Fischer-Tropsch production of hydrocarbons from methanol

Abstract

The present disclosure generally relates to processes for integrated Fischer-Tropsch synthesis of hydrocarbons using methanol. In particular, the present disclosure relates to a process comprising: providing a first feed stream comprising methanol; contacting the first feed stream with a methanol decomposition catalyst to form a first product stream comprising CO and H2; providing a second feed stream comprising H2 and at least a portion of CO of the first product stream; the second feed stream is contacted with a Fischer-Tropsch catalyst to provide a second product stream comprising C5 + hydrocarbons.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority of European patent application No. 22190315.6 filed on August 12, 2022, the entire contents of which are incorporated herein by reference.

[0003] Public background Technical Field

[0004] The present disclosure relates to an integrated process for the Fischer-Tropsch synthesis of hydrocarbons from methanol. Background Art

[0005] The conversion of synthesis gas (i.e. a mixture of carbon monoxide and hydrogen, also known as syngas) to hydrocarbons by the Fischer-Tropsch process has been known for decades, but has historically lagged behind other hydrocarbon synthesis technologies. The growing importance of alternative energy sources has led to a renewed interest in the Fischer-Tropsch (FT) process because it enables a direct and environmentally acceptable route to high quality fuels and feedstock chemicals.

[0006] The FT process is known for producing straight chain hydrocarbons for fuels, as well as oxygenates that can be used in fuels and can also serve as valuable feedstock chemicals. Hydrocarbon fuels derived from the FT process are generally better able to meet increasingly stringent environmental regulations than conventional refinery-produced fuels because FT-derived fuels generally have lower levels of sulfur, nitrogen, and aromatic compounds that contribute to potent pollutants such as SO2, NO x The products derived from the FT process generally have a higher octane rating 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 in the synthesis of lubricants.

[0007] Synthesis gas is conventionally produced from fossil fuel sources, primarily through the gasification of coal. However, the handling properties of synthesis gas are poor because it must be transported in a low-density gas phase, or liquefied at high pressure.

[0008] Therefore, there is a need to develop improved schemes for the production and handling of syngas and the subsequent use of the syngas in the Fischer-Tropsch synthesis reaction. Summary of the invention

[0009] The present inventors have identified a method for efficiently converting methanol to hydrocarbons via methanol decomposition to produce synthesis gas. Advantageously, this method can be carried out at lower temperatures than conventional synthesis routes and does not require a reverse water gas shift (rWGS) process.

[0010] Therefore, in one aspect, the present disclosure provides a method for performing integrated Fischer-Tropsch synthesis, the method comprising:

[0011] providing a first feed stream comprising methanol;

[0012] 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 H2;

[0013] providing a second feed stream comprising H2 and at least a portion of the CO of the first product stream;

[0014] The second feed stream is contacted with a Fischer-Tropsch catalyst to perform Fischer-Tropsch synthesis to provide a 5+ A second product stream of hydrocarbons.

[0015] Other aspects of the present disclosure will be apparent to those skilled in the art based on the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1-4 A schematic diagram of a process according to an exemplary embodiment of the present disclosure is provided. DETAILED DESCRIPTION

[0017] The present disclosure relates to a technology for preparing hydrocarbons from methanol. The Fischer-Tropsch production of hydrocarbons from synthesis gas is well known in the art. However, synthesis gas (a mixture of H2 and CO) is difficult to store and transport at an effective density. In addition, environmentally friendly CO production modes, such as from carbon dioxide via a reverse water gas shift reaction, require high operating temperatures. In contrast, methanol is a common and inexpensive commodity chemical that can be produced from a variety of sources, including fermentation, biomass pyrolysis, catalytic reactions of synthesis gas, and CO2 hydrogenation. Methanol, which is a liquid at ambient temperature and pressure, can optionally be transported by low-pressure pipelines, ships, or trucks, so being a liquid generally improves transportation efficiency. Methanol can then be subjected to a methanol decomposition step to generate H2 and CO in a 2:1 ratio. At least CO of the methanol decomposition product can then be used in a Fischer-Tropsch synthesis reaction to generate hydrocarbons; H2 from methanol decomposition is also ideally used for Fischer-Tropsch synthesis. For example, some Fischer-Tropsch processes operate at H2:CO of 2:1 or greater, such as 2.2:1 or 3:1. In such a case, the H2 and CO mixture from the decomposition of methanol can be supplemented by a hydrogen source (such as green hydrogen from a recycle stream or produced using renewable energy) to form a Fischer-Tropsch reaction mixture.

[0018] Accordingly, in one aspect, the present disclosure provides a method for performing integrated Fischer-Tropsch synthesis, the method comprising:

[0019] providing a first feed stream of methanol;

[0020] 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 H2;

[0021] providing a second feed stream comprising H2 and at least a portion of the CO of the first product stream;

[0022] The second feed stream is contacted with a Fischer-Tropsch catalyst to perform Fischer-Tropsch synthesis to provide a 5+ A second product stream of hydrocarbons.

[0023] As used herein, "feed stream" is used to refer to the total material input to a process step, such as methanol decomposition or a Fischer-Tropsch reaction, whether provided as a single physical stream or multiple physical streams, and whether provided via a single inlet or multiple inlets. Similarly, "product stream" is used to refer to the total material output from a process step, such as methanol decomposition or a Fischer-Tropsch reaction, whether provided as a single physical stream or multiple physical streams, and whether provided via a single reactor outlet or multiple reactor outlets.

[0024] Methanol is a hygroscopic compound that is highly miscible with water. Therefore, many commercial methanol sources and methanol production methods may contain significant amounts of water, or significant water content may be obtained during storage and transportation. In some embodiments, the entrained water may be harmful to subsequent processes. For example, the excess water present in the methanol decomposition process step may undesirably cause CO to be converted back to CO2 via the water-gas shift reaction. In addition, external water may react with methanol in the methanol steam reforming reaction to form CO2 and hydrogen, thereby destroying process efficiency. Therefore, in various embodiments as described in addition herein, the method further includes separating at least a portion of water from the first feed stream. For example, in specific 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 as described in addition herein, the first feed stream has a water content of not more than 10 mol%, such as not more than 2 mol%, or not more than 1 mol%, or not more than 0.5 mol%.

[0025] In embodiments where water from the first feed stream is separated, the water can be disposed of as waste, or recycled into other processes. For example, in various embodiments, the separated water is directed to an electrolysis reactor to form H2 gas, for example for use in this integrated process or for use in other processes. In certain embodiments, the separated water undergoes a purification step prior to introduction into the electrolysis reactor.

[0026] The first feed stream introduces methanol to decompose into CO and H2. Methanol decomposition is a process different from methanol reforming. In methanol reforming, methanol and water react to produce CO2 and H2. Therefore, in various embodiments as described herein, methanol reforming is not used. For example, in specific embodiments, no more than 10% of the H2 is derived from methanol reforming (e.g., no more than 5% or no more than 1%).

