Hydrogen production using methanol

Abstract

The present disclosure relates generally to methods of producing hydrogen. In particular, the present disclosure relates to a 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; storing at least a portion of the methanol of the first product stream; providing a second feed stream comprising at least a portion of the stored methanol; dehydrogenating at least a portion of the methanol of the second feed stream in a methanol dehydrogenation reaction zone to form a second product stream comprising H2 and CO2; providing a third feed stream comprising at least a portion of the H2 of the second product stream; reacting the hydrogen of the third feed stream with one or more co-reactants in a hydrogen reaction zone to provide a third product stream, the third product stream comprising one or more products, the products including reacted hydrogen atoms from the hydrogen of the third feed stream.

Description

Technical Field

[0001] This disclosure relates to an integrated method for producing hydrogen using methanol intermediates. Technical Background

[0002] Molecular hydrogen is a highly relevant compound, serving both as an energy source and a key feedstock in various industrial processes, such as Fischer-Tropsch synthesis and the Haber-Bosch process. The growing importance of renewable energy has led to renewed interest in hydrogen. As a fuel, hydrogen is highly desirable because it can react with oxygen, for example in hydrogen fuel cells, to provide energy, forming water as the only byproduct. Hydrogen can be produced by electrolyzing water using energy from renewable resources such as solar or wind power. Therefore, hydrogen represents a fuel / reagent that can be considered environmentally friendly in both its production and consumption.

[0003] Many industrial processes that rely on hydrogen operate essentially continuously. Energy from renewable resources, such as solar and wind power, can be intermittent, and therefore, hydrogen produced using energy from renewable resources may be too unreliable to fully meet the needs of such industrial processes.

[0004] While hydrogen can be stored for use during intermittent periods of renewable hydrogen production, this also has significant drawbacks. Compared to other fuels such as liquid hydrocarbons, hydrogen suffers from poor handling properties. H2 molecules are small and therefore can leak through a variety of dense materials, potentially causing problems such as hydrogen embrittlement, where the ductility of metals is reduced due to the absorption of hydrogen. Furthermore, as a gas, H2 is difficult to transport because it must be transported in a low-density gaseous phase or liquefied under high pressure.

[0005] Therefore, there is a need to develop improved solutions for hydrogen production and processing. Summary of the Invention

[0006] The inventors have determined methods for the efficient storage and transport of hydrogen via the intermediate role of methanol (MeOH). Advantageously, the intermediate role of methanol allows hydrogen produced using renewable energy sources to be transported and stored in the form of liquid methanol. Furthermore, these methods advantageously allow methanol to be converted back into hydrogen through various methods, such as methanol cracking or methanol electrolysis.

[0007] Therefore, in one aspect, this disclosure provides a method for producing hydrogen, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Provide a second feed stream that includes at least a portion of the methanol from the first product stream; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream containing H2 and CO2, wherein the dehydrogenation has a carbon product selectivity of at least 40% for CO2.

[0008] In another aspect, this disclosure provides a method for performing integrated hydrogenation, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Provide a second feed stream that includes at least a portion of the methanol from the first product stream; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream comprising H2 and CO2, wherein the dehydrogenation has a carbon product selectivity of at least 40% for CO2; Provide a third feed stream that includes at least a portion of H2 of the second product stream; In the hydrogen reaction zone, hydrogen from the third feed stream is reacted with one or more co-reactants to provide a third product stream comprising one or more products, the products including reacted hydrogen atoms from the hydrogen in the third feed stream.

[0009] Other aspects of this disclosure will be apparent to those skilled in the art from the following description.

[0010] Brief description of the attached figures Figure 1-4 A schematic diagram of a method according to an exemplary embodiment of the present disclosure is provided.

[0011] Detailed description This disclosure generally relates to technologies for using methanol as an intermediate for hydrogen, and particularly for its transportation and storage. Energy derived from renewable resources is often plagued by intermittent availability. For example, solar energy can only produce usable energy during the day, while wind energy is only effective during windy periods. Therefore, hydrogen streams produced using such energy sources can also be intermittent.

[0012] However, many industrial processes require largely continuous operation for high efficiency (both from a process and cost perspective), and frequent process interruptions can lead to increased energy consumption, decreased product output and / or quality, and / or increased wear and tear on process machinery, potentially resulting in reduced utilization and shortened lifespan of capital equipment. Furthermore, effective large-scale energy storage methods are often prohibitively expensive or inefficient. And the transportation and storage of hydrogen itself presents numerous complex challenges.

[0013] Advantageously, the inventors have recognized that methanol can serve as a storage and transport carrier for hydrogen because it can be readily transported and stored in liquid form. Therefore, stored methanol can act as a buffer against intermittent hydrogen production and can help manage energy-related intermittency, such as the intermittency of hydrogen produced through electrolysis powered by renewable energy sources.

[0014] Carbon dioxide is a widely available gas (currently present in the atmosphere at approximately 400 ppm) and is inert to many conversions. Furthermore, its tendency to absorb infrared radiation has led to its designation as a greenhouse gas. Therefore, there is a need to develop economical methods for utilizing carbon dioxide, especially waste carbon dioxide, which otherwise contributes to increasing atmospheric carbon dioxide concentrations. Carbon dioxide is produced by many industries, where it can be captured as a point source for use as a feedstock, for example, from facilities involved in steel production, fossil fuel power generation, cement production, fermentation processes, or fertilizer production. Carbon dioxide can also originate from direct air capture projects. One productive way to utilize captured carbon dioxide is to convert it and hydrogen into methanol. Methanol is liquid at ambient temperature and pressure and can optionally be transported via low-pressure pipelines, ships, or trucks, thus generally allowing for efficient transport as a liquid. Methanol is then combined with water and a dehydrogenation step can be performed to regenerate H2 along with CO2.

[0015] Hydrogen has a wide range of uses as a fuel and chemical feedstock. Methods for separating H2 from other gases (e.g., CO2) for use in subsequent hydrogen-consuming processes are known in the art. Alternatively, since CO2 is inert to many conversions and is actually a co-reactant in other conversions, it may not be necessary to separate CO2 from H2 before utilizing H2.

[0016] Of course, the net reaction of the hydrogenation and dehydrogenation steps is the conversion of hydrogen and carbon dioxide into hydrogen and carbon dioxide. But the key point is that the methanol intermediate between these steps is easier to store and transport than hydrogen.

[0017] Therefore, in one aspect, this disclosure provides an integrated method for producing hydrogen, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Provide a second feed stream that includes at least a portion of the methanol from the first product stream; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream comprising H2 and CO2, wherein the dehydrogenation has a carbon product selectivity of at least 40% for CO2.

[0018] As used herein, “feed stream” refers to the total material input of a process step (e.g., CO2 hydrogenation or methanol dehydrogenation), whether provided as a single physical stream or multiple physical streams, and whether through a single inlet or multiple inlets. For example, H2 and CO2 in a first feed stream may be provided to the hydrogenation reactor as a single physical stream (e.g., in a single pipe leading to the reactor) or as multiple physical streams (e.g., separate inlets for CO2 and H2, or one inlet for fresh CO2 and H2 and another for recycled CO2 and / or H2). Similarly, “product stream” refers to the total material output from a process step (e.g., CO2 hydrogenation or methanol dehydrogenation), whether provided as a single physical stream or multiple physical streams, and whether through a single reactor outlet or multiple reactor outlets.

[0019] Advantageously, the methods described herein can be substantially symmetrical in nature, with the streams entering CO2 hydrogenation and exiting methanol dehydrogenation having similar carbon compositions. Since most of the reactions described herein are equilibrium processes, they are naturally suited to symmetrical integration.

[0020] The first feed stream contains H2 and CO2 for subsequent contact with a hydrogenation catalyst for the production of methanol. Therefore, in various embodiments as further described herein, the first feed stream contains at least 10 mol% H2. For example, in various embodiments, the first feed stream contains at least 20 mol% H2, such as at least 30 mol% H2. In various embodiments as further described herein, the first feed stream contains at least 5 mol% CO2. For example, in various embodiments, the first feed stream contains at least 10 mol% CO2, such as at least 15 mol% CO2.

[0021] Typically, CO2 hydrogenation to produce methanol proceeds according to the following reaction: CO2 + 3 H2 → CH3OH + H2O. Therefore, in various embodiments further described herein, the H2:CO2 ratio of the first feed stream is at least 1:1 on a molar basis, for example, at least 1.5:1. For example, in various embodiments further described herein, the H2:CO2 ratio of the first feed stream is at least 2:1, for example, at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 8:1. In certain embodiments, the H2:CO2 ratio of the first feed stream is no more than 25:1, for example, no more than 20:1, or no more than 15:1, or no more than 12:1.

[0022] In some embodiments, the first feed stream contains other gases besides CO2 and H2. For example, in various embodiments, the first feed stream also contains one or more of CO, CH4, and N2. For example, in a particular embodiment, the first feed stream contains other gases (e.g., one or more of CO, CH4, and N2) besides CO2 and H2, in an amount up to 70 mol%. In various embodiments, the first feed stream contains no more than 1% O2, for example, no more than 0.1% O2, or no more than 0.01% O2, or substantially no O2. In various embodiments, the first feed stream contains no more than 20 mol% CO, for example, no more than 15 mol% CO, or no more than 10 mol% CO, or even no more than 5 mol% CO.

[0023] As otherwise described herein, the first feed stream is contacted with the hydrogenation catalyst. The hydrogenation catalyst can be selected by those skilled in the art; various catalysts for hydrogenating CO2 to methanol are known to those skilled in the art. Examples of suitable catalysts include Cu / ZnO catalysts, such as those supported on alumina or zirconium oxide.

[0024] Advantageously, the CO2 hydrogenation reaction can be carried out at relatively low temperatures, resulting in improved energy efficiency of the overall process. For example, in various embodiments as further described herein, the first feed stream is contacted with the hydrogenation catalyst at temperatures ranging from 200 to 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 first feed stream is contacted with the hydrogenation catalyst at pressures not exceeding 100 barg, such as not exceeding 80 barg, or not exceeding 60 barg.

[0025] As described herein, the hydrogenation of CO2 advantageously produces methanol with relatively high selectivity. Therefore, in various embodiments further described herein, the hydrogenation of CO2 is carried out with a carbon selectivity to methanol of at least 50%, for example, at least 55%, or at least 60%. For example, in certain embodiments, the hydrogenation of CO2 is carried out with a carbon selectivity to methanol of at least 65% (e.g., at least 70%, at least 75%, or at least 80%). Advantageously, the hydrogenation of CO2 can be carried out with low selectivity to methane. In various embodiments further described herein, the hydrogenation of CO2 is carried out with a carbon selectivity to methane of no more than 20%, for example, no more than 10%, or no more than 5%. As will be understood by those skilled in the art, the “carbon selectivity” (sometimes referred to simply as “selectivity” in this context) of a given species is the fraction of the carbon-containing reactants of the reaction converted to that species, i.e., excluding unreacted substances.

[0026] Importantly, the CO2 hydrogenation reaction described herein is not a reverse water-gas shift reaction. As is known in the art, a reverse water-gas shift reaction converts CO2 and H2 into CO and H2O. Therefore, in the various embodiments further described herein, the CO2 hydrogenation is carried out with a carbon selectivity to CO of no more than 20%, for example, no more than 10% or no more than 5%. In certain embodiments, the CO2 hydrogenation is carried out with a carbon selectivity to CO of no more than 2% or 1% or more.

[0027] During the CO2 hydrogenation reaction, at least a portion of the CO2 is hydrogenated to form MeOH and H2O. Advantageously, this method can be carried out with a relatively high CO2 conversion rate. Thus, in the various embodiments further described herein, the CO2 hydrogenation is carried out with a CO2 conversion rate of at least 25%, for example at least 35%, for example at least 45% or at least 50%.

[0028] Those skilled in the art will be 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. (ed.) 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.

[0029] CO2 hydrogenation produces a first product stream. In various embodiments further described herein, the first product stream contains at least 15 mol% methanol, for example at least 25 mol%, or at least 35 mol% methanol. As described herein, CO2 hydrogenation also has an advantageous low selectivity for other products, such as methane and / or carbon monoxide. Therefore, in various embodiments further described herein, the first product stream contains no more than 10 mol% methane, for example no more than 5 mol% methane, or no more than 2 mol% methane. In various embodiments further described herein, the first product stream contains no more than 10 mol% CO, for example no more than 5 mol% CO, or no more than 2 mol% CO. Of course, in some embodiments, more methane and / or CO may be present when provided as part of the first feed stream. As those skilled in the art will understand, the composition of the first product stream disclosed herein is calculated without regard to inert gases or unreacted CO2 and / or H2.

