Fischer-Tropsch production of hydrocarbons from carbon dioxide via 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 H2 and CO2; contacting the first feed stream with a hydrogenation catalyst to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst to form a second product stream comprising CO and H2; providing a third feed stream comprising H2 and at least a portion of CO of the second product stream; the third feed stream is contacted with a Fischer-Tropsch catalyst to provide a third 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. 22190306.5 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 carbon dioxide. 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 its subsequent use in Fischer-Tropsch synthesis reactions. Summary of the invention

[0009] The present inventors have identified a method for efficiently converting CO2 to hydrocarbons via methanol (MeOH) and syngas intermediates. 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 H2 and CO2;

[0012] contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol;

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

[0014] contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H2;

[0015] providing a third feed stream comprising H2 and at least a portion of the CO of the second product stream;

[0016] The third feed stream is contacted with a Fischer-Tropsch catalyst to perform Fischer-Tropsch synthesis to provide a 5+ A third product stream of hydrocarbons.

[0017] 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

[0018] Figure 1-5 A schematic diagram of a process according to an exemplary embodiment of the present disclosure is provided. DETAILED DESCRIPTION

[0019] The present disclosure relates to the technology of preparing hydrocarbons from carbon dioxide. Carbon dioxide is a widely available gas (currently present in the atmosphere at about 400ppm), which is inert to many conversions. In addition, the tendency of carbon dioxide to absorb infrared radiation leads to its designation as a greenhouse gas. Therefore, it is necessary to develop economical methods for utilizing carbon dioxide, especially waste carbon dioxide that would otherwise increase the rising carbon dioxide concentration in the atmosphere. Carbon dioxide is produced by many industries, where it can be captured as a point source to be used as a raw material, such as from places involved in steel production, fossil fuel power generation, cement production, fermentation processes or fertilizer production. Carbon dioxide can also be derived from direct air capture projects. Advantageously, hydrocarbon synthesis methods using waste carbon dioxide as feedstock have the potential to be low-carbon, carbon neutral or even have a negative carbon footprint. One way to achieve this is to convert carbon dioxide and hydrogen into methanol. Methanol, which is a liquid at ambient temperature and pressure, can optionally be transported by low-pressure pipelines, ships or trucks, so as a liquid, it is generally possible to improve transportation efficiency. Methanol can then be subjected to a methanol decomposition step to generate H2 and CO in a 2:1 ratio. A mixture of H2 and CO is commonly referred to as "synthesis gas" and has a wide range of uses. At least CO of the methanol decomposition product can then be used in the Fischer-Tropsch synthesis reaction to produce hydrocarbons; H2 from methanol decomposition is also ideally used in 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 cases, the H2 and CO mixture from methanol decomposition can be supplemented by a hydrogen source (such as green hydrogen from a recycled feed stream or produced with renewable energy) to form a Fischer-Tropsch reaction mixture.

[0020] Accordingly, in one aspect, the present disclosure provides a method for performing integrated Fischer-Tropsch synthesis, the method comprising:

[0021] Providing a first feed stream comprising H2 and CO2;

[0022] contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol;

[0023] providing a second feed stream comprising at least a portion of the methanol of the first product stream;

[0024] contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H2;

[0025] providing a third feed stream comprising H2 and at least a portion of the CO of the second product stream;

[0026] The third feed stream is contacted with a Fischer-Tropsch catalyst to perform Fischer-Tropsch synthesis to provide a 5+A third product stream of hydrocarbons.

[0027] As used herein, "feed stream" is used to represent the total material input to a process step, such as CO2 hydrogenation, methanol decomposition, or Fischer-Tropsch reaction, whether provided as a single physical stream or multiple physical streams, and whether provided via a single inlet or multiple inlets. For example, the H2 and CO2 of the first feed stream can be provided to the hydrogenation reactor in a single physical stream (e.g., in a single conduit leading to the reactor) or in multiple physical streams (e.g., separate inlets for CO2 and H2, or one inlet for fresh CO2 and H2 and another inlet for recycled CO2 and / or H2). Similarly, "product stream" is used to represent the total material output from a process step, such as hydrogenation of carbon dioxide, methanol decomposition, or 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.

[0028] Advantageously, the integrated process as described herein can be substantially asymmetric in nature: while methanol can be synthesized from a carbon species that is primarily CO2, it can subsequently be decomposed into a stream having CO as the primary carbon species. This is in contrast to symmetric processes, in which the streams entering methanol synthesis and leaving methanol decomposition have similar carbon compositions. Since most of the reactions described herein are equilibrium processes, they are naturally suitable for symmetric integration. However, the inventors have discovered that asymmetric processes, such as the asymmetric processes disclosed herein, can enhance control over stream composition and improve process efficiency.

[0029] The first feed stream comprises H2 and CO2 for subsequent contact with a hydrogenation catalyst to produce methanol. Thus, in various embodiments as further described herein, the first feed stream comprises at least 10 mol % H2. For example, in various embodiments, the first feed stream comprises at least 20 mol % H2, such as at least 30 mol % H2. In various embodiments as further described herein, the first feed stream comprises at least 5 mol % CO2. For example, in various embodiments, the first feed stream comprises at least 10 mol % CO2, such as at least 15 mol % CO2.

[0030] In general, CO2 is hydrogenated to produce methanol according to the following reaction: CO2+3H2→CH3OH+H2O. Thus, in various embodiments as otherwise described herein, the ratio of H2:CO2 of the first feed stream is at least 1:1, e.g., at least 1.5:1, on a molar basis. For example, in various embodiments as otherwise described herein, the ratio of H2:CO2 of the first feed stream is at least 2:1, e.g., at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 8:1. In specific embodiments, the ratio of H2:CO2 of the first feed stream is no greater than 25:1, e.g., no greater than 20:1, or no greater than 15:1, or 12:1.

[0031] In some embodiments, the first feed stream comprises other gases in addition to CO2 and H2. For example, in various embodiments, the first feed stream further comprises one or more of CO, CH4 and N2. For example, in specific embodiments, the first feed stream comprises other gases (e.g., one or more of CO, CH4 and N2) in an amount of up to 70 mol%. In various embodiments, the first feed stream comprises no more than 1% O2, such as no more than 0.1% O2, or no more than 0.01% O2, or substantially free of O2. In various embodiments, the first feed stream comprises no more than 20 mol% CO, such as no more than 15 mol% CO, or no more than 10 mol% CO, or even no more than 5 mol% CO.

[0032] As described herein, the first feed stream is contacted with a hydrogenation catalyst. The hydrogenation catalyst can be selected by one of ordinary skill in the art. Examples of suitable catalysts include Cu / ZnO catalysts, such as Cu / ZnO catalysts supported on alumina or zirconium oxide.

[0033] Advantageously, the CO2 hydrogenation reaction can be carried out at relatively low temperatures to improve the energy efficiency and integration of the entire process. For example, in various embodiments as described herein, the contact of the first feed stream with the hydrogenation catalyst is carried out at a temperature in the range of 200-500°C, such as 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C. In various embodiments, the contact of the first feed stream with the hydrogenation catalyst is carried out at a pressure of not more than 100 bar, such as not more than 80 bar or not more than 60 bar.