[0027] The water-gas shift reaction is another method of generating H2 by reacting carbon monoxide with water. The reaction is also reversible, in which carbon dioxide can react with hydrogen to form carbon monoxide and water. Both reactions are conventionally used in the art. Advantageously, the method of the present disclosure avoids the use of the water-gas shift reaction and the reverse water-gas shift reaction. Therefore, in various embodiments as described herein, less than 10% (e.g., less than 5% or less than 2%) of each of the H2, CO, and CO2 of the method is generated by the water-gas shift reaction or the reverse water-gas shift reaction, as appropriate. In the various methods disclosed herein, no dedicated water-gas shift reactor or reverse water-gas shift reactor is used (however, as one of ordinary skill in the art will recognize, the water-gas shift reaction or the reverse water-gas shift reaction can be operated to a lesser extent as a side reaction during certain processes).

[0028] As described herein, methanolysis is utilized to form a product stream comprising CO and H. Thus, in various embodiments as otherwise described herein, the first feed stream comprises at least 5 mol% methanol. For example, in specific 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.

[0029] Optionally, the first feed stream may also include one or more additional gases, which may be inert or reactive. In such an embodiment, the first feed stream may further include one or more of H2, CO, CH4, CO2 and N2. In a specific embodiment, the first feed stream comprises an inert carrier gas, wherein the inert carrier gas comprises 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 decomposition reaction and / or provide a desired first product stream for the Fischer-Tropsch process. In such an embodiment, the first feed stream further comprises H2 and / or CO. In various embodiments as further described herein, one or more of H2, CO, CH4, CO2 and N2 are present in the first feed stream in an amount of up to 50 mol %, for example, up to 40 mol % or up to 30 mol %.

[0030] In various embodiments, the first feed stream has a low water content. Any water present can react with CO to be converted into CO2 and H2 at least partially by a water-gas shift reaction, and water can also react with methanol by reforming to provide H2 and CO2. The generated H2 is not conducive to the decomposition of methanol into CO and H2 according to the reaction equilibrium of methanol decomposition. Therefore, in various embodiments as described herein, the first feed stream has a water concentration of not more than 5 mol%, for example, not more than 2 mol%, or not more than 1 mol%, or not more than 0.5 mol%, or not more than 0.3 mol%, or not more than 0.2 mol%, or not more than 0.1 mol%.

[0031] The first feed stream can be provided at an elevated temperature. For example, in various embodiments as otherwise described 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.

[0032] The first feed stream is contacted with a methanol decomposition catalyst. Any suitable decomposition catalyst may be used; a variety of them are known in the art. For example, the decomposition catalyst may include a transition metal, such as one or more transition metals selected from Groups 7-11 of the periodic table. In a particular embodiment, the methanol decomposition catalyst comprises one or more of Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ir, or Pt, or a mixture thereof. In some embodiments, the decomposition catalyst may comprise an intermetallic compound or alloy. For example, the catalyst may further comprise 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, wherein the carrier is a refractory oxide, such as diamond oxide, silicon dioxide, zirconium oxide, cerium dioxide, titanium dioxide, aluminum oxide, lanthanum oxide, or magnesium oxide. In some embodiments, the methanol decomposition catalyst is a copper / zinc oxide catalyst, such as on aluminum oxide.

[0033] Those of ordinary skill in the art are familiar with catalytic processes for decomposing methanol into CO and H. Various examples of catalysts and catalytic processes are described in U.S. Pat. No. 6,541,142, U.S. Pat. No. 9,833,773, U.S. Pat. No. 4,716,859, and Usami et al., "Catalytic methanol decomposition at low temperatures overpalladium supported on metal oxides." Appl. Cat. A 171(1):123-130 (1998), each of which is incorporated herein by reference in its entirety.

[0034] The contact of the first feed stream with the methanol decomposition catalyst is carried out at a temperature suitable for implementing efficient methanol decomposition. In various embodiments as described herein, the contact of the first feed stream with the methanol decomposition catalyst is carried out at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 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. The contact can be carried out at various suitable pressures in the range of, for example, 0 to 50 barg. In various embodiments as described herein, the contact with the methanol decomposition catalyst can be integrated with the Fischer-Tropsch reactor. Therefore, in such an embodiment, the contact with the methanol decomposition catalyst can be carried out at a relatively high pressure, for example, at most 50 barg, for example, in the range of 20 to 40 barg.

[0035] The methanol decomposition reaction generates CO and H2, ideally with very few other products. Therefore, in various embodiments as described herein, the decomposition of methanol is carried out with a carbon product selectivity of at least 50% for CO, for example, at least 60%, or at least 70%, or at least 80%, or at least 90% for CO. Advantageously, in various embodiments, the decomposition of methanol is carried out with a selectivity of no more than 20%, for example, no more than 15%, or no more than 10%, or no more than 5% for CO2. In various embodiments as described herein, the decomposition of methanol is carried out with a methanol conversion rate of at least 30%, for example, at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0036] As described herein, the decomposition of methanol generates CO and H2. Thus, in various embodiments as further described herein, the first product stream comprises a total of at least 20 mol% CO and H2, such as at least 35 mol%, or at least 50 mol%, or at least 65 mol%. Without wishing to be bound by theory, the decomposition of methanol under these conditions is expected to generate 2 mol H2 / mol CO. Thus, in various embodiments as further described herein, the first product stream has a hydrogen / carbon monoxide molar ratio in the range of 0.5:1 to 5:1, such as 1:1 to 3:1, or 1.5:1 to 2.5:1, or 1.5:1 to 3.5:1. Of course, in other embodiments, this molar ratio may be different, such as due to the inclusion of H2 or CO in the first feed stream.

[0037] In various embodiments, the first product stream contains no greater than 20 mol % CO2, e.g., no greater than 15 mol % CO2, or no greater than 10 mol % CO2, or no greater than 5 mol % CO2, excluding CO2 not derived from methanol decomposition (e.g., excluding any CO2 present in the first feed stream).

[0038] Advantageously, a proportion of the methanol is consumed during the methanolysis reaction. Thus, in various embodiments as otherwise described herein, the first product stream comprises no greater than 75 mol % methanol, e.g., no greater than 60 mol % methanol, no greater than 50 mol % methanol, or no greater than 25 mol % methanol.

[0039] In some embodiments, it is necessary to further remove methanol from the first product stream. For example, in various embodiments as described herein, the method further includes separating at least a portion of methanol from the first product stream, for example, 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, the methanol of the first product stream, for example, at least a portion of the methanol separated from the first product stream, can be transferred or recycled to other processes. For example, in various embodiments as described herein, the method further includes recycling at least a portion of the methanol separated from the first product stream to the first feed stream.