[0030] As described herein, the CO2 hydrogenation step produces both methanol and water. While an equivalence of water is typically required in the methanol dehydrogenation process, in some embodiments, the water formed may be undesirable in subsequent industrial processes where the hydrogen released from dehydrogenation is to be used. For example, in the context of Fischer-Tropsch synthesis, excess water present in the methanol dehydrogenation product stream may undesirably lead to the conversion of CO back to CO2 via the water-gas shift reaction. Furthermore, separating water from methanol avoids the need to store and transport additional volumes and masses of water; in some cases, separating water from methanol and reintroducing the desired amount of water for methanol dehydrogenation may be more cost-effective overall. Therefore, in various embodiments further described herein, the method also includes separating at least a portion of water from the first product stream. For example, in a particular embodiment, the method further includes separating at least 50%, or at least 75%, or at least 90% of the water in the first product stream. In various embodiments further described herein, this portion of the first product stream contained in the second feed stream has a water content of no more than 10 mol%, for example, no more than 2 mol%, or no more than 1 mol%, or no more than 0.5 mol.

[0031] In embodiments where water is separated from the CO2 hydrogenation step, the water may be disposed of as waste or recycled into other processes. For example, in various embodiments, the separated water is directed to an electrolytic reactor to generate H2 gas, for example, for this process or other processes. In some embodiments, the separated water undergoes a purification step before being introduced into the electrolytic reactor.

[0032] However, water is a reactant in many dehydrogenation processes that provide large amounts of CO2 combined with hydrogen. Separating water from the first product stream and then reintroducing it into the second feed stream typically involves cost and / or energy, and in some cases, the costs and energy involved may be significantly higher than those involved in storing and transporting water with methanol. Therefore, in various embodiments as further described herein, water is not separated from the first product stream. For example, in various embodiments, this portion of the first product stream contained in the second feed stream has a water content of at least 10 mol%, such as at least 20 mol%, or at least 30 mol%. In various embodiments, this portion of the first product stream contained in the second feed stream has a water content of at least 75%, such as at least 85%, or at least 90%, or at least 95% of the first product stream.

[0033] In various embodiments as further described herein, not all H2 gas from the input CO2 hydrogenation is reacted. Therefore, in such embodiments, the method may further include separating at least a portion of the H2 from the first product stream. For example, in certain embodiments as further described herein, the method may further include separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 from the first product stream. The separated H2 may optionally be purified and then optionally recycled. In various embodiments, at least a portion of the separated H2 may be recycled to the first feed stream and / or may be directed to another reactor. For example, in various embodiments, at least a portion of the H2 separated from the first product stream may be used to activate a methanol dehydrogenation catalyst (e.g., a methanol cracking catalyst).

[0034] Advantageously, some of the methods described herein can be integrated to improve efficiency. For example, in various embodiments further described herein, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out in the same plant. As those skilled in the art will understand, "same plant" means that the two processes occur within a small geographical area or industry, so that directly connecting the two without significant intermediate transport steps would be economical. Similarly, in various embodiments, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out within 1 km of each other. For example, in a particular embodiment further described herein, at least a portion of the methanol in the first product stream can be directly supplied to the second feed stream.

[0035] As described herein, hydrogen from the first product stream has various uses. Any or all of these can be utilized in a specific practical process. It is worth noting that the inventors recognize that the presence of hydrogen in the second feed stream may be detrimental to the conversion of methanol to carbon monoxide (i.e., since hydrogen is a coproduct in this reaction, the presence of hydrogen in the second feed stream will force the equilibrium to proceed in an undesirable reverse direction). Therefore, in various embodiments, this portion of the first product stream provided to the second feed stream contains no more than 50% of the first product stream hydrogen, for example, no more than 25%, no more than 10%, or no more than 5% of the first product stream hydrogen.

[0036] This portion of the first product stream provided to the second feed stream can advantageously be subjected to elevated temperatures and / or pressures. This can reduce capital costs by mitigating the heating and / or pressurization requirements of the second feed stream. Therefore, in various embodiments as further described herein (e.g., when methanol dehydrogenation is methanol cracking), this portion of the first product stream provided to 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. In other embodiments (e.g., when methanol dehydrogenation is methanol electrolysis), the portion of the first product stream provided to the second feed stream has a temperature in the range of 0-200°C, such as 0-150°C, 0-100°C, 0-50°C, 20-200°C, 20-150°C, 20-100°C, or 20-50°C. In a particular embodiment, the portion of the first product stream provided to the second feed stream is under a pressure of 0 to 50 barg, such as 1 to 50 barg.

[0037] Compared to gaseous compositions, compositions that are liquid at ambient temperature and pressure generally require lower capital expenditure for processing due to their increased density and reduced need for high pressure and / or low temperature. The inventors have noted that the methanol product from CO2 hydrogenation can be easily stored and / or transported. Therefore, in various embodiments as further described herein, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out in separate facilities. As used herein, "separate facilities" refers not merely to different catalyst beds or different containers, but to facilities different from those used for CO2 hydrogenation. In various embodiments, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out at a distance of more than 1 km from each other. In such various embodiments, methanol from the first product stream can be stored and / or transported before being provided to the second feed stream.

[0038] In various embodiments, regardless of whether the methanol dehydrogenation step and the contact of the first feed stream with the hydrogenation catalyst are carried out in the same or different facilities, or near or far from each other, at least a portion of the methanol in the first product stream is stored (e.g., in one or more tanks) before being provided to the second feed stream. Storage can last for any suitable period. In various embodiments, the stored portion of the methanol in 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 one week. In certain embodiments, the stored portion of the methanol is transported at least 1 km, e.g., at least 2 km, or at least 10 km, during the storage period. In some embodiments, the methanol may be transported via pipeline. Storing methanol within a single facility can, for example, allow for the dehydrogenation of the stored methanol when the hydrogen supply (e.g., via electrolysis using renewable energy) is insufficient to maintain process continuity. Furthermore, storage with transport can provide a convenient carrier for supplying hydrogen to locations remote from water electrolysis.

[0039] The second feed stream introduces methanol for dehydrogenation to provide CO2 and H2. Methanol dehydrogenation is a process distinct from methanol decomposition. In methanol decomposition, methanol reacts with water to produce CO and H2. Therefore, in the various embodiments described elsewhere herein, methanol decomposition is not utilized. For example, in certain embodiments, no more than 10% of the H2 is derived from methanol decomposition (e.g., no more than 5%, or no more than 1%).

[0040] A water-gas shift reaction is a method for producing H2 by reacting carbon monoxide with water. This reaction is also reversible, wherein carbon dioxide can react with hydrogen to form carbon monoxide and water. Both reactions are conventionally used in the art. Advantageously, the methods disclosed herein can be carried out substantially without the use of a water-gas shift reaction, a reverse water-gas shift reaction, or both. Thus, in various embodiments further described herein, less than 10% (e.g., less than 5%, or less than 2%) of H2 and CO2 are each generated by the water-gas shift reaction. In various embodiments further described herein, depending on the circumstances, less than 10% (e.g., less than 5%, or less than 2%) of CO are each generated by the reverse water-gas shift reaction. In the various methods disclosed herein, no dedicated water-gas shift reactor or reverse water-gas shift reactor is used (however, as those skilled in the art will understand, the water-gas shift reaction or reverse water-gas shift reaction may be operated to a lesser extent as a side reaction during certain processes).

[0041] Of course, in other methods, water-gas shift or reverse water-gas shift can be used in series with the methanol dehydrogenation process described in this article.

[0042] As described herein, methanol is dehydrogenated to form a product stream comprising CO2 and H2. Therefore, in various embodiments as further described herein, the second feed stream comprises at least 5 mol% methanol. For example, in a particular embodiment, the second feed stream comprises at least 7.5% methanol, such as at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0043] Typically, methanol dehydrogenation for the production of H2 and CO2 proceeds according to the following reaction: CH3OH + H2O → CO2 + 3 H2. Therefore, in various embodiments further described herein, the second feed stream contains water. For example, in some embodiments described herein, the water concentration of the second feed stream is at least 5 mol%, such as at least 7.5 mol%, or at least 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 25 mol%. In various embodiments, the second feed stream has a water-to-methanol molar ratio of at least 0.75, such as at least 0.85, or at least 0.95, or at least 1. In various embodiments as further described herein, the second feed stream has a water-to-methanol molar ratio in the range of 0.75-2, for example 0.85-2, or 0.95-2, or 1-2, or 0.75-1.6, or 0.85-1.6, or 0.95-1.6, or 1-1.6, or 0.75-1.3, or 0.85-1.3, or 0.95-1.3, or 1-1.3.

[0044] Optionally, the second feed stream may also contain one or more additional gases, which may be inert or reactive. In such embodiments, the second feed stream may also contain one or more of H2, CO, CH4, CO2, and N2. In a particular embodiment, the second feed stream contains an inert carrier gas, wherein the inert carrier gas contains one or more of CH4 and N2. Additionally or alternatively, H2 and / or CO2 may be added to the second feed stream to regulate the methanol reaction. In such embodiments, the second feed stream also contains H2 and / or CO2. In various embodiments further described herein, one or more of H2, CO, CH4, CO2, and N2 are present in the second feed stream in amounts up to 50 mol%, for example up to 40 mol%, or up to 30 mol%. Those skilled in the art can select specific additional gases in the second feed stream based on, for example, the intended use of the generated hydrogen and the process tolerance of the dehydrogenation method used.

[0045] In various embodiments further described herein, methanol dehydrogenation is carried out via methanol and hydrothermal catalytic conversion to H2 and CO2. Such processes are differently referred to in the art as methanol cracking, methanol reforming, and methanol steam reforming; the term "methanol cracking" is generally used in this disclosure to refer to this process step. In various embodiments further described herein, methanol dehydrogenation is carried out by contacting a second feed stream with a methanol cracking catalyst. Any suitable methanol cracking catalyst can be used; many are known in the art. For example, the methanol cracking catalyst may contain a transition metal, such as one or more transition metals selected from Groups 8-12 of the periodic table. In certain embodiments, the methanol cracking catalyst contains one or more of Cr, Ni, Cu, Zn, Pt, or mixtures thereof. In some embodiments, the methanol cracking catalyst may contain an intermetallic compound or alloy. For example, the catalyst may also contain one or more of Sc, Y, Ti, Zr, Ce, B, Al, Ga, In, Si, Ge, Sn, or Sb. Methanol cracking catalysts can be supported catalysts, wherein the support is a refractory oxide, such as diamond oxide, silica, zirconium oxide, cerium dioxide, titanium dioxide, alumina, lanthanum oxide, or magnesium oxide. In some embodiments, the methanol cracking catalyst is a copper / zinc oxide catalyst, for example, on alumina.

[0046] Those skilled in the art will be familiar with catalytic methods for cracking methanol into CO2 and H2. Various examples of catalysts and catalytic methods are described in U.S. Patent No. 9,174,199, Japanese Patent No. 6,936,338, and Palo et al., “Methanol Steam Reforming for Hydrogen Production” Chem. Rev. 107: 3992-4021 (2007), each of which is incorporated herein by reference in its entirety.

[0047] The second feed stream is contacted with the methanol cracking catalyst at a temperature suitable for achieving efficient methanol cracking. In various embodiments further described herein, the contact between the second feed stream and the methanol cracking catalyst is carried out at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C. Contact can be carried out at a variety of suitable pressures. For example, in various embodiments as described herein, the second feed is contacted with the methanol cracking catalyst at a pressure in the range of 0 to 50 barg, such as 1-30 barg, or 1-15 barg, or 1-10 barg, or 5-30 barg, or 5-15 barg, or 5-10 barg, or 10-25 barg.

[0048] As described herein, contacting the second feed stream with the methanol cracking catalyst can be carried out in the same facility as contacting the first feed stream with the hydrogenation catalyst. In such instances, coordinating the temperatures of the methanol cracking and hydrogenation reactions may be advantageous to avoid excessive heating and cooling capital and energy costs. Therefore, in specific embodiments as further described herein, contacting the second feed stream with the methanol cracking catalyst is carried out at a temperature within 75°C of the temperature at which the first feed stream is contacted with the hydrogenation catalyst, for example, within 50°C.

[0049] In various embodiments further described herein, methanol dehydrogenation is carried out by electrolysis of methanol and water to H2 and CO2. For example, in various embodiments further described herein, methanol dehydrogenation is carried out by methanol electrolysis in which at least a portion of the methanol of a second feed stream is brought into contact with an anode in a methanol electrolysis reaction zone having a cathode disposed therein and a voltage source applying a potential between the cathode and the anode.