[0034] As described herein, CO2 hydrogenation advantageously produces methanol with high selectivity. Therefore, in various embodiments as described in addition herein, CO2 hydrogenation is carried out with a selectivity of at least 50%, for example at least 55% or at least 60% to methanol. For example, in specific embodiments, CO2 hydrogenation is carried out with a selectivity of at least 65% (for example, at least 70%, or at least 75%, or at least 80%) to methanol. Advantageously, CO2 hydrogenation can be carried out with a low selectivity to methane. In various embodiments as described in addition herein, CO2 hydrogenation is carried out with a selectivity of not more than 20%, for example not more than 10% or not more than 5% to methane. As will be understood by those of ordinary skill in the art, "selectivity" to a given species is the fraction of the carbonaceous reactant of the reaction converted into the species, i.e., unreacted material is not counted.

[0035] Importantly, the CO2 hydrogenation reaction as described herein is not a reverse water gas shift reaction. As is known in the art, the reverse water gas shift reaction converts CO2 and H2 into CO and H2O. Thus, in various embodiments as otherwise described herein, the hydrogenation of CO2 is performed with a selectivity to CO of no more than 20%, e.g., no more than 10% or no more than 5% to CO. In specific embodiments, the hydrogenation of CO2 is performed with a selectivity to CO of no more than 2% or no more than 1% to CO.

[0036] During the CO2 hydrogenation reaction, at least a portion of the CO2 is hydrogenated to MeOH and H2O. Advantageously, the method can be performed with a relatively high CO2 conversion rate. Therefore, in various embodiments as further described herein, the hydrogenation of CO2 is performed with a CO2 conversion rate of at least 25%, such as at least 35%, such as at least 45% or at least 50%.

[0037] Those of ordinary skill in the art are familiar with catalytic methods for hydrogenating carbon dioxide to methanol. Various examples of catalysts and catalytic methods are described in R. Guil-López et al., Materials, 12, 3902 (2019); Xiao et al., In: Aresta et al. (eds.) An Economy Based on Carbon Dioxide and Water (2019); Marlin et al., Front. Chem. (2018); Rodriguez et al., ACS Cat. 5 (11), 6696 (2015); Choundhury, Chem. Cat. Chem. 4 (5), 609 (2012), each of which is incorporated herein by reference in its entirety.

[0038] CO2 hydrogenation produces a first product stream. In various embodiments as described in addition herein, the first product stream comprises at least 15 mol % methanol, such as at least 25 mol % or at least 35 mol % methanol. As described herein, CO2 hydrogenation also advantageously has low selectivity to other products such as methane and / or carbon monoxide. Therefore, in various embodiments as described in addition herein, the first product stream comprises no more than 10 mol % methane, such as no more than 5 mol % methane or no more than 2 mol % methane. In various embodiments as described in addition herein, the first product stream comprises no more than 10 mol % CO, such as no more than 5 mol % CO or no more than 2 mol % CO. Of course, in some embodiments, there may be more methane and / or CO, such as when provided as part of the first feed stream, such as as a recycle from a Fischer-Tropsch output. As will be appreciated by the skilled person, the composition of the first product stream as disclosed herein does not count inert gases or unreacted CO2 and / or H2.

[0039] As described herein, the CO2 hydrogenation step produces methanol and water. In some embodiments, the water formed 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 herein in addition, the method further includes separating at least a portion of water from the first product 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 product stream. In various embodiments as described herein in addition, the portion of the first product stream included in the second 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%.

[0040] In embodiments where water from the CO2 hydrogenation step 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 is subjected to a purification step prior to introduction into the electrolysis reactor.

[0041] In various embodiments as described in addition herein, not all H2 gases of the input CO2 hydrogenation react. Therefore, in such embodiments, the method may further include separating at least a portion of H2 from the first product stream. For example, in specific embodiments as described in addition herein, the method further includes separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 in the first product stream. The separated H2 can be optionally purified and then optionally recycled. In various embodiments, at least a portion of the separated H2 can be recycled to the first feed stream, and / or can be directed to another reactor. For example, in various embodiments, at least a portion of the separated H2 is directed to the Fischer-Tropsch reactor feed stream (for example, at least a portion of the H2 separated from the first product stream is supplied to the third feed stream). In specific embodiments, the method further includes activating the Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream. Additionally or alternatively, at least a portion of the H2 separated from the first product stream can be used to activate the methanol decomposition catalyst.

[0042] Advantageously, some processes described herein can be integrated to improve efficiency. For example, in various embodiments as described in addition herein, the contact of the second feed stream with the methanol decomposition catalyst and the contact of the first feed stream with the hydrogenation catalyst are carried out in the same manufacturing plant (plant). As those of ordinary skill in the art will recognize, "same manufacturing plant" means that the two processes are carried out in a small geographic area or real estate (property), so that the two will be economically directly connected without obvious intermediate transportation steps. For example, in a specific embodiment as described in addition herein, at least a portion of the methanol of the first product stream can be directly supplied to the second feed stream.

[0043] As described herein, there are many uses for hydrogen from the first product stream. Any or all of them can be utilized in a specific real-world process. It is noteworthy that the inventors recognize that the presence of the hydrogen in the second feed stream may be detrimental to the conversion of methanol into carbon monoxide (that is, because hydrogen is a co-product in the reaction, the presence of the hydrogen in the second feed stream will force the balance to the undesirable reverse direction). Therefore, in various embodiments, the part of the first product stream supplied to the second feed stream includes no more than 50% of the hydrogen of the first product stream, such as no more than 25%, no more than 10% or no more than 5% of the hydrogen of the first product stream.

[0044] The part of the first product stream supplied to the second feed stream can be advantageously at elevated temperature and / or pressure. This can reduce capital costs by alleviating the heating and / or pressurization requirements of the second feed stream. Therefore, in various embodiments as described herein in addition, the part of the first product stream supplied to the second feed stream has a temperature in the range of 200-500 ° C, such as 200-450 ° C, or 200-400 ° C, or 200-350 ° C, or 200-300 ° C, or 250-500 ° C, or 250-450 ° C, or 250-400 ° C, or 250-300 ° C, or 300-500 ° C, or 300-450 ° C, or 300-400 ° C. In a particular embodiment, the part of the first product stream supplied to the second feed stream is at a pressure of 0 to 50 barg, such as 1 to 50 barg.

[0045] Compared with gaseous compositions, compositions that are liquid at ambient temperature and pressure generally have lower operating capital expenditures due to their increased density and reduced demand for high pressure and / or low temperature. The inventors have noted that the methanol product of the CO2 hydrogenation can be simply stored and / or transported. Therefore, in various embodiments as described in addition herein, the contact of the second feed stream with the methanol decomposition catalyst and the contact of the first feed stream with the hydrogenation catalyst are carried out in different manufacturing plants. As used herein, different "manufacturing plants" are not just different catalyst beds or different containers, but places different from the places where carbon dioxide hydrogenation is carried out. In such embodiments, the manufacturing plant can be, for example, at least 1 km away from the place where hydrogenation is carried out. In various such embodiments, the methanol from the first product stream can be stored and / or transported before being supplied to the second feed stream.