[0040] As described herein, the methanol decomposition reaction produces CO and H2 in a 2:1 theoretical molar ratio, although the actual reaction output may be different. Depending on the desired ratio, this may result in excess hydrogen for subsequent processes. It is also worth noting that hydrogen may be present in the first feed stream to further increase the ratio in the first product stream. Therefore, in various embodiments as further described herein, the method further includes separating at least a portion of the H2 from the first product stream. The separated H2 may be suitable for various processes. Additionally or alternatively, in various embodiments as further described 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 first product stream.

[0041] As described herein, the second feed stream comprises at least a portion of the CO of the first product stream. Thus, in various embodiments as further described herein, at least 50% of the CO of the first product stream is supplied to the second feed stream. For example, in specific embodiments, at least 75%, such as at least 90%, or at least 95%, or at least 99% of the CO of the first product stream is supplied to the second feed stream. In various embodiments, substantially all of the CO of the first product stream is supplied to the second feed stream. Additionally or alternatively, in various embodiments as further described herein, the CO of the second feed stream may be partially supplied by a CO source other than the first product stream.

[0042] As described above, the second feed stream comprises H2 and CO, and the first product stream comprises H2. In various embodiments as described herein in addition, at least a portion of the H2 of the first product stream is supplied to the second feed stream. For example, in specific embodiments, 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 supplied to the second feed stream. In various embodiments, substantially all of the H2 of the first product stream is supplied to the second feed stream. Additionally or alternatively, in various embodiments as described herein in addition, the H2 of the second feed stream can be partially supplied by a hydrogen source other than the first product stream.

[0043] In various embodiments as otherwise described herein, the second feed stream may include other gases, such as CO2, CH4, or N2. In embodiments including other gases, the other gases 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 CO2, CH4, N2) may be supplied to the second feed stream from a source other than the first product stream.

[0044] Advantageously, the portion of the first product stream included in the second feed stream can be adjusted according to the process needs of the second feed stream. For example, in various embodiments as otherwise described herein, the portion of the first product stream included in the second feed stream has a 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.

[0045] As further described herein, the second feed stream is contacted with a Fischer-Tropsch catalyst. Thus, in various embodiments as further described herein, the second feed stream has a H2:CO molar ratio suitable for Fischer-Tropsch synthesis. For example, in various embodiments, the second feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1, for example, in the range of 1:1 to 2.5:1. In particular embodiments, the second feed stream has a H2:CO molar ratio of at least 1.2:1. For example, in various embodiments, the second feed stream may 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.

[0046] The Fischer-Tropsch catalyst can be selected by one of ordinary skill in the art. In various embodiments as described herein, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof (e.g., comprising cobalt or iron). In specific embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 2 to 30 wt%, such as 5 to 25 wt%, or 8 to 20 wt%, calculated as Co(0). In specific embodiments, the Fischer-Tropsch catalyst comprises iron in an amount in the range of 15 to 95 wt%, such as 25 to 95 wt%, or 30 to 90 wt%, calculated as Fe(0). In various embodiments as described herein, the Fischer-Tropsch catalyst further comprises manganese (e.g., manganese in an amount of 0.1 to 15 wt% or 1 to 10 wt%).

[0047] In various embodiments as further described herein, the Fischer-Tropsch catalyst is a supported catalyst wherein the carrier 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 particular embodiments, the carrier is a titanium dioxide carrier, or an aluminum oxide carrier, or a silicon dioxide carrier. In various embodiments, the carrier is a shaped particle, such as an extrudate. The catalyst can be prepared using conventional methods in the art.

[0048] Before use, some catalysts need to be activated. In various embodiments as described in addition herein, the Fischer-Tropsch catalyst is activated in a reducing atmosphere. In various embodiments, the catalyst is substantially reduced to generate a reduced catalyst material for catalyzing the Fischer-Tropsch reaction. In embodiments where the Fischer-Tropsch catalyst comprises cobalt, this method results in at least a portion of the cobalt being converted into cobalt metal. Ideally, reduction results in at least 50% of the cobalt being provided as cobalt (0). One of ordinary skill in the art can use conventional methods to reduce cobalt catalyst materials (e.g., materials based on cobalt oxide or cobalt hydroxide) to metallic form. In various embodiments as described in addition herein, the first reducing agent is hydrogen H2. Hydrogen can be mixed with other gases, such as an inert carrier gas. Examples of such inert carrier gases include nitrogen, carbon dioxide, argon or helium. Hydrogen can also be mixed with carbon monoxide, with or without the presence of one or more additional carrier gases. In various embodiments, reduction is achieved by contacting the first catalyst material with a first reducing gas, wherein the first reducing gas comprises a first reducing agent, wherein the first reducing gas comprises at least 50% by volume H2 (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 substantially 100% by volume H2). As described above, the H2 used for reduction can come from the first product stream. H2 can also be separated and recycled from the second product stream for reduction of the Fischer-Tropsch catalyst.

[0049] The temperature of the Fischer-Tropsch synthesis may suitably be in the range of 200-400° C., such as 200-300° C., or 210-400° C., or 210-300° C., or 220-400° C., or 220-300° C. In various embodiments as further described herein, the temperature of the Fischer-Tropsch synthesis is in the range of 200-250° C., for example 200-240° C., or 200-230° C., or 200-220° C., or 210-250° C., or 210-240° C., or 210-230° C., or 220-250° C., or 220-240° C., or 230-250° C. The pressure of the reaction may suitably be in the range of 10-50 barg, for example 20-50 barg, or 25-50 barg, or 10-40 barg, or 20-40 barg, or 25-40 barg or 10-35 barg, or 20-35 barg, or 25-35 barg. In a particular embodiment, contacting of the second feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20-40 barg.

[0050] Subject to the limitations described herein, one of ordinary skill in the art can implement the methods of the present disclosure using conventional Fischer-Tropsch catalysts and methods. Suitable techniques for catalyst preparation and hydrocarbon synthesis, particularly with respect to C 5+The synthesis of hydrocarbons and / or oxygenated compounds is well known in the art, for example as described in International Patent Application Publication No. 2019 / 154885, the entire text of which is incorporated herein by reference.

[0051] Advantageously, in various embodiments as otherwise described herein, 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 can be carried out in the same manufacturing plant. This can be, for example, in different beds in the same reactor, or in different reactors. In such embodiments, the two processes can be integrated to provide efficient conversion of methanol to hydrocarbons.

[0052] The Fischer-Tropsch process is commonly used to produce C 5+ Hydrocarbons, such as unsubstituted C 5+ Hydrocarbons (such as alkanes and alkenes) and oxygenated C5+ hydrocarbons (such as C 5+ The Fischer-Tropsch reaction as described herein is desirably operated with high selectivity to hydrocarbons. For example, in various embodiments as otherwise described herein, the contacting of the Fischer-Tropsch catalyst with the second feed stream is at least 30%, e.g., at least 50%, or at least 70% C 5+ The second product stream may be selectively carried out. As known in the art, the hydrocarbon composition of the second product stream may vary with the type of catalyst and process conditions. In various embodiments, the hydrocarbon composition comprises hydrocarbons (e.g., straight-chain hydrocarbons, branched-chain hydrocarbons, saturated or unsaturated hydrocarbons) and oxygen-containing derivatives thereof. In various embodiments as described herein, the hydrocarbon composition comprises at least one of alkanes, olefins and alcohols.