[0050] Electrolysis of aqueous methanol may require a lower operating voltage compared to water electrolysis. Therefore, electrolyzing methanol as a solution of water may be desirable. In the various examples described herein, the second feed stream has a water concentration of at least 75 mol%, for example, at least 80 mol%, or at least 90 mol%. Electrolysis is typically carried out on a liquid-phase rather than a gas-phase feed stream. Therefore, the second feed stream has a temperature that keeps the methanol and water in the second feed stream substantially in the liquid phase. In the various embodiments described herein, the second feed stream has a temperature not exceeding 100°C, for example, not exceeding 80°C, or not exceeding 65°C, or not exceeding 45°C. Pressure can be used for operation at temperatures above 65°C.

[0051] Various methods for methanol electrolysis are known in the art, and therefore, there are no particular limitations on contacting the second feed stream with the anode. In the various embodiments described herein, the anode comprises platinum and ruthenium. As mentioned above, electrolysis is typically carried out on a liquid rather than a gaseous feed stream. Therefore, in the various embodiments described herein, contacting the second feed stream with the anode is carried out at a temperature not exceeding 100°C, for example, not exceeding 80°C, or not exceeding 65°C, or not exceeding 45°C.

[0052] As mentioned above, the electrolysis of aqueous methanol may require a lower operating voltage compared to the electrolysis of water. Therefore, a sufficient potential exists between the anode and cathode for the aqueous methanol to be electrolyzed. For example, in the various embodiments described herein, contacting the second feed stream with the anode is performed at a potential between the cathode and anode greater than 0.02 V, such as greater than 0.05 V, or greater than 0.10 V, or greater than 0.20 V, or greater than 0.30 V, or greater than 0.50 V. However, since the electrolysis of aqueous methanol may require a lower operating voltage compared to the electrolysis of water, it may be desirable to apply a potential between the cathode and anode such that the water in the second feed stream is not electrolyzed. Therefore, in various embodiments as further described herein, the second feed stream is brought into contact with the anode at a potential between the cathode and the anode in the range of 0.02 to 2.0 V, for example, 0.02-1.4 V, or 0.02-1 V, or 0.1-2.0 V, or 0.1-1.4 V, or 0.3-2.0 V, or 0.3-1.4 V, or 0.3-1.0 V.

[0053] Electrolysis requires an electrolyte disposed between the cathode and anode to allow direct current to pass between them. A proton exchange membrane (PEM) is used to conduct protons from the anode to the cathode to generate H2. In the various embodiments described herein, the methanol electrolysis reaction zone has a proton exchange membrane disposed between the anode and cathode. In some embodiments, the proton exchange membrane is Nafion. The composition of the cathode is not particularly limiting and can depend on the composition of the anode. In some embodiments described herein, the cathode contains platinum or palladium.

[0054] One advantage of using electrolysis for methanol dehydrogenation is that the H2 and CO2 produced by methanol electrolysis can be separated during their generation. CO2 is produced when methanol is anolyzed, and CO2 cannot permeate through the proton exchange membrane to reach the cathode. Only protons can permeate through the proton exchange membrane to reach the cathode, where they are reduced to form H2 gas upon contact with the cathode. Therefore, CO2 can only be generated on the anode side of the methanol electrolysis reaction zone, while H2 can only be generated on the cathode side of the methanol electrolysis reaction zone. For example, in the various embodiments described herein, the second product stream is provided to multiple outlets that are geographically separated from each other. In some embodiments, a first portion of this product stream is provided to a first outlet, wherein the first outlet is positioned such that the cathode is disposed between the membrane and the first outlet, wherein the first portion of the second product stream is at least 90 mol% H2, for example at least 95 mol% H2, or at least 99 mol% H2, or substantially all of H2. Furthermore, in some embodiments, a second portion of the second product stream is provided to a second outlet, wherein the second outlet is positioned such that the anode is disposed between the membrane and the second outlet, wherein the second portion of the second product stream is no more than 10 mol% H2, for example, no more than 5 mol% H2, or no more than 1 mol% H2. For example, in some embodiments, the second portion of the second product stream is at least 90 mol% CO2, for example, at least 95 mol% CO2, or at least 99 mol% CO2.

[0055] Methanol dehydrogenation, whether via pyrolysis or electrolysis, produces CO2 and H2, ideally with CO2 as the major carbon product. Therefore, in the various embodiments further described herein, methanol dehydrogenation is carried out with a carbon product selectivity of at least 50% for CO2, for example, at least 60%, or at least 70%, or at least 80%, or at least 90%. Advantageously, in various embodiments, methanol dehydrogenation is carried out with a CO selectivity of no more than 20%, for example, no more than 15%, or no more than 10%, or no more than 5%.

[0056] The primary hydrogen product of methanol dehydrogenation is preferably H2. Therefore, in the various desirable embodiments further described herein, methanol dehydrogenation is carried out with a hydrogen product selectivity to H2 of at least 50%, for example at least 60%, or at least 70%, or at least 80%, or at least 90%. As used herein, the hydrogen product selectivity to H2 is calculated as follows: (Number of H2 moles in the second product stream - Number of H2 moles in the second feed stream) divided by [(Number of H2O moles in the second feed stream - Number of H2O moles in the second product stream) + 2 × (Number of CH3OH moles in the second feed stream - Number of CH3OH moles in the second product stream)].

[0057] In various embodiments as further described herein, methanol dehydrogenation is carried out with 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%.

[0058] As described herein, methanol dehydrogenation produces CO2 and H2. Therefore, in the various embodiments further described herein, the second product stream contains a total of at least 20 mol% CO2 and H2, for example, at least 35 mol%, or at least 50 mol%, or at least 65 mol%. Not wishing to be bound by theory, it is anticipated that methanol dehydrogenation under these conditions will produce 3 moles of H2 per mole of CO2. Therefore, in the various embodiments further described herein, the second product stream has a hydrogen to carbon dioxide molar ratio in the range of 0.5:1 to 6:1, for example, 1:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 3.5:1. Of course, in other embodiments, this molar ratio may differ, for example, as a result of the second feed stream containing H2 or CO2.

[0059] In various implementations, the second product stream contains no more than 20 mol% CO, such as no more than 15 mol% CO, or no more than 10 mol% CO, or no more than 5 mol% CO, excluding CO that is not derived from methanol dehydrogenation (e.g., any CO present in the second feed stream is excluded).

[0060] Advantageously, a certain proportion of methanol is consumed during the methanol dehydrogenation reaction. Therefore, in various embodiments as further described herein, the second product stream contains no more than 75 mol% methanol, for example, no more than 60 mol% methanol, no more than 50 mol% methanol, or no more than 25 mol% methanol. For example, in some embodiments, the second product stream contains no more than 15 mol% methanol, for example, no more than 10 mol% methanol, or no more than 5 mol% methanol, or no more than 2 mol% methanol.

[0061] In some embodiments, it is desirable to further remove methanol from the second product stream. For example, in various embodiments further described herein, the method further includes separating at least a portion of the methanol from the second product stream, such as separating at least 50%, at least 75%, at least 90%, or at least 95% of the methanol from the second product stream. Advantageously, the methanol in the second product stream, such as 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 further described herein, the method further includes recycling at least a portion of the methanol separated from the second product stream to a second feed stream, such as at least 50%, at least 75%, at least 90%, or at least 95% of the methanol in the second product stream.

[0062] As described herein, the methanol dehydrogenation reaction produces H2 and CO2 in a theoretical 3:1 molar ratio, although the actual reaction output may vary. This hydrogen can be used in subsequent processes. It is also noteworthy that hydrogen may already be present in the second feed stream, further increasing the hydrogen content in the second product stream. Therefore, in various embodiments as further described herein, the method also includes separating at least a portion of the H2 from the second product stream. For example, in some embodiments, at least 50%, or at least 75%, or at least 90% of the H2 is separated from the second product stream.

[0063] The method for separating hydrogen from the second product stream is not particularly limited, and various methods for separating hydrogen from gaseous mixtures are known in the art. In the various embodiments described herein, at least a portion of the hydrogen separated from the second product stream is separated using an H2-permeable membrane or using pressure swing adsorption. The hydrogen separated from the second product stream in this manner can be substantially pure. In some embodiments described herein, this portion separated from the second product stream is greater than 90 mol% H2, for example greater than 95 mol% H2, or greater than 99 mol% H2, or substantially entirely H2.

[0064] The separated H2 can be used in a variety of processes. For example, in a particular embodiment, at least a portion of the H2 separated from the second product stream is provided to the first feed stream. Additionally or alternatively, in various embodiments as further described herein, the method further includes activating the methanol cracking catalyst using at least a portion of the H2 separated from the second product stream.

[0065] As described above, methanol dehydrogenation produces CO2 and H2, ideally with CO2 as the major carbon product. Therefore, it may be desirable to separate CO2 from the second product stream rather than separating H2. In various embodiments further described herein, the method also includes separating at least a portion of the CO2 from the second product stream. For example, in a particular embodiment, at least a portion of the CO2 separated from the second product stream is treated using an amine scrubber. In some embodiments further described herein, at least a portion of the CO2 is separated from the second product stream by cooling it to a temperature below -78.5°C, for example, below -90.0°C or below -100.0°C.

[0066] The separated CO2 can be used in a variety of processes. For example, in a particular embodiment, at least a portion of the CO2 separated from the second product stream is provided to the first feed stream.

[0067] Of course, in many downstream applications of the generated hydrogen, CO2 is merely inert. However, in other applications, such as iron-based Fischer-Tropsch synthesis, CO2 is a desirable co-reactant. Therefore, in various embodiments, CO2 can be kept mixed with the hydrogen generated during methanol dehydrogenation.

[0068] Methanol dehydrogenation can be performed to provide hydrogen to downstream processes (e.g., hydrogen reactions). Therefore, in another aspect, this disclosure provides a method for performing integrated hydrogenation, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Provide a second feed stream that includes at least a portion of the methanol from the first product stream; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream comprising H2 and CO2, wherein the dehydrogenation has a carbon product selectivity of at least 40% for CO2; Provide a third feed stream that includes at least a portion of H2 of the second product stream; In the hydrogen reaction zone, hydrogen from the third feed stream is reacted with one or more co-reactants to provide a third product stream comprising one or more products, the products including reacted hydrogen atoms from the hydrogen in the third feed stream.

[0069] All details of the process up to the provision of a third feed stream can be found as described above and as otherwise herein.

[0070] In the various embodiments described herein, at least a portion of the H2 from the second product stream is supplied to the third feed stream. For example, in various embodiments, at least 50% of the H2 from the second product stream is supplied to the third feed stream, such as at least 75%, or at least 90%, or at least 95%, or at least 99%. In various embodiments, substantially all of the H2 from the second product stream is supplied to the third feed stream. Additionally or alternatively, in various embodiments further described herein, the H2 of the third feed stream may be at least partially supplied by a hydrogen source other than the second product stream.

[0071] In various embodiments as further described herein, the third feed stream may contain other gases, such as CO2, CH4, or N2. These other gases, in embodiments that include them, 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, and N2) are supplied to the third feed stream from sources other than the second product stream.

[0072] In some embodiments, as further described herein, the hydrogen reaction in the hydrogen reaction zone is a Fischer-Tropsch reaction carried out by contacting a third feed stream with a Fischer-Tropsch catalyst, and one or more co-reactants include one or more of CO and CO2. Those skilled in the art are familiar with various Fischer-Tropsch methods and can select specific FT reaction systems and parameters for use in the methods of this disclosure.

[0073] Therefore, in various embodiments as further described herein, the third feed stream has a molar H2:CO ratio suitable for Fischer-Tropsch synthesis. For example, in various embodiments, the molar H2:CO ratio of the third feed stream is 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 molar H2:CO ratio of at least 1.2:1. For example, in various embodiments, the third feed stream may have a molar H2:CO 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.

[0074] The Fischer-Tropsch catalyst can be selected by those skilled in the art. In various embodiments further described herein, the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or combinations thereof (e.g., cobalt or iron). In certain embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount ranging from 2 to 30 wt%, for example, from 5 to 25 wt%, or from 8 to 20 wt%, as Co(O). In certain embodiments, the Fischer-Tropsch catalyst comprises iron in an amount ranging from 15 to 95 wt%, for example, from 25 to 95 wt%, or from 30 to 90 wt%, as Fe(O). In various embodiments further described herein, the Fischer-Tropsch catalyst also comprises manganese (e.g., in an amount ranging from 0.1 to 15 wt%, or from 1 to 10 wt%). As those skilled in the art will understand, cobalt-based catalysts are particularly suitable for use in third feed streams in which a substantial proportion of carbon oxides is CO, for example, at least 50 mol%, at least 75 mol%, or at least 90 mol%. Iron-based catalysts are particularly suitable for use in third feed streams in which a significant proportion of carbon oxides are CO2, for example, at least 50 mol%, at least 75 mol%, or at least 90 mol%.