[0046] In various embodiments as described in addition herein, at least a portion of the methanol of the first product stream is stored (e.g., in one or more tanks) before being supplied to the second feed stream. This storage can last any suitable time. In various embodiments, the storage portion of the methanol of the first product stream is stored for at least one day, e.g., at least two days, or at least three days, or at least 1 week. In a specific embodiment, the storage portion of methanol is transported at least 1 km during storage, e.g., at least 2 km or at least 10 km. In some embodiments, methanol can be transported via pipeline.

[0047] The second 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%).

[0048] 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).

[0049] As described herein, methanolysis is utilized to form a product stream comprising CO and H. Thus, in various embodiments as otherwise described herein, the second feed stream comprises at least 5 mol% methanol. For example, in specific embodiments, the second feed stream comprises at least 7.5% methanol, e.g., at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0050] Optionally, the second feed stream may also include one or more additional gases, which may be inert or reactive. In such an embodiment, the second feed stream may further include one or more of H2, CO, CH4, CO2 and N2. In a particular embodiment, the second 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 second feed stream to regulate the decomposition reaction and / or provide a desired second product stream for the Fischer-Tropsch process. In such an embodiment, the second 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 second feed stream in an amount of up to 50 mol %, for example, up to 40 mol % or up to 30 mol %.

[0051] In various embodiments, the second 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 second 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%.

[0052] The second feed stream can be provided at an elevated temperature. For example, in various embodiments as otherwise described herein, the second feed stream has a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0053] The second feed stream is contacted with a methanol decomposition catalyst. Any suitable decomposition catalyst may be used; a variety of which 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 in which 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.

[0054] 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.

[0055] The contact of the second 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 second feed stream with the methanol decomposition catalyst is carried out at a temperature in the range of 200-500°C, such as 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, such as at most 50 barg, such as in the range of 20 to 40 barg.

[0056] As described herein, the contacting of the second feed stream with the methanol decomposition catalyst can be carried out in the same manufacturing plant as the contacting of the first feed stream with the hydrogenation catalyst. In such an example, it may be advantageous to coordinate the temperatures of the methanol decomposition reaction and the hydrogenation reaction to avoid excessive heating and cooling capital costs and energy costs. Therefore, in a specific embodiment as otherwise described herein, the contacting of the second feed stream with the methanol decomposition catalyst is carried out at a temperature within 75°C, such as within 50°C, of ​​the contacting temperature of the first feed stream with the hydrogenation catalyst.

[0057] 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%.

[0058] As described herein, the decomposition of methanol generates CO and H2. Thus, in various embodiments as further described herein, the second 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 second 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 second feed stream.

[0059] In various embodiments, the second 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 second feed stream, such as unreacted CO2 from methanol synthesis).

[0060] Advantageously, a proportion of the methanol is consumed during the methanolysis reaction. Thus, in various embodiments as otherwise described herein, the second 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.

[0061] In some embodiments, it is necessary to further remove methanol from the second product stream. For example, in various embodiments as described in addition herein, the method further includes separating at least a portion of methanol from the second 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 second product stream. Advantageously, the methanol of the second product stream, for example, at least a portion of the methanol separated from the second product stream, can be transferred or recycled to other processes. For example, in various embodiments as described in addition herein, the method further includes recycling at least a portion of the methanol separated from the second product stream to the second feed stream.

[0062] 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 second feed stream to further increase the ratio in the second product stream. Therefore, in various embodiments as further described herein, the method further includes separating at least a portion of the H2 from the second product stream. The separated H2 may be suitable for various processes. For example, in a particular embodiment, at least a portion of the H2 separated from the second product stream is supplied to the first feed stream. 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 second product stream.

[0063] As described herein, the third feed stream comprises at least a portion of the CO of the second product stream. Thus, in various embodiments as further described herein, at least 50% of the CO of the second product stream is supplied to the third 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 second product stream is supplied to the third feed stream. In various embodiments, substantially all of the CO of the second product stream is supplied to the third feed stream. Additionally or alternatively, in various embodiments as further described herein, the CO of the third feed stream may be partially supplied by a CO source other than the second product stream.

[0064] As described above, the third feed stream comprises H2 and CO, and the second product stream comprises H2. In various embodiments as described herein in addition, at least a portion of the H2 of the second product stream is supplied to the third 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 second product stream is supplied to the third feed stream. In various embodiments, substantially all of the H2 of the second product stream is supplied to the third feed stream. Additionally or alternatively, in various embodiments as described herein in addition, the H2 of the third feed stream can be partially supplied by a hydrogen source other than the second product stream.

[0065] In various embodiments as otherwise described herein, the third 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 second product stream and carried to the third feed stream. However, in other embodiments, one or more other gases (e.g., one or more of CO2, CH4, N2) may be supplied to the third feed stream from a source other than the second product stream.

[0066] Advantageously, the portion of the second product stream included in the third feed stream can be adjusted according to the process needs of the third feed stream. For example, in various embodiments as otherwise described herein, the portion of the second product stream included in the third 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.

[0067] As further described herein, the third feed stream is contacted with a Fischer-Tropsch catalyst. Thus, in various embodiments as further described herein, the third feed stream has a H2:CO molar ratio suitable for Fischer-Tropsch synthesis. For example, in various embodiments, the third feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1, for example, in the range of 1:1 to 2.5:1. In a particular embodiment, the third feed stream has a H2:CO molar ratio of at least 1.2:1. For example, in various embodiments, the third feed stream 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.

[0068] The Fischer-Tropsch catalyst can be selected by one of ordinary skill in the art. In various embodiments as further 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 %, e.g., 5 to 25 wt %, or 8 to 20 wt %, calculated as Co(0). In various embodiments as further described herein, the Fischer-Tropsch catalyst further comprises manganese (e.g., comprising manganese in an amount of 0.1 to 15 wt % or 1 to 10 wt %).

[0069] 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.

[0070] 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 of 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 of H2). As described above, the H2 used for reduction may come from the first product stream or the second product stream. H2 may also be separated and recycled from the third product stream for use in reducing the Fischer-Tropsch catalyst.

[0071] 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 third feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20-40 barg.

[0072] 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.

[0073] Advantageously, in various embodiments as otherwise described herein, the contacting of the third feed stream with the Fischer-Tropsch catalyst and the contacting of the second 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 an embodiment, the two processes can be integrated to provide efficient conversion of methanol to hydrocarbons.

[0074] 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+ alcohols, aldehydes, ketones, carboxylic acids). 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 third feed stream is at least 30%, e.g., at least 50%, or at least 70% C 5+The third product stream may be selectively carried out. As known in the art, the hydrocarbon composition of the third 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.

[0075] In general, longer chain hydrocarbons are more desirable than shorter chain hydrocarbons. Therefore, in various embodiments as described herein, the third product stream comprises C1-C4 hydrocarbons, and the method further comprises separating at least a portion of C1-C4 hydrocarbons from the third 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 first feed stream and / or the third 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 first feed stream and / or the third feed stream as described herein.

[0076] 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 third feed stream. Additionally or alternatively, at least a portion of the light hydrocarbon stream may be included in the first feed stream and / or the second feed stream to be delivered to the third feed stream.