[0053] In general, longer chain hydrocarbons are more desirable than shorter chain hydrocarbons. Therefore, in various embodiments as described herein, the second product stream comprises C1-C4 hydrocarbons, and the method further comprises separating at least a portion of C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream. In a particular embodiment, 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 at least a portion of the pOX stream is included in the second feed stream. For example, the catalytic partial oxidation of hydrocarbon feedstock is described in European Patent Application Publication No. 0303438A1, the entire text of which is incorporated herein by reference. Additionally or alternatively, in a particular embodiment, at least a portion of the light hydrocarbon stream can be directed to a steam reforming unit and / or an autothermal reforming unit, such as an electrically heated steam reforming unit. Then the resulting hydrogen and / or carbon oxides can be at least partially included in the second feed stream as described herein.

[0054] Light hydrocarbon streams contain many components, including short-chain (e.g., C1-C4) saturated hydrocarbons, short-chain olefins, and short-chain oxygenates. In particular, olefins (e.g., ethylene, propylene, butenes) and alcohols may also be recycled to the Fischer-Tropsch reactor to generate additional C 5+ Hydrocarbons. Thus, in various embodiments as otherwise described herein, the method further comprises including at least a portion of the light hydrocarbon stream in the second feed stream. Additionally or alternatively, at least a portion of the light hydrocarbon stream may be included in the first feed stream to be transferred to the second feed stream.

[0055] In various embodiments, the second product stream may contain unreacted H2. In various embodiments as described herein, the method further includes separating at least a portion of the H2 of the second product stream. The separated H2 can then be directed to a process that requires it. For example, in a particular embodiment, at least a portion of the H2 separated from the second product stream is supplied to the second feed stream. As mentioned above, at least a portion of the H2 separated from the second product stream can be used to activate the Fischer-Tropsch catalyst.

[0056] In various embodiments, the second product stream may contain unreacted CO. In various embodiments as otherwise described herein, the method further comprises separating at least a portion of the CO of the second product stream. The separated CO can then be directed to a process requiring it. For example, in a particular embodiment, at least a portion of the CO separated from the second product stream is supplied to the second feed stream.

[0057] In various embodiments, the second product stream may include CO 2. Thus, in various embodiments as otherwise described herein, the method further comprises separating at least a portion of the CO 2 from the second product stream. The separated CO 2 can then be directed to a process requiring it.

[0058] It may be desirable to provide C from a second product stream 5+ The hydrocarbon product stream, i.e., a stream containing at least 70 wt. % C 5+ Hydrocarbons, such as at least 80 wt% C 5+ hydrocarbons, or at least 85 wt% C 5+ As one of ordinary skill in the art will appreciate, this can be done by separating off at least a portion of the other components, such as C1-C4 hydrocarbons, CO, CO2 and H2, for example as described above.

[0059] In addition, in some cases it may be desirable to 5+ The hydrocarbon product stream is further converted. Hydroprocessing, i.e., 5+ Contacting a hydrocarbon product stream with hydrogen and a hydrotreating catalyst may be used for this purpose. Thus, in various embodiments, the process as otherwise described herein comprises contacting a hydrocarbon product stream with hydrogen and a hydrotreating catalyst. 5+The hydrocarbon product stream is contacted with hydrogen and a hydrotreating catalyst to hydrotreat the C 5+ Hydrocarbon product stream. Various hydrotreating process steps can be used. For example, hydrocracking can be used to provide products with lower molecular weights, such as converting higher molecular weight waxes into lower molecular weight products for use as fuels, such as aviation fuel, diesel fuel, or gasoline. Hydrodeoxygenation can be used to convert oxygenates into non-oxygenated hydrocarbons. Hydrotreating can also be used to convert olefins into alkanes. Hydroisomerization can be used to change a mixture of hydrocarbon isomers. At least a portion of the H2 used in the hydrotreating can be H2 separated from one or both of the first product stream and the second product stream as described above.

[0060] As will be appreciated by those of ordinary skill 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 otherwise described herein, at least a portion of the second product stream C 5+ The hydrocarbons provide one or more products. The one or more products may be, for example, one or more of a fuel (eg, diesel fuel, gasoline, or aviation fuel), a wax, or an oil (eg, for lubrication or metalworking).

[0061] The methods described herein can be performed at high throughput. For example, in various embodiments as otherwise described herein, CO2 hydrogenation, MeOH decomposition and / or Fischer-Tropsch synthesis are performed at 2000 hr. -1 Up to 20,000hr -1 For example, in various such embodiments, the contacting is carried out at a GHSV of 4000 hr. -1 Up to 18,000hr -1 , or 6000hr -1 Up to 16,000hr -1 , or 8000hr -1 Up to 12,000hr -1 , or 2000hr -1 Up to 12,000hr -1 , or 4000hr -1 Up to 10,000hr -1 , or 6000hr -1 Up to 10,000hr -1 , or 2000hr -1 Up to 8,000hr -1 , or 4000hr -1 Up to 8,000hr -1 , or 2000hr -1 Up to 6000hr -1 Of course, higher and lower airspeeds may also be used, depending on the system.

[0062] Hydrogen gas can be added to the second feed stream to increase the H2:CO ratio. Conventional H2 gas is most commonly derived from natural gas, typically by steam reforming of methane, partial oxidation of hydrocarbons and / or gasification of coal. However, as conventionally performed, these methods each release a large amount of CO2 into the atmosphere and rely on fossil fuels as starting materials and / or energy sources. In contrast, other H2 sources that are preferred from an environmental perspective are known. Therefore, in various embodiments as further described herein, at least a portion of the H2 (e.g., at least 50%, at least 75%, at least 90% or at least 95%) of the first feed stream and / or the second feed stream comes from renewable resources.

[0063] As is known in the art, hydrogen can be provided with color-based names depending on its production source. Examples of hydrogen types include green hydrogen, blue hydrogen, gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0064] One potential source of green hydrogen is through water electrolysis. Many electrolysis methods are known in the art. For example, pure water can be electrolyzed to produce hydrogen and oxygen, or other solutions, such as salt solutions, can be electrolyzed to produce hydrogen and another product (e.g., chlorine). In a particular embodiment, hydrogen is formed by electrolysis of a salt solution. Water electrolysis is further described in U.S. Patent No. 4,312,720, U.S. Patent No. 4,021,323, and U.S. Patent No. 4,094,751, each of which is incorporated herein by reference in its entirety.