[0075] In various embodiments as further described herein, the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, alumina, silica, magnesium oxide, and zinc oxide (e.g., comprising at least one of titanium oxide, alumina, and silica). For example, in certain embodiments, the support is a titanium dioxide support, or an alumina support, or a silica support. In various embodiments, the support is shaped particles, such as extrudates. The catalyst can be prepared using methods conventional in the art.

[0076] Before use, some catalysts require activation. In various embodiments, as further described herein, the Fischer-Tropsch catalyst is activated in a reducing atmosphere. In various embodiments, the catalyst is substantially reduced to produce a reduced catalyst material for Fischer-Tropsch reaction catalysis. In embodiments where the Fischer-Tropsch catalyst contains cobalt, the process results in at least a portion of the cobalt being converted to cobalt metal. Desiredly, the reduction results in at least 50% of the cobalt being provided in the form of cobalt (0). Those skilled in the art can use conventional methods to reduce cobalt catalyst materials (e.g., materials based on cobalt oxide or cobalt hydroxide) to a metallic form. In various embodiments, as further described herein, the first reducing agent is hydrogen, H2. Hydrogen may be mixed with other gases, such as inert carrier gases. Examples of such inert carrier gases include nitrogen, carbon dioxide, argon, or helium. Hydrogen may also be mixed with carbon monoxide, with or without one or more additional carrier gases. In various embodiments, reduction is achieved by contacting a first catalyst material with a first reducing gas, wherein the first reducing gas contains a first reducing agent and contains at least 50 vol% H2 (e.g., at least 60 vol%, or at least 70 vol%, or at least 80 vol%, or at least 90 vol%, or at least 95 vol%, or substantially 100 vol% H2). In some embodiments as described herein, the H2 used for reduction may be derived from a second product stream. H2 may also be separated from a third product stream and recycled for the reduction of the Fischer-Tropsch catalyst.

[0077] The temperature for Fischer-Tropsch synthesis can suitably be in the range of 200-400°C, for example, 200-300°C, or 210-400°C, or 210-300°C, or 220-400°C, or 220-300°C. In various embodiments further described herein, the temperature for 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 reaction pressure can 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, the third feed stream is contacted with the Fischer-Tropsch catalyst at a pressure in the range of 20-40 barg.

[0078] Within the limitations set forth herein, those skilled in the art can modify conventional Fischer-Tropsch catalysts and methods to achieve the methods of this disclosure. Used for catalyst preparation and hydrocarbon synthesis (particularly concerning C).5+ Suitable techniques for the synthesis of hydrocarbons and / or oxygen-containing compounds are well known in the art, for example, as described in International Patent Application Publication No. 2019 / 154885, which is hereby incorporated herein by reference in its entirety.

[0079] Advantageously, in various embodiments as further described herein, the contact of the third feed stream with the Fischer-Tropsch catalyst and the methanol dehydrogenation of the second feed stream can be carried out in the same facility. This can be, for example, in different beds within the same reactor, or in different reactors. In such embodiments, the two processes can be integrated to provide efficient conversion of methanol to hydrocarbons.

[0080] The Fischer-Tropsch process is commonly used in the manufacture of C 5+ Hydrocarbons, such as unsubstituted C 5+ Hydrocarbons (such as alkanes and alkenes) and oxygen-containing carbon 5+ Hydrocarbons (e.g., C) 5+ Alcohols, aldehydes, ketones, and carboxylic acids). The Fischer-Tropsch reaction described herein is desirablely operated with high selectivity for hydrocarbons. For example, in various embodiments further described herein, the Fischer-Tropsch catalyst is contacted with a third feed stream at C 5+ The selectivity is at least 30%, for example at least 50%, or at least 70%. The hydrocarbon composition of the third product stream can vary depending on the type of catalyst and process conditions known in the art. In various embodiments, the hydrocarbon composition comprises hydrocarbons (e.g., straight-chain hydrocarbons, branched hydrocarbons, saturated or unsaturated hydrocarbons) and their oxygen-containing derivatives. In various embodiments further described herein, the hydrocarbon composition comprises at least one of alkanes, alkenes, and alcohols.

[0081] Generally, longer-chain hydrocarbons are preferred over shorter-chain hydrocarbons. Therefore, in various embodiments as further described herein, the third product stream comprises C1-C4 hydrocarbons, and the method further includes separating at least a portion of the C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream. In a particular embodiment, the method further includes 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 third feed stream. For example, catalytic partial oxidation of hydrocarbon feedstocks is described in European Patent Application Publication No. 0303438A1, which is incorporated herein by reference in its entirety. Additionally or alternatively, in a particular embodiment, at least a portion of the light hydrocarbon stream may be directed to a steam reforming unit and / or an autothermal reforming unit, such as an electrically heated steam reforming unit. The resulting hydrogen and / or carbon oxides may then be at least partially included in the third feed stream, as further described herein.

[0082] Light hydrocarbon streams contain many components, including short-chain (e.g., C1-C4) saturated hydrocarbons, short-chain olefins, and short-chain oxygen-containing compounds. In particular, olefins (e.g., ethylene, propylene, butene) and alcohols can also be recycled to the Fischer-Tropsch reactor to generate additional C24 hydrocarbons. 5+ Hydrocarbons. Therefore, in various embodiments as further described herein, the method further includes including at least a portion of the light hydrocarbon stream in a third feed stream. Additionally or alternatively, at least a portion of the light hydrocarbon stream may be included in a second feed stream to be transferred to the third feed stream.

[0083] In various embodiments, the third product stream may contain unreacted H2. In various embodiments further described herein, the method also includes separating at least a portion of the H2 from the third product stream. The separated H2 can then be directed to a process in which it is needed. For example, in a particular embodiment, at least a portion of the H2 separated from the third product stream is provided to the third feed stream. And as mentioned above, at least a portion of the H2 separated from the third product stream can be used to activate a Fischer-Tropsch catalyst.

[0084] In various embodiments, the third product stream may contain unreacted CO. In various embodiments further described herein, the method also includes separating at least a portion of the CO from 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 provided to the third feed stream.

[0085] In various embodiments, the third product stream may contain CO2. Therefore, in various embodiments as further described herein, the method also includes separating at least a portion of the CO2 from the third product stream. The separated CO2 can then be directed to the process where it is needed.

[0086] It might be desirable to provide C from third-party product logistics. 5+ Hydrocarbon product stream, i.e., containing at least 70 wt% C 5+ Hydrocarbons, for example, at least 80 wt% C 5+ Hydrocarbons, or at least 85 wt% C 5+ Hydrocarbons. As those skilled in the art will understand, this can be done by isolating at least a portion of other components, such as C1-C4 hydrocarbons, CO, CO2, and H2, as described above.

[0087] Furthermore, in some cases it might be desirable to favor C. 5+ The hydrocarbon product stream undergoes further transformation. Hydrogenation, i.e., hydrogenation, is used to convert C... 5+Hydrocarbon product streams can be contacted with hydrogen and a hydrotreating catalyst for this purpose. Therefore, in various embodiments, as otherwise described herein, the method includes contacting C... 5+ Hydrocarbon product streams are contacted with hydrogen and hydrotreating catalysts to treat C 5+ Hydrocarbon product streams are subjected to hydrotreating. 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 oxygenated compounds into non-oxygenated hydrocarbons. Hydrotreating can also be used to convert alkenes into alkanes. Hydroisomerization can be used to modify mixtures of hydrocarbon isomers. At least a portion of the H2 used in hydrotreating can be H2 provided by one or both of the second and third product streams as described above.

[0088] As those skilled in the art will understand, the Fischer-Tropsch method described herein can be used to provide a variety of final products. For example, in various embodiments as further described herein, at least a portion of C from a third product stream... 5+ Hydrocarbons provide one or more products. These products may be one or more of, for example, fuels (such as diesel fuel, gasoline, or aviation fuel), waxes, or oils (such as those used for lubrication or metalworking).

[0089] The methods described herein can be performed at high throughput. For example, in various embodiments as further described herein, CO2 hydrogenation, MeOH dehydrogenation, and / or Fischer-Tropsch synthesis can be carried out at 2000 hr. -1 Up to 20,000 hr -1 The exposure is carried out under GHSV conditions within the specified range. For example, in various implementations of this type, the contact is carried out at 4000 hr. -1 Up to 18,000 hr -1 or 6000 hr -1 Up to 16,000 hr -1 or 8000hr -1 Up to 12,000 hr -1 or 2000 hr -1 Up to 12,000 hr -1 or 4000 hr -1 Up to 10,000 hr -1 or 6000 hr -1 Up to 10,000 hr -1 or 2000 hr -1 Up to 8,000 hr -1 or 4000 hr -1 Up to 8,000 hr -1 or 2000 hr -1Up to 6000 hr -1 This is performed within the GHSV range. Of course, depending on the system, higher and lower space velocities can also be used.

[0090] Hydrogen can be added to the third feed stream to increase the H2:COx ratio. Conventional H2 is most commonly derived from natural gas, typically through methane steam reforming, partial hydrocarbon oxidation, and / or coal gasification. However, each of these methods releases significant amounts of CO2 into the atmosphere when carried out conventionally and relies on fossil fuels as starting materials and / or energy sources. In contrast, other known H2 sources are more environmentally friendly. Therefore, in the various embodiments further described herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the H2 in the second and / or third feed streams is derived from renewable resources.

[0091] In various embodiments, similar catalysts can be used for some reactions. For example, in some embodiments, the methanol cracking catalyst and the Fischer-Tropsch synthesis catalyst have the same composition. In a particular embodiment, the methanol cracking catalyst and the Fischer-Tropsch synthesis catalyst are the same catalyst.

[0092] The Haber-Bosch process is another hydrogen-dependent industrial method that includes an ammonia synthesis step in which hydrogen and nitrogen are combined to produce ammonia. Ammonia serves as a precursor for other nitrogen-containing compounds, such as nitrates and urea, many of which can be used as fertilizers. Therefore, in various embodiments as further described herein, the hydrogen reaction is carried out through ammonia synthesis by contacting a third feed stream with an ammonia synthesis catalyst, wherein one or more co-reactants comprise N2.

[0093] As described above, the third feed stream may contain N2, either carried over from the methanol dehydrogenation reaction or added from another source before being introduced into the hydrogen reaction zone. Therefore, in the various embodiments described herein, the N2 co-reactant for ammonia synthesis is provided by the third feed stream. The third feed stream may contain sufficient N2 for ammonia synthesis. For example, in the various embodiments described herein, the third feed stream contains 10-50 mol% N2, such as 15-45 mol%, or 20-40 mol%, or 25-35 mol%. Ammonia synthesis proceeds according to the equation: N2 + 3 H2 → 2 NH3, and therefore, the third feed stream may contain appropriate amounts of both H2 and N2 for ammonia synthesis. For example, in the various embodiments described herein, the third feed stream has an H2:N2 ratio in the range of 1:2 to 10:1, such as 1:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 3.5:1.

[0094] Oxygen-containing molecules, such as CO, CO2, and H2O, are known in the art to be poisons for ammonia synthesis catalysts. Therefore, it may be desirable to limit the amount of CO, CO2, and H2O in the third feed stream. For example, in the various embodiments described herein, the third feed stream contains less than 10 mol% CO, CO2, and H2O, such as less than 5 mol% CO, CO2, and H2O, or less than 1 mol% CO, CO2, and H2O, or substantially no CO, CO2, and H2O.

[0095] Any suitable ammonia synthesis catalyst can be used; many are known in the art. For example, ammonia synthesis catalysts may contain transition metals such as iron or ruthenium. In certain embodiments, the ammonia synthesis catalyst contains 5-25 wt% Fe on an elemental basis. In some embodiments, the ammonia synthesis catalyst may also contain a promoter. For example, in some embodiments, the ammonia synthesis is a promoting catalyst and also contains alkali metals, alkaline earth metals, and / or molybdenum. The ammonia synthesis catalyst may be a supported catalyst, wherein the support is a refractory oxide, such as graphite, silica, zirconium oxide, cerium dioxide, titanium dioxide, alumina, lanthanum oxide, or magnesium oxide.