[0077] In various embodiments, the third product stream may contain unreacted H2. In various embodiments as described elsewhere herein, the method further includes separating at least a portion of the H2 of the third 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 third product stream is supplied to the first feed stream and / or the third feed stream. As mentioned above, at least a portion of the H2 separated from the third product stream can be used to activate the Fischer-Tropsch catalyst.

[0078] In various embodiments, the third product stream may contain unreacted CO. In various embodiments as otherwise described herein, the method further includes separating at least a portion of the CO of the third product stream. The separated CO can then be directed to a process that requires it. For example, in a particular embodiment, at least a portion of the CO separated from the third product stream is supplied to the third feed stream.

[0079] In various embodiments, the third product stream may include CO2. Thus, in various embodiments as otherwise described herein, the method further comprises separating at least a portion of CO2 from the third product stream. The separated CO2 can then be directed to a process requiring it. For example, in a particular embodiment, at least a portion of the CO2 separated from the third product stream is supplied to the first feed stream.

[0080] It may be desirable to provide C from a third 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+ , for example 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.

[0081] In addition, in some cases it may be desirable to 5+ The hydrocarbon product stream is further converted. Hydroprocessing, i.e., 5+ A hydrocarbon product stream contacted with hydrogen and a hydrotreating catalyst may be used for this purpose. Thus, in various embodiments, the process as otherwise described herein comprises contacting the 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 more of the first product stream, the second product stream, and the third product stream as described above.

[0082] 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 third 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).

[0083] 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 be used depending on the system.

[0084] The inventors have noted that carbon dioxide is the main input of carbon for the methods described herein, and carbon dioxide can be advantageously provided by a variety of sources. Importantly, at least a portion of the carbon dioxide (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the first feed stream can come from a renewable source.

[0085] Carbon dioxide is a common waste material, and it is usually desirable to remove it from waste streams rather than discharge it into the atmosphere. This capture of carbon dioxide is crucial for the implementation of many renewable measures because it helps to reduce the carbon footprint of related processes. Advantageously, the carbon dioxide utilized in the method described herein can be carbon dioxide collected from the atmosphere or carbon dioxide that would otherwise be released into the atmosphere, such as from combustion or other industrial processes. Carbon dioxide can be captured, wherein it is collected or absorbed after being released from an industrial process, or harvested directly from the atmosphere. Carbon dioxide capture methods are known to those skilled in the art. In various embodiments, at least a portion of the CO2 of the first feed stream comes from direct air capture. Additionally or alternatively, carbon dioxide is typically washed from industrial effluents, especially processes that generate a large amount of carbon dioxide as a by-product. Therefore, in various embodiments as described herein in addition, at least a portion of the CO2 of the first feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) is captured from a manufacturing plant, such as a bioethanol plant, a steel plant or a cement plant.

[0086] As mentioned above, renewable sources can be used to provide CO to the claimed method. For example, biomass is an attractive source of renewable carbon dioxide for the methods described herein. One source of biomass is agricultural products in the form of dedicated energy crops, such as switchgrass, miscanthus, bamboo, sorghum, tall fescue, Kochia scoparia, wheatgrass, poplar, willow, silver maple, eastern cottonwood, green ash, black walnut, sweetgum and sycamore. Another biomass source is agricultural waste or crop residues. Conventional agricultural activities, including the production of food, feed, fiber and forest products, generate a large amount of waste plant materials. Examples of such materials include corn stalks, wheat stalks, oat stalks, barley stalks, sorghum stubble and straw. The third biomass source is the forestry residues left after timber operations. Biomass can also be in the form of commercial waste, industrial waste, sewage sludge and municipal waste, including commercial and residential garbage, including yard trimming waste, paper and cardboard, plastics, rubber, leather, textiles and food waste. Therefore, in various embodiments as described herein, at least a portion of the CO2 of the first feed stream is derived from a renewable source. For example, in a specific embodiment, at least a portion of the CO2 of the first feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) is derived from biomass, such as agricultural biomass or municipal waste biomass. The other source of agricultural biomass is obvious to those skilled in the art, depending on local availability, economics and process compatibility.

[0087] In order to generate carbon dioxide from carbonaceous materials such as biomass, the material is usually gasified. Gasification involves heating the material under controlled conditions to generate a gas stream of carbon monoxide, hydrogen and carbon dioxide. Other reactants of controlled amounts can be used, such as oxygen and / or steam to regulate the process. Gasification conditions are adjusted according to the carbonaceous material of gasification to efficiently generate gaseous products. In various embodiments, the carbon dioxide of the first feed stream includes carbon dioxide from biomass gasification, such as at least 50%, at least 75%, at least 90% or at least 95% of the carbon dioxide from biomass gasification. Biomass can be any source as described above, or can be combined from a variety of sources.

[0088] 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 preferred from an environmental perspective are known. Therefore, in various embodiments as otherwise 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, the second feed stream, and / or the third feed stream is from renewable resources.

[0089] 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.

[0090] 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.

[0091] In order to qualify as green hydrogen, the electricity used for water electrolysis must come from a renewable source, that is, 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 first feed stream and / or the third 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 first feed stream and / or the third 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.

[0092] 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 third product stream.

[0093] 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 third 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.

[0094] 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 first feed stream and / or the third feed stream is blue hydrogen.

[0095] 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 first feed stream and / or the third feed stream is gray hydrogen.

[0096] 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 first feed stream and / or the third feed stream is black hydrogen and / or brown hydrogen.

[0097] 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 first feed stream and / or the third feed stream is powdered hydrogen. Powdered hydrogen is also known as purple hydrogen or red hydrogen.

[0098] Blue green hydrogen is generated 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 first feed stream and / or the third feed stream is blue green hydrogen.

[0099] 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 first feed stream and / or the third feed stream is white hydrogen.

[0100] 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 hydrogenation catalyst is arranged, the second reaction zone comprises a second reactor in which a methanol decomposition catalyst is arranged, and the third reaction zone comprises a third 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 hydrogenation catalyst is arranged, the second reaction zone comprises a second catalyst bed in which a methanol decomposition catalyst is arranged, and the third reaction zone comprises a third catalyst bed in which a Fischer-Tropsch catalyst is arranged. For example, in a specific embodiment, the first catalyst bed, the second catalyst bed, and the third catalyst bed are arranged in the same reactor, for example, in a catalyst stack or a catalyst bed section. In some embodiments, the second reactor bed and the third reactor bed are disposed in the same reactor, and the first catalyst bed is disposed in a different reactor from the second and third catalyst beds. For example, in a particular embodiment, the first reactor is located in a first manufacturing plant, and the second and third reactors are located in a second manufacturing plant.

[0101] As described herein, in some embodiments, various catalyst beds may be located in different reactors. Positioning the catalyst bed in a separate reactor 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 reactor 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, the second catalyst bed, and the third catalyst bed are not blended. When the 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, the second catalyst bed, and the third catalyst bed are arranged in separate reactors.

[0102] 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.