[0065] In order to qualify as green hydrogen, the electricity used for water electrolysis must come from a renewable source, i.e., a source that does not rely on the combustion of fossil fuels. Exemplary sources of renewable power include solar power through photovoltaic capture or solar thermal technology, wind power, geothermal energy capture, hydroelectric energy, or other renewable sources. Hydrogen used for water electrolysis using solar power is sometimes referred to as yellow hydrogen. Suitable renewable energy sources are known to those skilled in the art and may optionally be selected through certification by appropriate agencies. Therefore, in various embodiments as further described herein, at least a portion of the H2 of the second feed stream is green hydrogen and / or yellow hydrogen. For example, in specific embodiments, the method further includes providing at least a portion of the H2 of the second feed stream by electrolysis of water. In various embodiments, the electrolysis of water is performed using electricity derived at least in part from a renewable source.

[0066] Certain recycle streams may also be suitable for powering water electrolysis, as appropriate. For example, in various embodiments as otherwise described herein, water electrolysis is performed using electricity generated at least in part from steam produced by combustion of a light hydrocarbon stream provided at least in part by the second product stream.

[0067] The electrolysis of water conventionally produces H2 and O2 gases. As described further herein, in some embodiments, the method further comprises oxidizing at least a portion of a light hydrocarbon stream (e.g., derived from a second product stream) to provide a pOX stream. In such embodiments, O2 can be used for oxidation. Therefore, in a particular embodiment, at least a portion of the O2 generated by the electrolysis of water is supplied to a partial oxidation reactor.

[0068] Blue hydrogen is defined as hydrogen made in a process that is dependent to some extent on fossil fuels but is overall carbon neutral (i.e., does not result in any net introduction of carbon dioxide into the atmosphere). In various embodiments as described herein, the hydrogen used in the method as described herein comprises blue hydrogen. An example of blue hydrogen is hydrogen made from fossil fuel-derived hydrocarbons such as methane gas, wherein the resulting carbon product is captured or otherwise utilized. For example, steam reforming of methane can be performed to produce 3 moles of hydrogen and 1 mole of carbon monoxide for each mole of methane. Steam reforming of methane is highly endothermic and requires a large amount of energy input. Of course, the energy required to carry out these processes must come from a renewable source, or a source with sufficient carbon capture technology. Therefore, in various embodiments as described herein, at least a portion of the hydrogen (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) is formed by steam reforming of methane. Steam reforming of methane to produce hydrogen is discussed in International Patent Application Publication No. 2004 / 022480, the entire text of which is incorporated herein by reference. Thus, in various embodiments as otherwise described herein, at least a portion of the H2 of the second feed stream is blue hydrogen.

[0069] Gray hydrogen is the most conventional source of H2. Gray hydrogen is made from natural gas / methane by steam reforming, but compared to blue hydrogen, the greenhouse gases (e.g., CO2) produced are not captured. In various embodiments as otherwise described herein, at least a portion of the H2 of the second feed stream is gray hydrogen.

[0070] Black hydrogen and brown hydrogen are made from black coal or lignite, respectively, typically by gasification thereof without any carbon capture. In various embodiments as otherwise described herein, at least a portion of the H2 of the second feed stream is black hydrogen and / or brown hydrogen.

[0071] Powdered hydrogen is generated by water electrolysis, wherein the energy required for electrolysis is generated by nuclear energy. In various embodiments as further described herein, at least a portion of the H2 of the second feed stream is powdered hydrogen. Powdered hydrogen is also known as purple hydrogen or red hydrogen.

[0072] Blue green hydrogen is produced by pyrolysis of methane, wherein the byproducts are hydrogen and solid elemental carbon. In various embodiments as otherwise described herein, at least a portion of the H2 of the second feed stream is blue green hydrogen.

[0073] White hydrogen is naturally occurring hydrogen that can be released by hydraulic fracturing. In various embodiments as otherwise described herein, at least a portion of the H2 of the second feed stream is white hydrogen.

[0074] As described herein, the disclosed method includes three central reactions in various embodiments: hydrogenation of CO2, methanol decomposition, and Fischer-Tropsch synthesis. As described herein, these reactions can be advantageously carried out in different spatial arrangements relative to each other. As known in the art, the reaction zone consists of one or more catalyst beds, and one or more reaction zones can be in the same manufacturing plant. Different manufacturing plants are usually geographically separated so that raw materials cannot be transferred between them without intermediate transportation and storage steps. Therefore, in various embodiments as further described herein, the first reaction zone comprises a first reactor in which a methanol decomposition catalyst is arranged, and wherein the second reaction zone comprises a second reactor in which a Fischer-Tropsch catalyst is arranged. In various embodiments as further described herein, the first reaction zone comprises a first catalyst bed in which a methanol decomposition catalyst is arranged, and the second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is arranged. For example, in a specific embodiment, the first catalyst bed and the second catalyst bed are arranged in the same reactor, for example, in a catalyst stack or a catalyst bed section.

[0075] As described herein, in some embodiments, various catalyst beds may be located in different reactors. Positioning the catalyst beds in separate reactors may have various process advantages. For example, this separation enables each unit to experience reactor downtime (e.g., for maintenance) independently of each other. In addition, the reactors can be maintained at different temperatures to maximize the selectivity and efficiency of each process. Exothermic and endothermic chemical reactions require temperature control to maintain a stable operating temperature. The separate processes carried out in separate reactors simplify temperature control because different catalysts will change activity at different rates over time. Therefore, in certain embodiments as described in addition herein, the first catalyst bed and the second catalyst bed are not blended. When catalysts for different processes share the same catalyst bed, blending of catalysts occurs. As used herein, two different catalyst beds in a reactor are not blended. In certain embodiments as described in addition herein, the first catalyst bed and the second catalyst bed are arranged in separate reactors.

[0076] In certain embodiments, similar catalysts can be used for some reactions. For example, in some embodiments, the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition. In certain embodiments, the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst are the same catalyst.

[0077] An exemplary embodiment is shown in a diagrammatic view. Figure 1 , which depicts method 100 as contained within a single manufacturing plant 141. Figure 1 In an embodiment of the present invention, the crude methanol stream 111 is subjected to an optional water removal step, and the water is directed to the electrolysis reactor 160 via the dehydration stream 112. The first feed stream is directed to the methanol decomposition reaction zone 120 (herein, the methanol decomposition reactor), where it is contacted with the methanol decomposition catalyst 123 to decompose at least a portion of the methanol to form a first product stream 122 comprising CO and H2. The first feed stream 121 can also be supplemented by introducing other gases, such as CO and / or H2, via a supplemental feed (not shown). In Figure 1 In an embodiment of the present invention, the first product stream 122 is directed from the first reaction zone 120 to a second feed stream 131. The second feed stream 131 comprises H2 (e.g., from the first product stream) and at least a portion of CO of the first product stream. The second feed stream 131 may also be supplemented by introducing other gases, such as CO and / or H2, via a supplemental feed (not shown). The second feed stream 131 is directed 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 is contacted with the Fischer-Tropsch catalyst 133 to provide a feed stream comprising C 5+ A second product stream 132 of hydrocarbons. Figure 1 In an embodiment, a 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 generator 170. Additionally or alternatively, a light hydrocarbon stream 137, optionally containing gaseous products, is separated from the second product stream 132 and recycled back to the second feed stream 131. Examples of gaseous products for recycling include CO, H2, CH4, CO2, C2H4, C3H6, C3H8, C3H7OH, and H2O. The CO2 generator 170 uses the light hydrocarbon stream to produce electricity 172 that is supplied to the electrolysis reactor 160 (e.g., by burning the light hydrocarbon stream to form steam, which in turn can drive a turbine). As one of ordinary skill in the art will recognize, the Fischer-Tropsch reaction produces water as a byproduct; Figure 1 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 the water stream 138. The electrolysis reactor uses electricity derived at least in part from the light hydrocarbon stream (although other sources of electricity, including renewable sources, can be used) to electrolyze water (here separated from the crude methanol stream and / or the second product stream) to provide hydrogen.