[0096] Those skilled in the art will be familiar with catalysts and catalytic methods for the synthesis of ammonia from H2 and N2. Various examples of catalysts and catalytic methods are described in U.S. Patent Nos. 9,150,423, 10,322,940, and Humphreys et al., “Development and Recent Progress on Ammonia Synthesis Catalysts for Haber-Bosch Process” Adv. Energy Sustainability Res. 2: 2000043 (2021), each of which is incorporated herein by reference in its entirety.

[0097] Contacting the third feed stream with the ammonia synthesis catalyst can be carried out at temperatures and pressures sufficient to provide ammonia in the third product stream. The reaction conditions used to achieve this are not particularly limiting. For example, in the various embodiments described herein, contacting the third feed stream with the ammonia synthesis catalyst is carried out at temperatures in the range of 200-600°C, such as 200-550°C, or 200-500°C, or 250-550°C, or 250-500°C, or 200-450°C, or 250-450°C. In the various embodiments further described herein, contacting the third feed stream with the ammonia synthesis catalyst is carried out at pressures in the range of 30 to 200 barg, such as 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg.

[0098] In some cases, integrating methanol dehydrogenation and ammonia synthesis to improve efficiency may be desirable. Therefore, in the various embodiments described herein, the third feed stream is contacted with the ammonia synthesis catalyst and methanol dehydrogenation is carried out in the same facility.

[0099] Ammonia synthesis combines H2 and N2 to provide ammonia, ideally with minimal other products. For example, in the various embodiments described herein, the third product stream contains more than 30 mol% ammonia, such as more than 50 mol%, or more than 75 mol%, or more than 90 mol%.

[0100] As mentioned above, ammonia is an important precursor to nitrogen fertilizers. Nitrogen fertilizers can be provided in many forms, such as as ammonia, as ammonium salts, as nitrates, or as urea. In some embodiments as described herein, the method further includes converting at least a portion of the ammonia in the third product stream into nitrates or urea.

[0101] Hydrogenation of unsaturated organic molecules is an established method in both the chemical and petroleum refining industries. Unsaturated organic molecules, such as those containing at least one double and / or triple bond, and / or aromatic molecules, can be hydrogenated in which pairs of hydrogen atoms are incorporated into the organic molecule, for example, by reducing one or more multiple bonds (i.e., double or triple bonds) or by destroying aromaticity. The scope of hydrogenation of unsaturated organic molecules is not particularly limited; for example, it can hydrogenate unsaturated molecules obtained from petroleum refining or hydrogenate complex unsaturated small molecules. In the various embodiments described herein, the hydrogenation of unsaturated organic compounds is carried out by contacting a third feed stream with a hydrogenation catalyst, wherein one or more co-reactants comprise the unsaturated organic compound, and one or more products comprising the reacted hydrogen atoms from the third feed stream hydrogen contain the hydrogenated organic compound. The hydrogenated unsaturated organic compounds are not particularly limiting. For example, in the various embodiments described herein, the unsaturated organic compound contains one or more of the following functional groups: carbonyl, imine, nitro, olefin, alkyne, aromatic, and heteroaromatic.

[0102] The type and properties of hydrogenation catalysts are not particularly limiting; and a variety of hydrogenation catalysts are known in the art. For example, hydrogenation catalysts may comprise metals. In the various embodiments described herein, the hydrogenation catalyst comprises ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, rhenium, or combinations thereof. The hydrogenation catalyst may be a heterogeneous hydrogenation catalyst. Alternatively, the hydrogenation catalyst may be a homogeneous hydrogenation catalyst in which the metal comprising the hydrogenation catalyst is in unimolecular form, optionally supported by ligands. In some embodiments further described herein, the hydrogenation catalyst is a supported catalyst, wherein the support is a refractory oxide, such as silica, zirconium oxide, cerium dioxide, titanium dioxide, alumina, lanthanum oxide, or magnesium oxide.

[0103] Oxygen-containing molecules, such as CO, CO2, O2, and H2O, are known in the art to be potential poisons for hydrogenation catalysts. Therefore, it may be desirable to limit the amount of CO, CO2, O2, and H2O in the third feed stream. For example, in the various embodiments described herein, the third feed stream contains less than 10 mol% CO, CO2, O2, and H2O, such as less than 5 mol% CO, CO2, O2, and H2O, or less than 1 mol% CO, CO2, O2, and H2O, or substantially no CO, CO2, O2, and H2O.

[0104] Hydrotreating is a term known in the art that encompasses catalytic methods for treating hydrocarbon feedstocks. These catalytic methods, such as hydrotreating and hydrocracking, remove sulfur, oxygen, nitrogen, and metals from hydrocarbon feedstocks by replacing heteroatoms (i.e., sulfur, oxygen, and nitrogen) with hydrogen atoms. Furthermore, these catalytic methods saturate olefins in hydrocarbon-based feedstocks. Hydrotreating is important for reducing emissions when hydrocarbons are used as fuels because the removal of sulfur and nitrogen reduces SOx and NOx emissions during hydrocarbon fuel combustion. Hydrotreating can also improve the processing of hydrocarbon-based feedstocks for other refining-related methods because sulfur removal prevents poisoning of downstream reforming catalysts. Therefore, in the various embodiments described herein, the reaction with hydrogen is a hydrotreating process carried out by contacting a third feedstream with a hydrotreating catalyst, wherein one or more co-reactants comprise petroleum-derived or renewable-derived hydrocarbon feedstocks, and one or more products comprising the reacted hydrogen atoms from the third feedstream hydrogen comprise the hydrotreating hydrocarbon feedstock.

[0105] Hydrotreating of hydrocarbon feedstocks is discussed in U.S. Patent No. 8,143,438, which is incorporated herein by reference in its entirety.

[0106] As discussed above, hydrotreating is typically used to remove sulfur, oxygen, nitrogen, and metals from hydrocarbon feedstocks and to saturate the hydrocarbon feedstock with olefins. Therefore, the hydrocarbon feedstock co-reactants used in hydrotreating as described herein will contain sulfur, oxygen, nitrogen, and olefins. For example, in the various embodiments described herein, the hydrocarbon feedstock contains sulfur, oxygen, and / or nitrogen in amounts ranging from 0.05 wt% to 20 wt%, for example, from 0.05 wt% to 10 wt%, or from 0.05 to 5 wt%. In the various embodiments further described herein, the degree of unsaturation of the hydrocarbon feedstock is in the range of 0.05 to 20 atomic% unsaturation, for example, from 0.05 to 10 atomic% unsaturation, or from 0.05 to 5 wt% unsaturation.

[0107] Conditions for hydrotreating, such as temperature and pressure, can vary as is known in the art. Hydrotreating is carried out at temperatures and pressures sufficient to provide hydrotreated hydrocarbons. For example, in various embodiments as described herein, the third feed stream is contacted with the hydrotreating catalyst at temperatures ranging from 300 to 600°C, such as 300 to 550°C, or 350 to 550°C, or 350 to 500°C, or 300 to 450°C, or 350 to 450°C. In various embodiments further described herein, the third feed stream is contacted with the hydrotreating catalyst at pressures ranging from 30 to 200 barg, such as 40 to 190 barg, or 50 to 180 barg, or 80 to 160 barg. Hydrotreating of hydrocarbon feedstocks is discussed in U.S. Patent No. 9,187,702, which is incorporated herein by reference in its entirety.

[0108] Hydrogen is highly relevant not only as a reagent in a variety of industrial processes but also as a fuel. The growing importance of environmentally responsible renewable energy has led to renewed attention on hydrogen. As a fuel, hydrogen is ideal because it can react cleanly with oxygen in a hydrogen fuel cell to provide energy, forming water as the only byproduct. Therefore, in various embodiments as further described herein, the reaction of hydrogen is the reaction of hydrogen with oxygen to produce energy, wherein said one or more co-reactants include oxygen, and wherein said one or more products include water.

[0109] In some embodiments, as further described herein, the hydrogen reaction zone is a hydrogen fuel cell. The location of the hydrogen fuel cell is not particularly limiting, as renewed focus on hydrogen as a clean fuel source has led to its adoption in both the transportation and energy sectors. Hydrogen can be used to fuel power plants as well as various vehicles. For example, in various embodiments, as further described herein, at least a portion of the hydrogen in the second product stream is stored in a hydrogen fuel tank before being provided to the hydrogen fuel cell in the third feed stream. In some embodiments, the hydrogen fuel cell is in a vehicle, such as a bus or car. In some embodiments, as further described herein, the hydrogen fuel cell is in a power plant.

[0110] Hydrogen is also used as rocket fuel, where it is burned with oxygen in a combustion engine to produce steam as a propellant. Hydrogen used as rocket fuel is typically stored in liquid form before use. Therefore, in the specific embodiments described herein, the hydrogen reaction zone is the hydrogen combustion engine in the rocket. Furthermore, in the specific embodiments described herein, at least a portion of the hydrogen in the second product stream is stored in a hydrogen fuel tank before being supplied to the hydrogen combustion engine in the third feed stream, wherein this portion of the hydrogen in the second product stream and the hydrogen fuel tank are cooled to a temperature not exceeding -252.8°C.

[0111] The inventors have noted that carbon dioxide is the primary carbon input for the methods described herein, and that carbon dioxide can advantageously be provided from a variety of sources. Importantly, at least a portion of the carbon dioxide in the first feed stream (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) can be derived from renewable sources.

[0112] Carbon dioxide is a common waste and is generally desirable to remove from waste streams rather than release into the atmosphere. Advantageously, the carbon dioxide utilized in the methods described herein can be carbon dioxide collected from the atmosphere or otherwise already released into the atmosphere, such as from combustion or other industrial processes. Carbon dioxide can be captured, where it is collected or absorbed after release from industrial processes, or captured 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 in the first feed stream is obtained from direct air capture. Additionally or alternatively, carbon dioxide is often washed out from industrial effluents, particularly in methods that produce large amounts of carbon dioxide as a byproduct. Thus, in various embodiments as further described herein, at least a portion of the CO2 in 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, steel mill, or cement plant.

[0113] As mentioned above, renewable sources can be used to provide CO2 to the methods for which protection is sought. 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, wheatgrass, poplar, willow, silver maple, eastern cottonwood, green ash, black walnut, sweetgum, and sycamore. Another source of biomass is agricultural waste or crop residues. Conventional agricultural activities, including the production of food, feed, fiber, and forest products, generate large amounts of waste plant material. Examples of such materials include corn stalks, wheat straw, oat straw, barley straw, sorghum stubble, and rice straw. A third source of biomass is forestry residues left after timber harvesting. Biomass can also be in the form of commercial waste, industrial waste, sewage sludge, and municipal waste, including commercial and residential waste such as yard cuts, paper and cardboard, plastics, rubber, leather, textiles, and food waste. Therefore, in various embodiments as further described herein, at least a portion of the CO2 in the first feed stream is derived from a renewable source. For example, in certain embodiments, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the CO2 in the first feed stream is derived from biomass, such as agricultural biomass or municipal waste biomass. Additional sources of agricultural biomass will be apparent to those skilled in the art, as determined by local availability, economics, and methodological compatibility.

[0114] To generate carbon dioxide from carbon-containing materials (such as biomass), the material is typically gasified. Gasification involves heating the material under controlled conditions to produce a gaseous stream of carbon monoxide, hydrogen, and carbon dioxide. Controlled amounts of other reactants, such as oxygen and / or steam, can be used to modulate the method. The gasification conditions are adjusted according to the carbon-containing material being gasified to efficiently produce the gaseous product. In various embodiments, the carbon dioxide in the first feed stream comprises carbon dioxide from biomass gasification, for example, at least 50%, at least 75%, at least 90%, or at least 95% of the carbon dioxide originating from biomass gasification. The biomass can be any source as described above, or a combination of multiple sources can be used.

[0115] Conventional H2 is most commonly derived from natural gas, typically through methane steam reforming, partial hydrocarbon oxidation, and / or coal gasification. However, each of these methods releases significant amounts of CO2 into the atmosphere when carried out conventionally and relies on fossil fuels as starting materials and / or energy sources. In contrast, other known H2 sources are more environmentally friendly. Therefore, in the various embodiments further described herein, at least a portion (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) of the H2 in the first feed stream and / or the second feed stream is derived from renewable resources.

[0116] As is known in the art, hydrogen can be given a color-based name depending on its production origin. 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.