[0103] An exemplary embodiment is shown in a diagrammatic view. Figure 1 , which depicts a process 100 contained within a single manufacturing plant 141. A first feed stream 111 comprising H2 and CO2 is directed to a hydrogenation reaction zone 110 (here, a hydrogenation reactor) and is contacted with a hydrogenation catalyst 113 under conditions suitable for producing a first product stream 112 comprising methanol. The first product stream typically also contains other substances. For example, in Figure 1 In an embodiment of the present invention, the first product stream comprises CO2; at least a portion of the CO2 is separated from the first product stream and recycled to the first feed stream 111 via the CO2 recycle 114. Similarly, the first product stream may comprise H2 (e.g., unreacted H2) and / or CO (e.g., a recycle stream from a third product stream). Here, at least a portion of the H2 and / or CO is separated from the first product stream and recycled to the first feed stream 111 via the H2 and / or CO recycle stream 115. Figure 1 In the embodiment of the present invention, the H2 bypass 124 removes at least a portion of the H2 from the first product stream 112 and introduces it into the third feed stream 131 for use as a Fischer-Tropsch reactant. The H2 activation stream 134 removes at least a portion of the H2 from the first product stream 112 and introduces it into the third reaction zone to activate the Fischer-Tropsch catalyst 133 as needed. Figure 1 The embodiment of presents three different uses of hydrogen separated from the first product stream 112; one of ordinary skill in the art will recognize that many real-world processes do not include any, one, two, or all of these three. Any water present can be removed from the first product stream 112 by water separation stream 116 to provide a predominantly dry second feed stream (121), and optionally the water feed stream 116 can be fed to the electrolysis reactor 160.

[0104] exist Figure 1 In an embodiment of the present invention, the remainder of the first product stream 112 (i.e., after the above-described separation) is supplied to a second feed stream 121. The second feed stream 121 includes at least a portion of the methanol of the first product stream and is directed to a methanol decomposition reaction zone 120 (here, a methanol decomposition reactor) where it is contacted with a methanol decomposition catalyst 123 to decompose at least a portion of the methanol to form a second product stream 122 comprising CO and H2. The second feed stream 121 may also be supplemented by introducing other gases, such as CO and / or H2, via a supplemental feed (not shown). Figure 1In an embodiment, the second product stream 122 is directed from the second reaction zone 120 to a third feed stream 131. The third feed stream 131 comprises H2 (e.g., from the second product stream) and at least a portion of CO of the second product stream. The third 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 third feed stream 131 may also be supplemented by introducing other gases, such as CO and / or H2, via a supplemental feed (not shown). The third feed stream 131 is contacted with the Fischer-Tropsch catalyst 133 to provide a feed stream comprising C 5+ A third product stream 132 of hydrocarbons. Figure 1 In an embodiment, a third product stream 132 is directed from the third reaction zone 130. Here, a light hydrocarbon stream 136 is separated from the third product stream 132 and directed to a generator 170. Additionally or alternatively, a light hydrocarbon stream 137, optionally containing gaseous products, is separated from the third product stream 132 and recycled back to the third feed stream 131. Examples of gaseous products for recycling include CO, H2, CH4, CO2, C2H4, C3H6, C3H8, C3H7OH, and H2O. The CO2 recycle stream 138 can be used to recycle CO2 from the third product stream 132 to the first feed stream 111. The 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 third 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 first product stream and / or the third product stream) to provide hydrogen. The H2 gas from the electrolysis reactor 160 is sent back to the first feed stream via the electrolysis H2 stream 117.

[0105] As described above, methanol can be formed in a first manufacturing plant by hydrogenation of carbon dioxide 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. An example of such an embodiment is shown in a schematic view at Figure 2Here, the carbon dioxide hydrogenation step of method 200 is carried out in a first manufacturing plant 241. A first feed stream 211 comprising carbon dioxide and hydrogen is directed to a hydrogenation reaction zone 210 (here, a hydrogenation reactor) containing a CO2 hydrogenation catalyst 213. The first feed stream 211 is contacted with the CO2 hydrogenation catalyst 213 to hydrogenate at least a portion of the CO2 to generate a first product stream 212 comprising methanol. The first product stream 212 may be subjected to various separations as described herein (not shown), and the methanol of the first product stream may then be stored for later use, and / or transported to another manufacturing plant. For example, in Figure 2 In the embodiment of the present invention, at least a portion of the first product stream 212 (the portion containing methanol) is loaded into a storage tank 217 and then transported to a second manufacturing plant 243 by a truck 218. This portion of the first product stream is supplied to a second feed stream 221, and the second 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 second product stream 222 containing CO and H2. Here, at least a portion of the second product stream 222 is supplied to a third feed stream 231. The third 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 second product stream 222 containing CO and H2. 5+ A third product stream 232 of hydrocarbons.

[0106] Another exemplary embodiment is shown in a diagrammatic view. Figure 3Here, in the method 300, a first feed stream 311 is directed to a first reaction zone 310 and contacted with a CO2 hydrogenation catalyst 313 to hydrogenate at least a portion of the CO2 of the first feed stream to form a first product stream 312 comprising methanol. The first product stream 312 is withdrawn from the first reaction zone 310 and added to an additional gas stream 324, and the resulting mixture is provided as a second feed stream 321. The second feed stream 321 is directed to a methanol decomposition reaction zone 320, where a second product stream 322 is provided with a methanol decomposition catalyst 323. Here, the second 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 second product stream and recycled to the second feed stream 321 via a methanol recycle 325. It is noteworthy that at least a portion of the H2 of the second product stream 322 can be separated and recycled to the first feed stream 311 via the H2 recycle 326. At least a portion of the H2 of the second product stream 322 can also or alternatively be supplied to the third reaction zone 330 to activate the Fischer-Tropsch catalyst 333 via the H2 stream 327. The remainder of the second product stream 322 is provided as a portion of the third feed stream 331, and the third feed stream 331 is introduced into the Fischer-Tropsch reaction zone 330. A portion of the third feed stream 331 also has an additional gas stream 335, which provides additional H2 and / or CO to the Fischer-Tropsch reaction zone via a separate inlet. The third feed stream is contacted with the Fischer-Tropsch catalyst 333 in the Fischer-Tropsch reaction zone to provide a catalyst comprising C 5+ A third product stream 332 of hydrocarbons. The third 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 third feed stream 331 via the CO stream 351. At least a portion of the CO2 generated by the partial oxidation unit 350 is included in the first feed stream 311 via the CO2 stream 352.

[0107] 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 4In the method 400, CO2 hydrogenation is carried out in one reactor, and methanol decomposition and Fischer-Tropsch synthesis are carried out in another reaction. A first feed stream 411 comprising CO2 and H2 is directed to a first reaction zone 410 (here a hydrogenation reactor) and contacted with a hydrogenation catalyst 413 to provide a first product stream comprising methanol. The first product stream 412 is supplied as a second feed stream 421 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 second feed stream 421 is contacted with a methanol decomposition catalyst 423 to provide a second product stream 422 comprising CO and H2. The second product stream is supplied as a third feed stream 431 to the Fischer-Tropsch reaction zone, which is contacted with a Fischer-Tropsch catalyst 433 to provide a second product stream 422 comprising CO and H2. 5+ A third product stream 432 of hydrocarbons. Here, at least a portion of the third product stream C 5+ The hydrocarbons are directed to a hydroprocessing unit 460 where they are hydroprocessed to provide a final product stream 465. Here, at least a portion of the H2 of the first product stream is separated and directed to the hydroprocessing unit 460 via stream 462. H2 may also be supplied to the hydroprocessing unit in a portion of the third product stream directed to the hydroprocessing unit.