[0078] As described above, methanol can be formed in a first manufacturing plant and then transported (e.g., via a vehicle or pipeline) to a second manufacturing plant where the methanol is decomposed and the resulting carbon monoxide is used in a Fischer-Tropsch reaction to provide hydrocarbons. Figure 2In the embodiment of the present invention, methanol is loaded into a storage tank 217 and then transported to a second manufacturing plant 243 by a truck 218. The first feed stream 221 is directed to a methanol decomposition reaction zone 220, where it is contacted with a methanol decomposition catalyst 223 to generate a first product stream 222 comprising CO and H2. Here, at least a portion of the first product stream 222 is supplied to a second feed stream 231. The second feed stream 231 is directed to a Fischer-Tropsch reaction zone 230, where it is contacted with a Fischer-Tropsch catalyst 233 to obtain a first product stream 222 comprising CO and H2. 5+ A second product stream 232 of hydrocarbons.

[0079] Another exemplary embodiment is shown in a diagrammatic view. Figure 3 Here, in the method 300, an additional gas stream 324 is added to the crude methanol stream 312 (optionally dehydrated, not shown), and the resulting mixture is provided as a first feed stream 321. The first feed stream 321 is directed to a methanol decomposition reaction zone 320, where a first product stream 322 is provided with a methanol decomposition catalyst 323. Here, the first product stream 322 is withdrawn from the methanol decomposition reaction zone, and unreacted methanol (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) is substantially separated from the first product stream and recycled to the first feed stream 321 via a methanol recycle 325. At least a portion of the H2 of the first product stream 322 may also or alternatively be supplied to a second reaction zone 330 to activate the Fischer-Tropsch catalyst 333 via a H2 stream 327. The remainder of the first product stream 322 is provided as a portion of a second feed stream 331, which is directed to the Fischer-Tropsch reaction zone 330. A portion of the second feed stream 331 also includes an additional gas stream 335, which provides additional H2 and / or CO to the Fischer-Tropsch reaction zone via a separate inlet. The second feed stream is contacted with the Fischer-Tropsch catalyst 333 in the Fischer-Tropsch reaction zone to provide a gas stream comprising C 5+ A second product stream 332 of hydrocarbons. The second product stream 332 is directed from the Fischer-Tropsch reaction zone, from which a light hydrocarbon stream 336 is separated and directed to a partial oxidation unit 350. As one of ordinary skill in the art will recognize, the partial oxidation unit oxidizes the light hydrocarbons to provide CO2 and CO; at least a portion of the CO generated by the partial oxidation unit 350 is included in the second feed stream 331 via the CO stream 351.

[0080] As mentioned above, various catalysts can be provided together in the same reactor. An example of such an embodiment is shown in a schematic view. Figure 4Here, in method 400, a first feed stream 421 is supplied to a stacked bed reactor 425, which includes a methanol decomposition reaction zone 420 (here, the first bed of the stacked bed reactor, which includes a methanol decomposition catalyst 423) and a Fischer-Tropsch reaction zone 430 (here, the second bed of the stacked bed reactor, which includes a Fischer-Tropsch catalyst 433). The first feed stream 421 is contacted with the methanol decomposition catalyst 423 to provide a first product stream 422 comprising CO and H2. The first product stream is supplied as a second feed stream 431 to the Fischer-Tropsch reaction zone, which is contacted with the Fischer-Tropsch catalyst 433 to provide a first product stream 422 comprising CO and H2. 5+ A second product stream 432 of hydrocarbons is obtained. Here, at least a portion of the second product stream C 5+ The hydrocarbons are directed to a hydroprocessing unit 460 where they are hydroprocessed to provide a final product stream 465. H2 may also be supplied to the hydroprocessing unit in the portion of the second product stream directed to the hydroprocessing unit.

[0081] Various exemplary embodiments of the present disclosure include, but are not limited to, the embodiments listed below, which may be combined in any number and in any combination that are not technically or logically contradictory.

[0082] Embodiment 1. A method for performing integrated Fischer-Tropsch synthesis, the method comprising:

[0083] providing a first feed stream comprising methanol;

[0084] 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 H2;

[0085] providing a second feed stream comprising H2 and at least a portion of the CO of the first product stream;

[0086] The second feed stream is contacted with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a 5+ A second product stream of hydrocarbons.

[0087] Embodiment 2. The method of Embodiment 1, further comprising separating at least a portion of the water from the first product stream (eg, at least 50%, at least 75%, or at least 90% of the water in the first product stream).

[0088] Embodiment 3. The process of Embodiment 1 or Embodiment 2, wherein the first feed stream has a water content of not greater than 10 mol %, eg, not greater than 2 mol % or not greater than 0.5 mol %.

[0089] Embodiment 4. A process according to any one 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.

[0090] Embodiment 5. A process according to 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.

[0091] Embodiment 6. A method according to any of Embodiments 1-5, wherein the first feed stream further comprises one or more of H2, CO, CH4, CO2 and N2.

[0092] Embodiment 7. The method according to any of Embodiments 1-6, wherein the first feed stream has a water concentration of no greater than 5 mol%, eg, no greater than 2 mol% or no greater than 1 mol%.

[0093] Embodiment 8. A process according to 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.

[0094] Embodiment 9. The method according to any of Embodiments 1-8, wherein the methanol decomposition catalyst is a copper / zinc oxide catalyst, such as on alumina.

[0095] Embodiment 10. A process according to any one of Embodiments 1-9, wherein contacting of the first feed stream with the methanol decomposition 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.

[0096] Embodiment 11. A method according to any of Embodiments 1-10, wherein the decomposition of methanol is carried out with a carbon product selectivity to CO of at least 50%, such as at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0097] Embodiment 12. A method according to any of Embodiments 1-11, wherein the decomposition of methanol is carried out with a selectivity to CO2 of not more than 20%, eg, not more than 15%, not more than 10% or not more than 5%.