[0117] One potential source of green hydrogen is through the electrolysis of water. Many electrolysis methods are known in the art. For example, electrolysis can be carried out on pure water to produce hydrogen and oxygen, or on other solutions (e.g., brine solutions) to produce hydrogen and another product (e.g., chlorine). In a particular embodiment, hydrogen is formed by the electrolysis of a brine solution. Water electrolysis is further described in U.S. Patent Nos. 4,312,720, 4,021,323, and 4,094,751, each of which is incorporated herein by reference in its entirety.

[0118] To qualify as green hydrogen, the electricity used for water electrolysis must be derived from a renewable source, i.e., a source that does not rely on the combustion of fossil fuels. Exemplary sources of renewable electricity include solar, wind, geothermal, hydroelectric, or other renewable sources via photovoltaic capture or solar thermal technologies. Hydrogen produced using solar energy for water electrolysis is sometimes referred to as yellow hydrogen. Suitable renewable energy sources are known to those skilled in the art and may optionally be selected through certification by an appropriate authority. Thus, in various embodiments as further described herein, at least a portion of the H2 in the first feed stream is green hydrogen and / or yellow hydrogen. For example, in a particular embodiment, the method further includes providing at least a portion of the H2 in the first feed stream through the electrolysis of water. In various embodiments, the electrolysis of water is carried out using electricity at least partially derived from a renewable source.

[0119] Blue hydrogen is defined as hydrogen produced to some extent by means of fossil fuels, but in a manner that is carbon neutral overall (i.e., does not result in any net introduction of carbon dioxide into the atmosphere). In various embodiments as further described herein, the hydrogen utilized in methods as further described herein comprises blue hydrogen. One example of blue hydrogen is hydrogen produced from fossil fuel-derived hydrocarbons (e.g., methane gas), where the resulting carbon products are captured or otherwise utilized. For example, steam reforming of methane can be carried out to produce three moles of hydrogen and one mole of carbon monoxide for every mole of methane. Methane steam reforming is highly endothermic and requires a large energy input. Of course, the energy required to carry out these methods must be from a renewable source or a source with sufficient carbon capture technology. Therefore, in various embodiments as further 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. The production of hydrogen by steam reforming of methane is discussed in International Patent Application Publication No. 2004 / 022480, which is incorporated herein by reference in its entirety. Therefore, in various embodiments as otherwise described herein, at least a portion of the H2 in the first feed stream is blue hydrogen.

[0120] Gray hydrogen is the source of most conventional H2. Gray hydrogen is produced from natural gas / methane via steam reforming, but unlike blue hydrogen, it does not capture any of the resulting greenhouse gases (e.g., CO2). In various embodiments as further described herein, at least a portion of the H2 in the first feed stream is gray hydrogen.

[0121] Black hydrogen and brown hydrogen are produced from black coal or brown coal, respectively, typically through their gasification without any carbon capture. In various embodiments as further described herein, at least a portion of the H2 in the first feed stream is black hydrogen and / or brown hydrogen.

[0122] Powdered hydrogen is produced by water electrolysis, where the energy required for electrolysis is generated by nuclear energy. In various embodiments further described herein, at least a portion of the H2 in the first feed stream is powdered hydrogen. Powdered hydrogen is also known as purple hydrogen or red hydrogen.

[0123] Turquoise hydrogen is produced by the pyrolysis of methane, with hydrogen and solid elemental carbon as byproducts. In various embodiments further described herein, at least a portion of the H2 in the first feed stream is turquoise hydrogen.

[0124] White hydrogen is naturally occurring hydrogen gas that can be released via hydraulic fracturing. In various embodiments further described herein, at least a portion of the H2 in the first feed stream is white hydrogen.

[0125] As described herein, the disclosed methods, in various embodiments, comprise two central reactions: the hydrogenation of CO2 and the dehydrogenation of methanol. As described herein, these reactions can advantageously be carried out in spatial arrangements relatively different from each other. As is known in the art, reaction zones consist of one or more catalyst beds, and one or more reaction zones may be located within the same facility. Different facilities are typically geographically separated, preventing the transfer of feedstocks between them without intermediate transport and storage steps. Therefore, in various embodiments further described herein, a first reaction zone comprises a first reactor in which a hydrogenation catalyst is disposed, and a second reaction zone comprises a second reactor in which a methanol cracking catalyst is disposed. In various embodiments further described herein, a first reaction zone comprises a first catalyst bed in which a hydrogenation catalyst is disposed, and a second reaction zone comprises a second catalyst bed in which a methanol cracking catalyst is disposed. In a particular embodiment, the first reactor is located in a first facility, and the second reactor is located in a second facility.

[0126] As described herein, in some embodiments, various catalyst beds may be located in different reactors. Placing catalyst beds in separate reactors can offer various methodological advantages. For example, this separation allows each unit to experience reactor downtime independently (e.g., for maintenance). Furthermore, the reactors can be maintained at different temperatures to maximize the selectivity and efficiency of the individual methods. Exothermic and endothermic chemical reactions require temperature control to maintain stable operating temperatures. Separate processes conducted in separate reactors result in simplified temperature control because different catalysts will change activity at different rates over time. Therefore, in some embodiments as further described herein, the first and second catalyst beds are not blended. Catalyst blending occurs when catalysts used for different methods share the same catalyst bed. As used herein, two different catalyst beds within a reactor are not blended. In some embodiments as further described herein, the first and second catalyst beds are located in separate reactors.

[0127] An example implementation plan is in Figure 1 The diagram illustrates a process 100 contained within a single facility 141. A first feed stream 111 containing H2 and CO2 is introduced into a hydrogenation reaction zone 110 (here, a hydrogenation reactor) and contacted therewith with a hydrogenation catalyst 113 under conditions suitable for generating a first product stream 112 containing methanol. The first product stream will also typically contain other substances. For example, in... Figure 1In one embodiment, the first product stream contains CO2; at least a portion of the CO2 is separated from the first product stream and recycled to the first feed stream 111 via CO2 recycling 114. Similarly, the first product stream may contain H2 (e.g., unreacted H2) and / or CO. 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 H2 and / or CO recycling stream 115. Any water present may optionally be removed from the first product stream 112 via water separation stream 116 before the second feed stream (121). Furthermore, water feed stream 116 may optionally be fed to electrolytic reactor 160.

[0128] exist Figure 1 In one embodiment, the remainder of the first product stream 112 (i.e., after the separation described above) is provided to the second feed stream 121. The second feed stream 121 contains at least a portion of the methanol from the first product stream and can be supplemented via supplementary feed 118 by introducing other gases (e.g., CO2 and / or H2 and / or water). The second feed stream 121 is introduced into the methanol dehydrogenation reaction zone 120 (here, the methanol dehydrogenation reactor), where it is contacted with the methanol cracking catalyst 123 to decompose at least a portion of the methanol to form a second product stream 122 containing CO2 and H2. At least a portion of the CO2 can be separated from the second product stream via CO2 recirculation 124 and recycled back to the first feed stream 111 via CO2 recirculation stream 114. Alternatively and / or additionally, at least a portion of the H2 from the second product stream 122 can be separated and provided to an external reactor or process via H2 stream 125. H2 gas from the electrolysis reactor 160 is returned to the first feed stream via electrolytic H2 stream 117.

[0129] As described above, methanol can be formed via hydrogenation of carbon dioxide in a first facility, and then transported (e.g., via vehicle or pipeline) to a second facility, where the methanol is dehydrogenated and the resulting H2 and / or CO2 is used in downstream processes. Examples of such embodiments are... Figure 2 The diagram is shown in the figure. Here, the carbon dioxide hydrogenation step of process 200 is carried out in the first facility 241. A first feed stream 211 containing carbon dioxide and hydrogen is introduced into 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 produce a first product stream 212 containing methanol. The first product stream 212 may undergo various separations as described herein (not shown), and the methanol in the first product stream may then be stored for further use and / or transported to another facility. For example, in Figure 2In one embodiment, at least a portion of the first product stream 212 (containing methanol) is loaded into a storage tank 217 and then transported by truck 218 to a second facility 242. This portion of the first product stream is provided to a second feed stream 221, which is introduced into a methanol dehydrogenation reaction zone 220, where it contacts a methanol cracking catalyst 223 to generate a second product stream 222 containing CO2 and H2.

[0130] Another example implementation scheme is in Figure 3 The diagram is shown below. Here, in process 300, a first feed stream 311 is introduced into a first reaction zone 310 and contacted with a CO2 hydrogenation catalyst 313 to hydrogenate at least a portion of the CO2 in the first feed stream to form a first product stream 312 containing methanol. The first product stream 312 is discharged from the first reaction zone 310, and an additional gas stream 324 is added, with the resulting mixture provided as a second feed stream 321. The second feed stream 321 is introduced into a methanol dehydrogenation reaction zone 320, where a second product stream 322 is provided using a methanol cracking catalyst 323. Here, the second product stream 322 is discharged from the methanol dehydrogenation reaction zone, and unreacted methanol is substantially separated from the second product stream (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) and recycled to the second feed stream 321 via a methanol recycling 325. Notably, at least a portion of the H2 in the second product stream 322 can be separated and recycled to the first feed stream 311 via an H2 recycling stream 326. At least a portion of H2 in the second product stream 322 may also, or alternatively, be provided to an external reactor or process via H2 stream 327.

[0131] Another example implementation, in which methanol dehydrogenation is methanol electrolysis, in Figure 4 The diagram is shown below. Here, in process 400, a first feed stream 411 is introduced into a first reaction zone 410 and contacted with a CO2 hydrogenation catalyst 413 to hydrogenate at least a portion of the CO2 in the first feed stream to form a first product stream 412 containing methanol. The first product stream 412 is discharged from the first reaction zone 410, and an additional water stream 424 is added, with the resulting mixture provided as a second feed stream 421. The second feed stream 421 is introduced into a methanol electrolysis reaction zone, in which an anode 423a, a cathode 423b, and a proton exchange membrane 423c are provided. The second feed stream 421 is contacted with the anode 423a to provide the second product stream as two separate streams, a CO2 product stream 422a and an H2 product stream 422b. At least a portion of the CO2 product stream 422a can be separated and recycled back to the first feed stream 411 via a CO2 recycling 425.

[0132] Various exemplary embodiments of this disclosure include, but are not limited to, the embodiments listed below, which can be combined in any number and in any technically or logically consistent combination.

[0133] Implementation Scheme 1. A method for producing H2, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Provide a second feed stream that includes at least a portion of the methanol from the first product stream; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream containing H2 and CO2.

[0134] Implementation Scheme 2. The method according to Implementation Scheme 1, wherein the first feed stream contains at least 10 mol% H2, for example at least 20 mol% H2, or at least 30 mol% H2.

[0135] Implementation Scheme 3. The method according to Implementation Scheme 1 or Implementation Scheme 2, wherein the first feed stream contains at least 5 mol% CO2, for example at least 10 mol% CO2, or at least 15 mol% CO2.

[0136] Implementation Scheme 4. The method according to any one of Implementation Schemes 1-3, wherein the H2:CO2 ratio 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, or at least 5:1, or at least 6:1, or at least 8:1.

[0137] Implementation Scheme 5. The method according to any one of Implementation Schemes 1-4, wherein the H2:CO2 ratio of the first feed stream is not more than 25:1, for example not more than 20:1, or not more than 15:1, or not more than 12:1.

[0138] Implementation Scheme 6. The method according to any one of Implementation Schemes 1-5, wherein the first feed stream further comprises one or more of CO, CH4 and N2.

[0139] Implementation Scheme 7. The method according to any one of Implementation Schemes 1-6, wherein the first feed stream contains no more than 1% O2, for example no more than 0.1% O2, or no more than 0.01% O2, or substantially no O2.

[0140] Implementation Scheme 8. The method according to any one of Implementation Schemes 1-7, wherein the first feed stream contains no more than 20 mol% CO, for example no more than 15 mol% CO, or no more than 10 mol% CO, or no more than 5 mol% CO.

[0141] Implementation Scheme 9. The method according to any one of Implementation Schemes 1-8, wherein the hydrogenation catalyst is a copper / zinc oxide catalyst, for example, supported on alumina or zirconium oxide.

[0142] Implementation Scheme 10. The method according to any one of Implementation Schemes 1-9, wherein the first feed stream is contacted with the hydrogenation catalyst at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0143] Implementation Scheme 11. The method according to any one of Implementation Schemes 1-10, wherein the hydrogenation of CO2 is carried out with a carbon selectivity to methanol of at least 50%, for example at least 65% or at least 80%.

[0144] Implementation Scheme 12. The method according to any one of Implementation Schemes 1-11, wherein the hydrogenation of CO2 is carried out with a carbon selectivity to methane of not more than 20%, for example not more than 10% or not more than 5%.