[0108] In some embodiments, the conversion of CO2 to hydrocarbons via a methanol intermediate can be carried out in a single reactor with various catalysts arranged, for example, in series. Figure 5 In an embodiment of the present invention, the process 500 utilizes a synthesis gas source stream 512, which enters the reactor 525 as a first feed stream 521 at a zone 520. The first feed stream 521 is contacted with a hydrogenation catalyst 513, and then directly passed to a methanol decomposition catalyst 523, and finally to a Fischer-Tropsch catalyst 533. The resulting gas mixture is discharged from the zone 530 as a third product stream 532. The recycle stream 513 removes CO2 gas, optionally mixed with light hydrocarbons and other gases, and is recycled to the CO2 source stream 512.

[0109] 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.

[0110] Embodiment 1. A method for performing integrated Fischer-Tropsch synthesis, the method comprising:

[0111] Providing a first feed stream comprising H2 and CO2;

[0112] contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol;

[0113] providing a second feed stream comprising at least a portion of the methanol of the first product stream;

[0114] contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H2;

[0115] providing a third feed stream comprising H2 and at least a portion of the CO of the second product stream;

[0116] The third 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 third product stream of hydrocarbons.

[0117] Embodiment 2. A process according to Embodiment 1, wherein the first feed stream comprises at least 10 mol % H2, e.g., at least 20 mol % H2, or at least 30 mol % H2.

[0118] Embodiment 3. A process according to Embodiment 1 or Embodiment 2, wherein the first feed stream comprises at least 5 mol % CO 2 , eg, at least 10 mol % CO 2 , or at least 15 mol % CO 2 .

[0119] Embodiment 4. A method according to any of Embodiments 1-3, wherein the ratio of H2:CO2 of the first feed stream is at least 1:1, for example at least 1.5:1, at least 2:1, at least 2.5:1, at least 3:1, or at least 4:1.

[0120] Embodiment 5. A method according to any of Embodiments 1-4, wherein the first feed stream further comprises one or more of CO, CH4 and N2.

[0121] Embodiment 6. A process according to any of Embodiments 1-5, wherein the first feed stream comprises no greater than 20 mol % CO, e.g., no greater than 15 mol % CO, or no greater than 10 mol % CO, or no greater than 5 mol % CO.

[0122] Embodiment 7. The method according to any of Embodiments 1-6, wherein the hydrogenation catalyst is a copper / zinc oxide catalyst, for example supported on alumina or zirconia.

[0123] Embodiment 8. A method according to any of Embodiments 1-7, wherein contacting of the first feed stream with the hydrogenation catalyst is carried out at a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0124] Embodiment 9. A process according to any one of Embodiments 1-8, wherein the hydrogenation of CO2 is carried out with a selectivity to methanol of at least 50%, eg, at least 65% or at least 80%.

[0125] Embodiment 10. The process according to any of Embodiments 1-9, wherein the hydrogenation of CO2 is carried out with a selectivity to methane of not more than 20%, eg, not more than 10% or not more than 5%.

[0126] Embodiment 11. A process according to any of Embodiments 1-10, wherein the hydrogenation of CO2 is carried out with a selectivity to CO of not more than 20%, eg, not more than 10% or not more than 5%.

[0127] Embodiment 12. A method according to any of Embodiments 1-11, wherein the hydrogenation of CO2 is carried out at a CO2 conversion of at least 25%, such as at least 35%, such as at least 45% or at least 50%.

[0128] Embodiment 13. The process of any of Embodiments 1-12, wherein the first product stream comprises at least 15 mol% methanol, eg, at least 25 mol% or at least 35 mol% methanol.

[0129] Embodiment 14. The method of any of Embodiments 1-13, wherein the first product stream comprises no greater than 10 mol% methane, eg, no greater than 5 mol% methane or no greater than 2 mol% methane.

[0130] Embodiment 15. The method of any of Embodiments 1-14, wherein the first product stream comprises no greater than 10 mol % CO, eg, no greater than 5 mol % CO or no greater than 2 mol % CO.

[0131] Embodiment 16. The method of any of Embodiments 1-15, further comprising separating at least a portion of the water from the first product stream (e.g., at least 50%, at least 75%, or at least 90% of the water in the first product stream).

[0132] Embodiment 17. The method of any of Embodiments 1-16, wherein the portion of the first product stream included in the second feed stream has a water content of no greater than 10 mol %, eg, no greater than 2 mol % or no greater than 0.5 mol %.

[0133] Embodiment 18. A method according to any of Embodiments 1-17, further comprising separating at least a portion of the H2 from the first product stream (e.g., at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 in the first product stream).

[0134] Embodiment 19. The method of Embodiment 18, further comprising recycling at least a portion of the H2 separated from the first product stream to the first feed stream.

[0135] Embodiment 20. The method of Embodiment 18 or Embodiment 19, further comprising supplying at least a portion of the H2 separated from the first product stream to a third feed stream.

[0136] Embodiment 21. The method of any of Embodiments 18-20, further comprising activating the Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream.

[0137] Embodiment 22. The method of any of Embodiments 18-21, further comprising activating the methanol decomposition catalyst using at least a portion of the H2 separated from the first product stream.

[0138] Embodiment 23. The method of any of Embodiments 1-22, wherein the portion of the first product stream supplied to the second feed stream comprises no more than 50% of the hydrogen of the first product stream, e.g., no more than 25%, no more than 10%, or no more than 5% of the hydrogen of the first product stream.

[0139] Embodiment 24. The method of any of Embodiments 1-23, wherein the contacting of the second feed stream with the methanol decomposition catalyst and the contacting of the first feed stream with the hydrogenation catalyst are performed in the same manufacturing plant.

[0140] Embodiment 25. The method of any of Embodiments 1-24, wherein at least a portion of the methanol of the first product stream is supplied directly to the second feed stream.

[0141] Embodiment 26. A process according to Embodiment 25, wherein the portion of the first product stream supplied to the second feed stream has a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0142] Embodiment 27. The method according to any of Embodiments 1-26, wherein the contacting of the second feed stream with the methanol decomposition catalyst and the contacting of the first feed stream with the hydrogenation catalyst are performed in different manufacturing plants.

[0143] Embodiment 28. The method of any of Embodiments 1-27, wherein at least a portion of the methanol of the first product stream is stored (eg, in one or more tanks) prior to being supplied to the second feed stream.

[0144] Embodiment 29. The method according to Embodiment 28, wherein the stored portion of the methanol of the first product stream is stored for at least one day, such as at least two days or at least 1 week.

[0145] Embodiment 30. The method according to embodiment 28 or embodiment 29, wherein the stored portion of methanol is transported at least 1 km, such as at least 2 km or at least 10 km during storage.