[0098] Embodiment 13. A method according to any of Embodiments 1-12, wherein the decomposition of methanol is carried out at a methanol conversion rate of at least 30%, such as at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0099] Embodiment 14. A method according to any of Embodiments 1-13, wherein the first product stream comprises a total of at least 20 mol% CO and H2, for example at least 35 mol%, or at least 50 mol%, or at least 65 mol%.

[0100] Embodiment 15. A method according to any of Embodiments 1-13, wherein the first product feed stream contains no more than 20 mol% CO2, for example no more than 15 mol% CO2, or no more than 10 mol% CO2, or no more than 5 mol% CO2, excluding CO2 not derived from methanol decomposition.

[0101] Embodiment 16. The process of any of Embodiments 1-15, wherein the first product stream has a hydrogen / carbon monoxide molar ratio in the range of 0.5:1 to 5:1, eg, 1:1 to 3:1, 1.5:1 to 2.5:1.

[0102] Embodiment 17. The method of any of Embodiments 1-16, wherein the first product stream comprises no greater than 75 mol% methanol, e.g., no greater than 60 mol% methanol, or no greater than 50 mol% methanol, or no greater than 25 mol% methanol.

[0103] 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).

[0104] 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.

[0105] Embodiment 20. The method of any of Embodiments 1-19, further comprising separating at least a portion of the H2 from the first product stream.

[0106] Embodiment 21. The method of any of Embodiments 19 and 20, further comprising activating the Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream.

[0107] Embodiment 22. The method of any of Embodiments 1-21, wherein at least 50% of the CO of the first product stream is supplied to the second feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0108] Embodiment 23. The method of any of Embodiments 1-22, wherein at least a portion of the H2 of the first product stream is supplied to the second feed stream.

[0109] Embodiment 24. The method of any of Embodiments 1-23, wherein at least 50% of the H2 of the first product stream is supplied to the second feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0110] Embodiment 25. The method of any of Embodiments 1-24, wherein H2 is supplied to the second feed stream from a hydrogen source other than the first product stream.

[0111] Embodiment 26. The method of any of Embodiments 1-25, wherein CO is supplied to the second feed stream from a CO source other than the first product stream.

[0112] Embodiment 27. The method of any of Embodiments 1-26, wherein one or more of CO2, CH4, and N2 is supplied to the second feed stream from a source other than the first product stream.

[0113] Embodiment 28. The method of any of Embodiments 1-27, 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, for example, in the range of 1:1 to 2.5:1.

[0114] Embodiment 29. The method of any of Embodiments 1-28, wherein the second feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1.

[0115] Embodiment 30. The method of any of Embodiments 1-29, wherein the second feed stream has a H2:CO molar ratio in the range of 1:1 to 2.5:1.

[0116] Embodiment 31. The method of any of Embodiments 1-30, wherein the second feed stream has a H2:CO molar ratio of at least 1.2:1, e.g., in the range of 1.2:1-2.5:1.

[0117] Embodiment 32. The method of any one of Embodiments 1-31, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0118] Embodiment 33. The method of any of Embodiments 1-32, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 5-25 wt. %, calculated as Co(0).

[0119] Embodiment 34. The method of any of Embodiments 1-32, wherein the Fischer-Tropsch catalyst comprises iron in an amount in the range of 25-95 wt. % calculated as Fe(0).

[0120] Embodiment 35. The method of any one of Embodiments 32-34, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0121] Embodiment 36. The method of any one of Embodiments 32-35, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, magnesium oxide, silicon oxide, and zinc oxide.

[0122] Embodiment 37. The method of any one of Embodiments 32-36, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0123] Embodiment 38. The method of any one of Embodiments 32-37, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titania support.

[0124] Embodiment 39. The method of any one of Embodiments 1-38, wherein the Fischer-Tropsch catalyst is activated in a reducing atmosphere.

[0125] Embodiment 40. The method of Embodiment 39, wherein the reducing atmosphere comprises at least a portion of the hydrogen from the first product stream.

[0126] Embodiment 41. The method of any of Embodiments 1-40, wherein contact of the second feed stream with the Fischer-Tropsch catalyst is carried out at a temperature in the range of 150-400°C (for example, in the range of 150-350°C, or 150-300°C, or 150-250°C, or 150-200°C, or 200-400°C, or 200-350°C, or 200-300°C, or 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0127] Embodiment 42. The method of any of Embodiments 1-41, wherein contacting the second feed stream with the Fischer-Tropsch catalyst is carried out at a temperature in the range of 200-350°C.

[0128] Embodiment 43. The method of any one of Embodiments 1-42, wherein contact of the second feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 10-50 barg (e.g., 20-50 barg, or 25-50 barg, or 10-40 barg, or 20-40 barg, or 25-40 barg or 10-35 barg, or 20-35 barg, or 25-35 barg).

[0129] Embodiment 44. The method of any of Embodiments 1-43, wherein contacting the second feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20-40 barg.

[0130] Embodiment 45. The method of any of Embodiments 1-44, 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 are performed in the same manufacturing plant.

[0131] Embodiment 46. The method of any one of Embodiments 1-45, wherein the contacting of the Fischer-Tropsch catalyst with the second feed stream is at least 30%, such as at least 50% or at least 70% C 5+ Selective.

[0132] Embodiment 47. The method of any one of Embodiments 1-46, wherein the C of the second product stream 5+ Hydrocarbons contain C 5+ Oxygen-containing compounds.

[0133] Embodiment 48. The method of any of Embodiments 1-47, further comprising separating at least a portion of the C1-C4 hydrocarbons from the second product stream to provide a light hydrocarbon stream.

[0134] 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 a second feed stream.

[0135] Embodiment 50. The method of Embodiment 49 or Embodiment 50, further comprising including at least a portion of the light hydrocarbon stream in a second feed stream.

[0136] Embodiment 51. The method of any of Embodiments 1-50, further comprising separating at least a portion of the H2 of the second product stream.

[0137] 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.

[0138] 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 the Fischer-Tropsch catalyst.

[0139] Embodiment 54. The method of any of Embodiments 1-53, further comprising separating at least a portion of the CO of the second product stream.

[0140] Embodiment 55. The method of Embodiment 54, wherein at least a portion of the CO separated from the second product stream is supplied to the second feed stream.

[0141] Embodiment 56. The method of any one of Embodiments 1-55, further comprising providing a second product stream comprising at least 80 wt% C 5+ Hydrocarbons, such as at least 90 wt.% C 5+ C 5+ A hydrocarbon product stream.

[0142] Embodiment 57. The method of any one of Embodiments 1-56, further comprising: 5+ The hydrocarbon product stream is contacted with hydrogen and a hydrotreating catalyst to hydrotreat the C 5+ At least a portion of a hydrocarbon second product stream.

[0143] Embodiment 58. The method of Embodiment 57, wherein at least a portion of the hydrogen used in the hydrotreating is provided by the first product stream or the second product stream.