[0145] Implementation Scheme 13. The method according to any one of Implementation Schemes 1-12, wherein the hydrogenation of CO2 is carried out with a carbon selectivity for CO of not more than 20%, for example not more than 10% or not more than 5%.

[0146] Implementation Scheme 14. The method according to any one of Implementation Schemes 1-13, wherein the hydrogenation of CO2 is carried out with a CO2 conversion rate of at least 25%, for example at least 35%, for example at least 45% or at least 50%.

[0147] Implementation Scheme 15. The method according to any one of Implementation Schemes 1-14, wherein the first product stream comprises at least 15 mol% methanol, for example at least 25 mol% or at least 35 mol% methanol.

[0148] Implementation Scheme 16. The method according to any one of Implementation Schemes 1-15, wherein the first product stream contains no more than 10 mol% methane, for example no more than 5 mol% methane, or no more than 2 mol% methane.

[0149] Implementation Scheme 17. The method according to any one of Implementation Schemes 1-16, wherein the first product stream contains no more than 10 mol% CO, for example no more than 5 mol% CO, or no more than 2 mol% CO.

[0150] Implementation Scheme 18. The method according to any one of Implementation Schemes 1-17 further includes separating at least a portion of water (e.g., at least 50%, at least 75%, or at least 90% of the water in the first product stream) from the first product stream.

[0151] Implementation Scheme 19. The method according to any one of Implementation Schemes 1-18, wherein the portion of the first product stream contained in the second feed stream has a water content of at least 10 mol%, for example, at least 20 mol%, or at least 30 mol%.

[0152] Implementation Scheme 20. The method according to any one of Implementation Schemes 1-19, wherein the portion of the first product stream included in the second feed stream has a water content of at least 75%, for example at least 85%, or at least 90%, or at least 95% of the first product stream.

[0153] Implementation Scheme 21. The method according to any one of Implementation Schemes 1-20 further includes separating at least a portion of 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 H2 in the first product stream).

[0154] Implementation Scheme 22. The method according to Implementation Scheme 21 further includes recycling at least a portion of the H2 separated from the first product stream back to the first feed stream.

[0155] Implementation Scheme 23. The method according to any one of Implementation Schemes 1-22, wherein the portion of the first product stream provided to the second feed stream contains no more than 50% of the first product stream hydrogen, for example no more than 25%, no more than 10%, or no more than 5% of the first product stream hydrogen.

[0156] Implementation Scheme 24. The method according to any one of Implementation Schemes 1-23, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out in the same facility.

[0157] Implementation Scheme 25. The method according to any one of Implementation Schemes 1-24, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out within 1 km of each other.

[0158] Implementation Scheme 26. The method according to any one of Implementation Schemes 1-25, wherein at least a portion of the methanol in the first product stream is directly supplied to the second feed stream.

[0159] Implementation Scheme 27. The method according to Implementation Scheme 26, wherein the portion of the first product stream provided to 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.

[0160] Implementation Scheme 28. The method according to Implementation Scheme 26, wherein the portion of the first product stream provided to the second feed stream has a temperature in the range of 0-200°C, for example 0-150°C, or 0-100°C, or 0-50°C, or 20-200°C, or 20-150°C, or 20-100°C, or 20-50°C.

[0161] Implementation Scheme 29. The method according to any one of Implementation Schemes 1-28, wherein the dehydrogenation and contacting the first feed stream with the hydrogenation catalyst are carried out in different facilities.

[0162] Implementation Scheme 30. The method according to any one of Implementation Schemes 1-29, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out at a distance of more than 1 km from each other.

[0163] Implementation Scheme 31. The method according to any one of Implementation Schemes 1-30, wherein at least a portion of the methanol in the first product stream is stored (e.g., in one or more tanks) before being provided to the second feed stream.

[0164] Implementation Scheme 32. The method according to Implementation Scheme 31, wherein the storage portion of the first product stream methanol is stored for at least one day, for example, at least two days or at least one week.

[0165] Implementation Scheme 33. The method according to Implementation Scheme 31 or Implementation Scheme 32, wherein the storage portion of the methanol is transported for at least 1 km, for example at least 2 km or at least 10 km, during storage.

[0166] Implementation Scheme 34. The method according to any one of Implementation Schemes 31-33, wherein the second feed stream is provided and dehydrogenated during intermittent periods of hydrogen generation using energy from renewable resources (e.g., by electrolysis using renewable energy).

[0167] Implementation Scheme 35. The method according to any one of Implementation Schemes 1-34, wherein the second feed stream comprises at least 5 mol% methanol, for example at least 7.5 mol% methanol, or at least 10 mol% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0168] Implementation Scheme 36. The method according to any one of Implementation Schemes 1-35, wherein the second feed stream further comprises H2O, and one or more of H2, CO, CH4, CO2 and N2.

[0169] Implementation Scheme 37. The method according to any one of Implementation Schemes 1-30, wherein the second feed stream has a water concentration of at least 5 mol%, for example at least 7.5 mol%, or at least 10 mol%, or at least 15%, or at least 20%, or at least 25 mol%.

[0170] Implementation Scheme 38. The method according to any one of Implementation Schemes 1-36, wherein the molar ratio of water to methanol in the second feed stream is at least 0.75, for example at least 0.85, or at least 0.95, or at least 1.

[0171] Implementation Scheme 39. The method according to any one of Implementation Schemes 1-38, wherein the molar ratio of water to methanol in the second feed stream is in the range of 0.75-2, for example 0.85-2, or 0.95-2, or 1-2, or 0.75-1.6, or 0.85-1.6, or 0.95-1.6, or 1-1.6, or 0.75-1.3, or 0.85-1.3, or 0.95-1.3, or 1-1.3.

[0172] Implementation Scheme 40. The method according to any one of Implementation Schemes 1-39, wherein the methanol dehydrogenation is carried out by contacting the second feed stream with a methanol cracking catalyst disposed in the methanol dehydrogenation reaction zone.

[0173] Implementation Scheme 41. The method according to Implementation Scheme 40, the method further comprising activating the methanol cracking catalyst using at least a portion of the H2 separated from the first product stream.

[0174] Implementation Scheme 42. The method according to Implementation Scheme 40 or Implementation Scheme 41, wherein the methanol cracking catalyst comprises copper, for example on an alumina support.

[0175] Implementation Scheme 43. The method according to any one of Implementation Schemes 40-42, wherein the second feed stream is contacted with the methanol cracking catalyst at a temperature in the range of 200-500°C, for example, 200-450°C, or 200-400°C, or 200-350°C, or 200-300°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-300°C, or 300-500°C, or 300-450°C, or 300-400°C.

[0176] Implementation Scheme 44. The method according to any one of Implementation Schemes 40-43, wherein the second feed stream is contacted with the methanol cracking catalyst at a pressure in the range of 1-50 barg, for example 1-30 barg, or 1-15 barg, or 1-10 barg, or 5-30 barg, or 5-15 barg, or 5-10 barg, or 10-25 barg.

[0177] Implementation Scheme 45. The method according to any one of Implementation Schemes 40-44, wherein the second feed stream is contacted with the methanol cracking catalyst at a temperature within 75°C of the temperature at which the first feed stream is contacted with the hydrogenation catalyst, for example, within 50°C.

[0178] Implementation Scheme 46. The method according to any one of Implementation Schemes 1-39, wherein the methanol dehydrogenation is carried out by methanol electrolysis in which at least a portion of the methanol of the second feed stream is contacted with an anode in a methanol electrolysis reaction zone, wherein a cathode and a voltage source are provided therein, the voltage source being arranged to apply a potential between the anode and the cathode.

[0179] Implementation Scheme 47. The method according to Implementation Scheme 46, wherein the second feed stream has a water concentration of at least 75 mol%, for example at least 80 mol%, or at least 90 mol%.

[0180] Implementation Scheme 48. The method according to Implementation Scheme 46 or Implementation Scheme 47, wherein the temperature of the second feed stream is not greater than 100°C, for example not greater than 80°C, or not greater than 60°C, or not greater than 40°C.

[0181] Implementation Scheme 49. The method according to any one of Implementation Schemes 46-48, wherein the anode comprises platinum and ruthenium.

[0182] Implementation Scheme 50. The method according to any one of Implementation Schemes 46-49, wherein the second feed stream is brought into contact with the anode at a temperature not greater than 100°C, for example not greater than 80°C, or not greater than 65°C, or not greater than 45°C.

[0183] Implementation Scheme 51. The method according to any one of Implementation Schemes 46-50, wherein the second feed stream is contacted with the anode at a potential between the cathode and the anode of 0.02 to 2.0 V, for example 0.02-1.4 V, or 0.02-1 V, or 0.1-2.0 V, or 0.1-1.4 V, or 0.3-2.0 V, or 0.3-1.4 V, or 0.3-1.0 V.

[0184] Implementation Scheme 52. The method according to any one of Implementation Schemes 46-51, wherein a membrane disposed between the anode and the cathode is provided in the methanol electrolysis reaction zone.

[0185] Implementation Scheme 53. The method according to Implementation Scheme 52, wherein the membrane is proton-permeable.

[0186] Implementation Scheme 54. The method according to Implementation Scheme 52 or Implementation Scheme 53, wherein the cathode comprises platinum or palladium.

[0187] Implementation Scheme 55. The method according to any one of Implementation Schemes 52-54, wherein the second product stream is provided to a plurality of outlets that are geographically distant from each other.

[0188] Implementation Scheme 56. The method according to Implementation Scheme 55, wherein a first portion of the second product stream is provided to a first outlet, wherein the first outlet is positioned such that the cathode is disposed between the membrane and the first outlet, wherein the first portion of the second product stream is at least 90 mol% H2, for example at least 95 mol% H2, or at least 99 mol% H2, or substantially all of H2.

[0189] Implementation Scheme 57. The method according to Implementation Scheme 55 or Implementation Scheme 56, wherein a second portion of the second product stream is provided to a second outlet, wherein the second outlet is positioned such that the anode is disposed between the membrane and the second outlet, wherein the second portion of the second product stream is not more than 10 mol% H2, for example not more than 5 mol% H2, or not more than 1 mol% H2, or substantially H2-free.

[0190] Implementation Scheme 58. The method according to Implementation Scheme 57, wherein the second portion of the second product stream is at least 90 mol% CO2, for example at least 95 mol% CO2, or at least 99 mol% CO2.

[0191] Implementation Scheme 59. The method according to any one of Implementation Schemes 1-58, wherein the dehydrogenation of methanol is carried out with a selectivity of at least 50% for carbon products of CO2, for example at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0192] Implementation Scheme 60. The method according to any one of Implementation Schemes 1-59, wherein the dehydrogenation of methanol is carried out with a selectivity for carbon products of CO of not more than 20%, for example not more than 15%, not more than 10%, or not more than 5%.

[0193] Implementation Scheme 61. The method according to any one of Implementation Schemes 1-60, wherein the dehydrogenation of methanol is carried out with a selectivity for hydrogen products of H2 of at least 50%, for example at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0194] Implementation Scheme 62. The method according to any one of Implementation Schemes 1-61, wherein the dehydrogenation of methanol is carried out at 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%.

[0195] Implementation Scheme 63. The method according to any one of Implementation Schemes 1-62, wherein the second product stream comprises a total of at least 20 mol% of CO2 and H2, for example at least 35 mol%, or at least 50 mol%, or at least 65 mol%.

[0196] Implementation Scheme 64. The method according to any one of Implementation Schemes 1-63, wherein the second product stream contains no more than 20 mol% CO, for example no more than 15 mol% CO, or no more than 10 mol% CO, or no more than 5 mol% CO, excluding CO not derived from methanol dehydrogenation.

[0197] Implementation Scheme 65. The method according to any one of Implementation Schemes 1-64, wherein the second product stream has a hydrogen to carbon dioxide molar ratio in the range of 0.5:1 to 6:1, for example 1:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 3.5:1.

[0198] Implementation Scheme 66. The method according to any one of Implementation Schemes 1-65, wherein the second product stream contains no more than 75 mol% methanol, for example no more than 60 mol% methanol, or no more than 50 mol% methanol, or no more than 25 mol% methanol.

[0199] Implementation Scheme 67. The method according to any one of Implementation Schemes 1-65, wherein the second product stream contains no more than 15 mol% methanol, for example no more than 10 mol% methanol, or no more than 5 mol% methanol, or no more than 2 mol% methanol.

[0200] Implementation Scheme 68. The method according to any one of Implementation Schemes 1-67 further includes separating at least a portion of 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).

