments 1 to 53, further comprising separating at least a portion of the CO of the second product stream.

[0127] Embodiment 55: The method of embodiment 54, wherein at least a portion of the CO separated from the second product stream is provided to the second feed stream.

[0128] Embodiment 56: The method of any one of embodiments 1-55, further comprising providing a C5+ hydrocarbon product stream from the second product stream comprising at least 80 wt% C5+ hydrocarbons, e.g., at least 90 wt% C5+ hydrocarbons.

[0129] Embodiment 57: The method of any one of embodiments 1-56, further comprising hydrotreating at least a portion of the C5+ hydrocarbon second product stream by contacting the C5+ hydrocarbon product stream with hydrogen and a hydrotreating catalyst.

[0130] Embodiment 58: The method of embodiment 57, wherein at least a portion of the hydrogen used in hydrotreating is provided from the first product stream or the second product stream.

[0131] Embodiment 59: The method of any one of embodiments 1-58, wherein one or more products are provided from at least a portion of the C5+ hydrocarbons of the second product stream, and the one or more products are one or more of a fuel, a wax, or an oil.

[0132] Embodiment 60: The method of any one of embodiments 1 to 59, wherein at least a portion of the H2 of the second feed stream is from a renewable source.

[0133] Embodiment 61: The method of any one of embodiments 1 to 60, wherein at least a portion of the hydrogen in the second feed stream is green hydrogen.

[0134] Embodiment 62: The method of any one of embodiments 1 to 61, wherein at least a portion of the hydrogen in the second feed stream is blue hydrogen.

[0135] Embodiment 63: The method of any one of embodiments 1 to 62, wherein at least a portion of the hydrogen in the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0136] Embodiment 64: The method of any one of embodiments 1 to 63, further comprising providing at least a portion of the H2 in the second feed stream by electrolysis of water.

[0137] Embodiment 65: The method of embodiment 64, wherein the electrolysis of water is carried out using electricity derived at least in part from renewable resources.

[0138] Embodiment 66: The method of embodiment 64 or embodiment 65, 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 second product stream.

[0139] Embodiment 67: The method of any one of Embodiments 64 to 66, further comprising the step of Embodiment 49, wherein at least a portion of the O2 produced by water electrolysis is supplied to a partial oxidation reactor.

[0140] Embodiment 68: The method of any one of embodiments 1 to 67, wherein the first reaction zone comprises a first reactor having a methanol decomposition catalyst disposed therein, and the second reaction zone comprises a second reactor having a Fischer-Tropsch catalyst disposed therein.

[0141] Embodiment 69: The method of any one of embodiments 1 to 68, wherein the first reaction zone comprises a first catalyst bed disposed with a methanol decomposition catalyst, and the second reaction zone comprises a second catalyst bed disposed with a Fischer-Tropsch catalyst.

[0142] Embodiment 70: The method of embodiment 69, wherein the first catalyst bed and the second catalyst bed are immiscible.

[0143] Embodiment 71: The method of embodiment 69 or embodiment 70, wherein the first catalyst bed and the second catalyst bed are disposed in separate reactors.

[0144] Embodiment 72: The method of embodiment 68, wherein the first catalyst bed and the second catalyst bed are disposed in a catalyst stack or bed section within the same reactor.

[0145] Embodiment 73: The method of any one of embodiments 1 to 72, wherein the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition (e.g., are the same catalyst).

[0146] 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 processes 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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 a first feed stream comprising methanol; contacting the first 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 first product stream comprising CO and H; providing a second feed stream comprising H and at least a portion of the CO of the first product stream; contacting the second feed stream with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a second product stream comprising C5+ hydrocarbons.

2. 10. The method of claim 1, wherein the first 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.

3. 3. The method of claim 1 or claim 2, wherein the first feed stream has a water concentration of 5 mol % or less, such as 2 mol % or less, or 1 mol % or less.

4. 4. The method of any one of claims 1 to 3, wherein the decomposition of methanol is carried out with a carbon product selectivity relative to CO of at least 50%, such as at least 60%, or at least 70%, or at least 80%, or at least 90%.

5. 5. The method of any one of claims 1 to 4, wherein the first product stream comprises at least 20 mol% CO and H2 in total, e.g., at least 35 mol%, or at least 50 mol%, or at least 65 mol%.

6. 6. The method of any one of claims 1 to 5, wherein the first 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, 1.5:1 to 2.5:1, or 1.5:1 to 3.5:

1.

7. 7. The method of any one of claims 1 to 6, further comprising separating at least a portion of the H2 from the first product stream and activating a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream.

8. 8. The method of any one of claims 1 to 7, wherein at least 50%, such as at least 75%, or at least 90%, or at least 95%, or at least 99% of the H2 of the first product stream is provided in the second feed stream.

9. 9. The process of any one of claims 1 to 8, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 5 to 25 wt.%, calculated as Co(0).

10. 10. The method of any one of claims 1 to 9, further comprising separating at least a portion of the C1 to C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

11. 11. The method of claim 10, 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 CO, and including at least a portion of the pOX stream in the second feed stream.

12. 11. The method of claim 9 or claim 10, further comprising including at least a portion of the light hydrocarbon stream in a second feed stream.

13. 13. The method of any one of claims 1-12, further comprising hydrotreating at least a portion of the second product stream of C5+ hydrocarbons by contacting the C5+ hydrocarbon product stream with hydrogen and a hydrotreating catalyst.

14. 14. The method of claim 13, wherein at least a portion of the hydrogen used in hydrotreating is provided from the first product stream or the second product stream.

15. The method of any one of claims 1 to 14, wherein the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition (e.g., are the same catalyst).

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