[0144] Embodiment 59. The method of any one of Embodiments 1-58, wherein at least a portion of the second product stream C 5+ The hydrocarbons provide one or more products that are one or more of fuels, waxes, or oils.

[0145] Embodiment 60. The method of any of Embodiments 1-59, wherein at least a portion of the H2 of the second feed stream is from a renewable source.

[0146] Embodiment 61. The method of any of Embodiments 1-60, wherein at least a portion of the hydrogen of the second feed stream is green hydrogen.

[0147] Embodiment 62. The method of any of Embodiments 1-61, wherein at least a portion of the hydrogen in the second feed stream is blue hydrogen.

[0148] Embodiment 63. The method of any one of Embodiments 1-62, wherein at least a portion of the hydrogen of the second feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, blue-green hydrogen, yellow hydrogen and / or white hydrogen.

[0149] Embodiment 64. The method of any of Embodiments 1-63, further comprising providing at least a portion of the H2 to the second feed stream by electrolysis of water.

[0150] Embodiment 65. The method of Embodiment 64, wherein the electrolysis of water is performed using electricity derived at least in part from a renewable source.

[0151] 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 by the second product stream.

[0152] Embodiment 67. The method of any one of Embodiments 64-66, further comprising the steps of Embodiment 49, wherein at least a portion of the O2 generated by water electrolysis is supplied to a partial oxidation reactor.

[0153] Embodiment 68. The method of any of Embodiments 1-67, wherein the first reaction zone comprises a first reactor in which a methanol decomposition catalyst is disposed, and wherein the second reaction zone comprises a second reactor in which a Fischer-Tropsch catalyst is disposed.

[0154] Embodiment 69. The method of any of Embodiments 1-68, wherein the first reaction zone comprises a first catalyst bed in which a methanol decomposition catalyst is disposed, and the second reaction zone comprises a second catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0155] Embodiment 70. The method of Embodiment 69, wherein the first catalyst bed and the second catalyst bed are not intermixed.

[0156] 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.

[0157] Embodiment 72. The method of Embodiment 68, wherein the first catalyst bed and the second catalyst bed are arranged in the same reactor as a catalyst stack or bed section.

[0158] Embodiment 73. The method of any one of Embodiments 1-72, wherein the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition (eg, are the same catalyst).

[0159] The details shown herein are provided as examples and only for the purpose of illustrative discussion of various embodiments of the present disclosure, and are given in order to provide the most useful and understandable description of the principles and concepts of various embodiments of the present disclosure. In this regard, no attempt is made to display the details related to the methods of the present disclosure to a level of detail necessary for a basic understanding of the methods described herein, and the descriptions made in conjunction with the examples make it clear to those skilled in the art how several forms of the methods of the present disclosure can be specifically implemented in practice. Therefore, before describing the disclosed methods and apparatus, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and therefore can certainly vary. It is also to be understood that the terms used herein are only for the purpose of describing specific aspects, and are not intended to be limiting unless specifically defined herein.

[0160] The terms “a” and “an” and “the” and similar referents used in the context of describing the methods of the present disclosure (especially in the context of the following embodiments and claims) should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0161] Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order of steps. The use of any and all examples or exemplary wordings (e.g., "such as") provided herein is intended only to better illustrate the methods of the present disclosure rather than to impose limitations on the scope of the present disclosure. The wording in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the methods of the present disclosure.

[0162] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprises" or "including" and the like should be interpreted in an inclusive sense rather than an exclusive or exhaustive sense; that is, in the sense of "including but not limited to". Words using the singular or plural number also include the plural and singular, respectively. In addition, when used in this application, the words "herein," "above," and "below," and words of similar meaning shall refer to this application as a whole and not to any particular portion of this application.

[0163] As will be understood by those of ordinary skill in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of its specific specified elements, steps, ingredients, or components. As used herein, the transitional terms "comprising" or "including" are meant to include, but are not limited to, and allow for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of" does not include any unspecified elements, steps, ingredients, or components. 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 substantially affect the embodiment.

[0164] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0165] 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. Any numerical value, however, inherently contains various errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0166] The grouping of alternative elements or embodiments of the present disclosure should not be construed as limiting. Each group member may be mentioned and claimed individually or in any combination with other members of the group or other elements found herein. It is estimated that one or more members in the group may join the group or delete from the group for convenience and / or patentability reasons. When any such addition or deletion occurs, this specification is considered to contain the modified group, so the written description of all Markush groups used in the appended claims is met.

[0167] Some embodiments of various aspects of the present disclosure are described herein, including the best mode known to the inventors for implementing the methods described herein. Of course, the changes to these described embodiments will be apparent to those of ordinary skill in the art after reading the above description. The technician will utilize such changes as appropriate, so the method of the present disclosure can be implemented differently from the specific description herein. Therefore, the scope of the present disclosure includes all modifications and equivalents of the subject items listed in the claims attached hereto as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, the present disclosure covers any combination of the above-mentioned elements under all possible changes thereof.

[0168] As used herein, the phrase "at least a portion" is used to mean at least a desired fractional amount, up to a full possible amount.

[0169] Finally, it is to be understood that the various embodiments herein illustrate the method of the present disclosure. Other modifications that may be employed are within the scope of the present disclosure. Therefore, by way of example and not limitation, alternative configurations of the method may be utilized according to the teachings herein. Therefore, the method of the present disclosure is not limited to being exactly as shown and described.

Claims

1. A method for performing 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 H2; providing a second feed stream comprising H2 and at least a portion of the CO of the first product stream; The second feed stream is contacted with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reaction zone) to perform Fischer-Tropsch synthesis to provide a 5+ A second product stream of hydrocarbons.

2. The process 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. A process according to claim 1 or claim 2, wherein the first feed stream has a water concentration of no greater than 5 mol%, eg, no greater than 2 mol% or no greater than 1 mol%.

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

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

6. The process of any one of claims 1-5, wherein the first product stream has a hydrogen / carbon monoxide molar ratio 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. The method according to any one of claims 1 to 6, further comprising separating at least a portion of H2 from the first product stream, and using at least a portion of the H2 separated from the first product stream to activate the Fischer-Tropsch catalyst.

8. A process according to any one of claims 1 to 7, wherein at least 50% of the H2 of the first product stream is supplied to the second feed stream, for example at least 75%, or at least 90%, or at least 95%, or at least 99%.

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

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

11. The process 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 CO2, and including at least a portion of the pOX stream in the second feed stream.

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

13. The method according to any one of claims 1 to 12, further comprising: 5+ The hydrocarbon product stream is contacted with hydrogen and a hydrotreating catalyst to hydrotreat the C 5+ At least a portion of a hydrocarbon second product stream.

14. The process of claim 13, wherein at least a portion of the hydrogen used in the hydroprocessing is provided by the first product stream or the second product stream.

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

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