[0146] Embodiment 31. A method according to any of Embodiments 1-30, wherein the second feed stream comprises at least 5 mol% methanol, for example 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.

[0147] Embodiment 32. A method according to any of Embodiments 1-31, wherein the second feed stream further comprises one or more of H2, CO, CH4, CO2 and N2.

[0148] Embodiment 33. The method of any of Embodiments 1-32, wherein the second feed stream has a water concentration of no greater than 5 mol%, eg, no greater than 2 mol% or no greater than 1 mol%.

[0149] Embodiment 34. A method according to any of Embodiments 1-33, wherein the second feed stream has 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.

[0150] Embodiment 35. The method of any of Embodiments 1-34, wherein the methanol decomposition catalyst is a copper / zinc oxide catalyst, such as on alumina.

[0151] Embodiment 36. A method according to any of Embodiments 1-35, wherein contacting the second 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.

[0152] Embodiment 37. A process according to any of Embodiments 1-36, wherein contacting the second feed stream with the methanol decomposition catalyst is carried out at a temperature within 75°C, eg, within 50°C, of ​​the contacting temperature of the first feed stream with the hydrogenation catalyst.

[0153] Embodiment 38. A method according to any of Embodiments 1-37, wherein the decomposition of methanol is carried out with a carbon product selectivity to CO of at least 50%, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0154] Embodiment 39. A method according to any of Embodiments 1-38, 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%.

[0155] Embodiment 40. A method according to any of Embodiments 1-39, 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%.

[0156] Embodiment 41. A method according to any of Embodiments 1-40, wherein the second 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%.

[0157] Embodiment 42. A method according to any of Embodiments 1-41, wherein the second 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.

[0158] Embodiment 43. The method of any of Embodiments 1-42, wherein the second 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.

[0159] Embodiment 44. A method according to any of Embodiments 1-43, wherein the second product stream comprises no greater than 75 mol% methanol, eg, no greater than 60 mol% methanol, or no greater than 50 mol% methanol, or no greater than 25 mol% methanol.

[0160] Embodiment 45. The method of any of Embodiments 1-44, further comprising separating at least a portion of the methanol from the second product stream (e.g., at least 50%, at least 75%, or at least 90% of the methanol in the second product stream).

[0161] Embodiment 46. The method of Embodiment 45, further comprising recycling at least a portion of the methanol separated from the second product stream, for example at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream, to the second feed stream.

[0162] Embodiment 47. The method of any of Embodiments 1-46, further comprising separating at least a portion of the H2 from the second product stream.

[0163] Embodiment 48. The method of Embodiment 47, further comprising supplying H2 separated from the second product stream to the first feed stream.

[0164] Embodiment 49. The method of any of Embodiments 47 and 48, further comprising activating the Fischer-Tropsch catalyst using at least a portion of the H2 separated from the second product stream.

[0165] Embodiment 50. The method of any of Embodiments 1-49, wherein at least 50% of the CO of the second product stream is supplied to the third feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0166] Embodiment 51. The method of any of Embodiments 1-50, wherein at least a portion of the H2 of the second product stream is supplied to the third feed stream.

[0167] Embodiment 52. The method of any of Embodiments 1-51, wherein at least 50% of the H2 of the second product stream is supplied to the third feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0168] Embodiment 53. The method of any of Embodiments 1-52, wherein H2 is supplied to the third feed stream from a hydrogen source other than the second product stream.

[0169] Embodiment 54. The method of any of Embodiments 1-53, wherein CO is supplied to the third feed stream from a CO source other than the second product stream.

[0170] Embodiment 55. The method of any of Embodiments 1-54, wherein one or more of CO2, CH4, and N2 is supplied to the third feed stream from a source other than the second product stream.

[0171] Embodiment 56. The method of any of Embodiments 1-55, wherein the portion of the second product stream included in the third feed stream has an H2:CO ratio in the range of 0.5:1 to 5:1, for example, in the range of 1:1 to 2.5:1.

[0172] Embodiment 57. The method of any of Embodiments 1-56, wherein the third feed stream has a H2:CO molar ratio in the range of 0.5:1 to 5:1.

[0173] Embodiment 58. The method of any of Embodiments 1-57, wherein the third feed stream has a H2:CO molar ratio in the range of 1:1 to 2.5:1.

[0174] Embodiment 59. The method of any of Embodiments 1-58, wherein the third 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.

[0175] Embodiment 60. The method of any one of Embodiments 1-59, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0176] Embodiment 61. The method of any of Embodiments 1-60, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 5-25 wt. %, calculated as Co(0).

[0177] Embodiment 62. The method of any of Embodiments 1-61, wherein the Fischer-Tropsch catalyst comprises iron in an amount in the range of 25-95 wt. % calculated as Fe(0).

[0178] Embodiment 63. The method of any one of Embodiments 60-62, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0179] Embodiment 64. The method of any one of Embodiments 1-63, 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.

[0180] Embodiment 65. The method of any of Embodiments 1-64, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0181] Embodiment 66. The method of any of Embodiments 1-65, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titania support.

[0182] Embodiment 67. The method of any one of Embodiments 1-66, wherein the Fischer-Tropsch catalyst is activated in a reducing atmosphere.

[0183] Embodiment 68. The method of Embodiment 67, wherein the reducing atmosphere comprises at least a portion of the hydrogen from the second product stream and / or at least a portion of the hydrogen from the first product stream.

[0184] Embodiment 69. The method of any one of Embodiments 1-68, wherein contact of the third 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).

[0185] Embodiment 70. The method of any of Embodiments 1-69, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is carried out at a temperature in the range of 200-350°C.

[0186] Embodiment 71. The method of any one of Embodiments 1-70, wherein contact of the third 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).

[0187] Embodiment 72. The method of any of Embodiments 1-71, wherein contacting the third feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20-40 barg.

[0188] Embodiment 73. The method of any of Embodiments 1-72, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst and the contacting of the second feed stream with the methanol decomposition catalyst are performed in the same manufacturing plant.

[0189] Embodiment 74. The method of any one of Embodiments 1-73, wherein the contacting of the Fischer-Tropsch catalyst with the third feed stream is at least 30%, such as at least 50% or at least 70% C 5+ Selectively.

[0190] Embodiment 75. The method of any one of Embodiments 1-74, wherein C of the third product stream 5+ Hydrocarbons contain C 5+ Oxygen-containing compounds.

[0191] Embodiment 76. The method of any of Embodiments 1-75, further comprising separating at least a portion of the C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream.

[0192] Embodiment 77. The method of Embodiment 76, further comprising oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream or the third feed stream.

[0193] Embodiment 78. The method of Embodiment 76 or Embodiment 77, further comprising including at least a portion of the light hydrocarbon stream in a third feed stream.

[0194] Embodiment 79. The method of any of Embodiments 1-78, further comprising separating at least a portion of the H2 of the third product stream.

[0195] Embodiment 80. The method of Embodiment 79, wherein at least a portion of the H2 separated from the third product stream is supplied to the first feed stream and / or the third feed stream.

[0196] Embodiment 81. The method of Embodiment 79 or Embodiment 80, wherein at least a portion of the H2 separated from the third product stream is used to activate the Fischer-Tropsch catalyst.

[0197] Embodiment 82. The method of any of Embodiments 1-81, further comprising separating at least a portion of the CO of the third product stream.

[0198] Embodiment 83. The method of Embodiment 82, wherein at least a portion of the CO separated from the third product stream is supplied to the third feed stream.

[0199] Embodiment 84. The method of any of Embodiments 1-83, further comprising separating at least a portion of the CO2 of the third product stream.

[0200] Embodiment 85. The method of Embodiment 84, wherein at least a portion of the CO 2 separated from the third product stream is supplied to the first feed stream.

[0201] Embodiment 86. The method of any of Embodiments 1-85, further comprising providing a third product stream comprising at least 80 wt% C 5+ Hydrocarbons, such as at least 90 wt.% C 5+ C 5+ A hydrocarbon product stream.

[0202] Embodiment 87. The method of any one of Embodiments 1-86, 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 third product stream.

[0203] Embodiment 88. The method of Embodiment 87, wherein at least a portion of the hydrogen used in the hydrotreating is provided by any one of the first product stream, the second product stream, and the third product stream.

[0204] Embodiment 89. The method of any one of Embodiments 1-88, wherein at least a portion of the third product stream C 5+ The hydrocarbons provide one or more products that are one or more of fuels, waxes, or oils.

[0205] Embodiment 90. The method of any of Embodiments 1-89, wherein at least a portion of the CO2 of the first feed stream comes from a renewable source.

[0206] Embodiment 91. The method of any of Embodiments 1-90, wherein at least a portion of the CO2 of the first feed stream comes from direct air capture.

[0207] Embodiment 92. The method of any of Embodiments 1-91, wherein at least a portion of the CO2 of the first feed stream is captured from a manufacturing plant, such as a bioethanol plant, a steel plant, or a cement plant.

[0208] Embodiment 93. The method of any of Embodiments 1-92, wherein at least a portion of the H2 of the first feed stream and / or the third feed stream is from a renewable source.

[0209] Embodiment 94. The method of any of Embodiments 1-93, wherein at least a portion of the hydrogen of the first feed stream and / or the third feed stream is green hydrogen.

[0210] Embodiment 95. The method of any of Embodiments 1-94, wherein at least a portion of the hydrogen in the first feed stream and / or the third feed stream is blue hydrogen.

[0211] Embodiment 96. The method of any one of Embodiments 1-95, wherein at least a portion of the hydrogen of the first feed stream and / or the third feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, blue-green hydrogen, yellow hydrogen and / or white hydrogen.

[0212] Embodiment 97. The method of any of Embodiments 1-96, further comprising providing at least a portion of the H2 to the first feed stream and / or the third feed stream by electrolysis of water.

[0213] Embodiment 98. The method of Embodiment 97, wherein the electrolysis of water is performed using electricity derived at least in part from a renewable source.

[0214] Embodiment 99. The method of Embodiment 97 or Embodiment 98, 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 a third product stream.

[0215] Embodiment 100. The method of any one of Embodiments 97-99, further comprising the steps of Embodiment 77, wherein at least a portion of the O2 generated by water electrolysis is supplied to a partial oxidation reactor.

[0216] Embodiment 101. The method of any of Embodiments 1-100, wherein the first reaction zone comprises a first reactor in which a hydrogenation catalyst is disposed, the second reaction zone comprises a second reactor in which a methanol decomposition catalyst is disposed, and wherein the third reaction zone comprises a third reactor in which a Fischer-Tropsch catalyst is disposed.

[0217] Embodiment 102. The method of any of Embodiments 1-101, wherein the first reaction zone comprises a first catalyst bed in which a hydrogenation catalyst is disposed, the second reaction zone comprises a second catalyst bed in which a methanol decomposition catalyst is disposed, and the third reaction zone comprises a third catalyst bed in which a Fischer-Tropsch catalyst is disposed.

[0218] Embodiment 103. The method of Embodiment 102, wherein the first catalyst bed, the second catalyst bed, and the third catalyst bed are arranged in a catalyst stack or bed section in the same reactor.

[0219] Embodiment 104. The method of Embodiment 103, wherein the second catalyst bed and the third catalyst bed are disposed in the same reactor and the first catalyst bed is disposed in a different reactor than the second and third catalyst beds.

[0220] Embodiment 105. The method of any of Embodiments 102-104, wherein the first catalyst bed, the second catalyst bed, and the third catalyst bed are not intermixed.

[0221] Embodiment 106. The method of Embodiment 102, wherein the first catalyst bed, the second catalyst bed, and the third catalyst bed are disposed in separate reactors.

[0222] Embodiment 107. The method of any one of Embodiments 1-106, wherein the methanol decomposition catalyst and the Fischer-Tropsch synthesis catalyst have the same composition (eg, are the same catalyst).

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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 H2 and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reaction zone) to decompose at least a portion of the methanol to form a second product stream comprising CO and H2; providing a third feed stream comprising H2 and at least a portion of the CO of the second product stream; The third 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 third product stream of hydrocarbons.

2. The process of claim 1, wherein the first product stream comprises at least 15 mol% methanol, such as at least 25 mol% or at least 35 mol% methanol.

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

4. The process of any one of claims 1 to 3, wherein the portion of the first product stream included in the second feed stream has a water content of not greater than 10 mol %, such as not greater than 2 mol % or not greater than 0.5 mol %.

5. The process of any one of claims 1 to 4, wherein the second feed stream comprises at least 5 mol% methanol, e.g., at least 7.5% methanol, or at least 10 mol% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

6. The process of any one of claims 1 to 5, wherein the second feed stream has a water concentration of no greater than 5 mol%, such as no greater than 2 mol% or no greater than 1 mol%.

7. A process according to any one of claims 1 to 6, wherein contacting the second feed stream with the methanol decomposition catalyst is carried out at a temperature within 75°C, such as within 50°C, of ​​the contacting temperature of the first feed stream with the hydrogenation catalyst.

8. The method according to any one of claims 1 to 7, further comprising separating at least a portion of the methanol from the second product stream (e.g., at least 50%, at least 75%, or at least 90% of the methanol in the second product stream), and recycling at least a portion of the methanol separated from the second product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream, to the second feed stream.

9. The method according to any one of claims 1 to 8, further comprising separating at least a portion of H2 from the second product stream, and supplying the H2 separated from the second product stream to the first feed stream.

10. A process according to any one of claims 1 to 9, wherein the portion of the second product stream included in the third 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, such as in the range of 1.5:1 to 3.5:

1.

11. The process of any one of claims 1 to 10, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst and the contacting of the second feed stream with the methanol decomposition catalyst are carried out in the same manufacturing plant.

12. The process according to any one of claims 1 to 11, further comprising separating at least a portion of the C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream, and oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the first feed stream or the third feed stream.

13. The process of claim 12, further comprising including at least a portion of the light hydrocarbon stream in a third feed stream.

14. The process according to any one of claims 1 to 13, further comprising separating at least a portion of H2 from the third product stream, wherein at least a portion of the H2 separated from the third product stream is supplied to the first feed stream and / or the third feed stream.

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

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