[0201] Implementation Scheme 69. The method according to Implementation Scheme 68 further includes recycling at least a portion of the methanol separated from the second product stream to the second feed stream, for example, at least 50%, at least 75%, at least 90%, or at least 95% of the methanol in the second product stream.

[0202] Implementation Scheme 70. The method according to any one of Implementation Schemes 1-69 further includes separating at least a portion of H2 from the second product stream (e.g., at least 50%, or at least 75%, or at least 90% of H2 in the second product stream).

[0203] Implementation Scheme 71. The method according to Implementation Scheme 70, wherein at least a portion of H2 is separated from the second product stream using an H2-permeable membrane.

[0204] Implementation Scheme 72. The method according to Implementation Scheme 70, wherein at least a portion of H2 is separated from the second product stream using pressure swing adsorption.

[0205] Implementation Scheme 73. The method according to any one of Implementation Schemes 70-72, wherein the portion separated from the second product stream is greater than 90 mol% H2, for example greater than 95 mol% H2, or greater than 99 mol%, or substantially all of H2.

[0206] Implementation Scheme 74. The method according to Implementation Scheme 73 further includes providing at least a portion of the H2 separated from the second product stream to the first feed stream.

[0207] Implementation Scheme 75. The method according to any one of Implementation Schemes 1-74 further includes separating at least a portion of CO2 from the second product stream.

[0208] Implementation Scheme 76. The method according to Implementation Scheme 75, wherein at least a portion of the CO2 is separated from the second product stream using amine washing.

[0209] Implementation Scheme 77. The method according to Implementation Scheme 75, wherein at least a portion of the CO2 is separated from the second product stream by cooling the second product stream to a temperature below -78.5°C, for example below -90.0°C or below -100.0°C.

[0210] Implementation Scheme 78. The method according to any one of Implementation Schemes 75-77, further comprising providing at least a portion of the CO2 separated from the second product stream to the first feed stream.

[0211] Implementation Scheme 79. The method according to any one of Implementation Schemes 1-78, the method further comprising: Provide a third feed stream that includes at least a portion of H2 of the second product stream; In the hydrogen reaction zone, hydrogen from the third feed stream is reacted with one or more co-reactants to provide a third product stream comprising one or more products, the products including reacted hydrogen atoms from the hydrogen in the third feed stream.

[0212] Implementation Scheme 80. The method according to Implementation Scheme 79, wherein at least 50% H2 of the second product stream is provided to the third feed stream, for example at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0213] Implementation Scheme 81. The method according to Implementation Scheme 79 or Implementation Scheme 80, wherein H2 is provided to the third feed stream from a hydrogen source other than the second product stream.

[0214] Implementation Scheme 82. The method according to any one of Implementation Schemes 79-81, wherein CO is provided to the third feed stream from a CO source other than the second product stream.

[0215] Implementation Scheme 83. The method according to any one of Implementation Schemes 79-82, wherein CO2 is provided to the third feed stream from a CO2 source other than the second product stream.

[0216] Implementation Scheme 84. The method according to any one of Implementation Schemes 79-83, wherein one or more of CH4 and N2 are provided to the third feed stream from a source other than the second product stream.

[0217] Implementation Scheme 85. The method according to any one of Implementation Schemes 79-84, wherein the hydrogen reaction in the hydrogen reaction zone is a Fischer-Tropsch reaction by contacting the third feed stream with a Fischer-Tropsch catalyst, wherein the one or more co-reactants comprise one or more of CO and CO2, and one or more products comprising reacted hydrogen atoms from the hydrogen in the third feed stream comprise C 5+ hydrocarbon.

[0218] Implementation Scheme 86. The method according to Implementation Scheme 85, wherein the third feed stream has a molar H2:COx ratio in the range of 0.5:1 to 5:1.

[0219] Implementation Scheme 87. The method according to Implementation Scheme 85, wherein the third feed stream has a molar H2:COx ratio in the range of 1:1 to 2.5:1.

[0220] Implementation Scheme 88. The method according to Implementation Scheme 85, wherein the third feed stream has a molar H2:COx ratio of at least 1.2:1, for example in the range of 1.2:1 to 2.5:1.

[0221] Implementation Scheme 89. The method according to any one of Implementation Schemes 85-88, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0222] Implementation Scheme 90. The method according to any one of Implementation Schemes 85-88, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount ranging from 5 to 25 wt%, calculated as Co(0).

[0223] Implementation Scheme 91. The method according to any one of Implementation Schemes 85-88, wherein the Fischer-Tropsch catalyst comprises iron in an amount ranging from 25 to 95 wt%, calculated as Fe(O).

[0224] Implementation Scheme 92. The method according to any one of Implementation Schemes 89-91, wherein the Fischer-Tropsch catalyst further comprises manganese.

[0225] Implementation Scheme 93. The method according to any one of Implementation Schemes 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one selected from titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, magnesium oxide, silicon oxide, and zinc oxide.

[0226] Implementation Scheme 94. The method according to any one of Implementation Schemes 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst, and wherein the support comprises at least one of titanium oxide, alumina, and silicon oxide.

[0227] Implementation Scheme 95. The method according to any one of Implementation Schemes 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst and wherein the support is a titanium dioxide support.

[0228] Implementation Scheme 96. The method according to any one of Implementation Schemes 89-95, wherein the Fischer-Tropsch catalyst is activated in a reducing atmosphere.

[0229] Implementation Scheme 97. The method according to Implementation Scheme 96, wherein the reducing atmosphere comprises at least a portion of hydrogen from the second product stream.

[0230] Implementation Scheme 98. The method according to any one of Implementation Schemes 85-97, wherein the third feed stream is contacted with the Fischer-Tropsch catalyst at a temperature in the range of 150-400°C (e.g., 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 200-250°C, or 250-400°C, or 250-350°C, or 250-300°C, or 300-400°C).

[0231] Implementation Scheme 99. The method according to any one of Implementation Schemes 85-97, wherein the contact between the third feed stream and the Fischer-Tropsch catalyst is carried out at a temperature in the range of 200-350°C.

[0232] Implementation Scheme 100. The method according to any one of Implementation Schemes 85-99, wherein the third feed stream is contacted with the Fischer-Tropsch catalyst 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).

[0233] Implementation Scheme 101. The method according to any one of Implementation Schemes 84-98, wherein the contact of the third feed stream with the Fischer-Tropsch catalyst is carried out at a pressure in the range of 20-40 barg.

[0234] Implementation Scheme 102. The method according to any one of Implementation Schemes 85-101, wherein contacting the third feed stream with the Fischer-Tropsch catalyst and dehydrogenation of the second feed stream are carried out in the same facility.

[0235] Implementation Scheme 103. The method according to any one of Implementation Schemes 85-102, wherein the Fischer-Tropsch catalyst is contacted with the third feed stream at C 5+ The selectivity is at least 30%, for example, at least 50%, or at least 70%.

[0236] Implementation Scheme 104. The method according to any one of Implementation Schemes 85-103, wherein the C of the third product stream 5+ Hydrocarbons contain C 5+ Oxygen-containing compounds.

[0237] Implementation Scheme 105. The method according to any one of Implementation Schemes 85-104 further includes separating at least a portion of C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream.

[0238] Implementation Scheme 106. The method according to Implementation Scheme 105 further includes oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream containing CO and / or CO2, and including at least a portion of the pOX stream in the third feed stream.

[0239] Implementation Scheme 107. The method according to Implementation Scheme 105 or Implementation Scheme 106 further includes including at least a portion of the light hydrocarbon stream in the third feed stream.

[0240] Implementation Scheme 108. The method according to any one of Implementation Schemes 85-107, further comprising separating at least a portion of H2 from the third product stream.

[0241] Implementation Scheme 109. The method according to Implementation Scheme 108, wherein at least a portion of the H2 separated from the third product stream is recycled back to the third feed stream.

[0242] Implementation Scheme 110. The method according to Implementation Scheme 108 or Implementation Scheme 109, wherein at least a portion of the H2 separated from the third product stream is used to activate the Fischer-Tropsch catalyst.

[0243] Implementation Scheme 111. The method according to any one of Implementation Schemes 85-110, further comprising separating at least a portion of CO from the third product stream.

[0244] Implementation Scheme 112. The method according to Implementation Scheme 111, wherein at least a portion of the CO separated from the third product stream is provided to the third feed stream.

[0245] Implementation Scheme 113. The method according to any one of Implementation Schemes 85-112, further comprising providing from the third product stream a content of at least 80 wt% C 5+ Hydrocarbons, for example, at least 90 wt% C 5+ C of hydrocarbons 5+ Hydrocarbon product logistics.

[0246] Implementation Scheme 114. The method according to Implementation Scheme 113 further includes causing the C 5+ Hydrocarbon product streams are contacted with hydrogen and a hydrotreating catalyst to hydrotreat the C 5+ At least a portion of the hydrocarbon product stream.

[0247] Implementation Scheme 115. The method according to Implementation Scheme 114, wherein at least a portion of the hydrogen used in the hydrogenation process is provided by the second product stream or the third product stream.

[0248] Implementation Scheme 116. The method according to any one of Implementation Schemes 84-115, wherein at least a portion C of the third product stream is... 5+ Hydrocarbons provide one or more products, which are one or more of fuels, waxes, or oils.

[0249] Implementation Scheme 117. The method according to any one of Implementation Schemes 84-116, wherein at least a portion of H2 in the third feed stream originates from a renewable source.

[0250] Implementation Scheme 118. The method according to any one of Implementation Schemes 79-84, wherein the reaction of hydrogen is carried out by contacting the third feed stream with an ammonia synthesis catalyst, and wherein the one or more co-reactants comprise N2, and wherein one or more products comprising reacted hydrogen atoms from the third feed stream hydrogen contain ammonia.

[0251] Implementation Scheme 119. The method according to Implementation Scheme 118, wherein the third feed stream contains N2 in the range of 10-50 mol%, for example 15-45 mol%, or 20-40 mol%, or 25-35 mol%.

[0252] Implementation Scheme 120. The method according to Implementation Scheme 118 or Implementation Scheme 119, wherein the third feed stream has an H2:N2 ratio in the range of 1:2 to 10:1, for example 1:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 3.5:1.

[0253] Implementation Scheme 121. The method according to Implementation Scheme 120, wherein the third feed stream contains less than 10 mol% CO, CO2 and H2O, for example less than 5 mol% CO, CO2 and H2O, or less than 1 mol% CO, CO2 and H2O, or substantially free of CO, CO2 and H2O.

[0254] Implementation Scheme 122. The method according to any one of Implementation Schemes 118-121, wherein the ammonia synthesis catalyst contains 5-25 wt% Fe on an elemental basis.

[0255] Implementation Scheme 123. The method according to Implementation Scheme 122, wherein the ammonia synthesis catalyst is a promoting catalyst and further comprises aluminum, potassium, calcium, molybdenum and / or magnesium.

[0256] Implementation Scheme 124. The method according to any one of Implementation Schemes 118-123, wherein the third feed stream is contacted with the ammonia synthesis catalyst at a temperature in the range of 200-600°C, for example, 200-550°C, or 200-500°C, or 250-550°C, or 250-500°C, or 200-450°C, or 250-450°C.

[0257] Implementation Scheme 125. The method according to any one of Implementation Schemes 118-124, wherein the third feed stream is contacted with the ammonia synthesis catalyst at a pressure in the range of 30 to 200 barg, for example 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg.

[0258] Implementation Scheme 126. The method according to any one of Implementation Schemes 118-125, wherein the third feed stream is contacted with the ammonia synthesis catalyst and the methanol dehydrogenation step is carried out in the same facility.

[0259] Implementation Scheme 127. The method according to any one of Implementation Schemes 118-126, wherein the third product stream comprises ammonia in an amount greater than 30 mol%, for example greater than 50 mol%, or greater than 75 mol%, or greater than 90 mol%.

[0260] Implementation Scheme 128. The method according to any one of Implementation Schemes 118-127, wherein the ammonia is further converted into urea or nitrate.

[0261] Implementation Scheme 129. The method according to any one of Implementation Schemes 79-83, wherein the reaction of hydrogen is the hydrogenation of an unsaturated organic compound by contacting the third feed stream with a hydrogenation catalyst, wherein one or more co-reactants comprise the unsaturated organic compound, and wherein one or more products comprising reacted hydrogen atoms from the third feed stream hydrogen are hydrogenated organic compounds.

[0262] Implementation Scheme 130. The method according to Implementation Scheme 129, wherein the unsaturated organic compound is one or more of carbonyl compounds, imine compounds, olefin compounds, alkyne compounds, nitro compounds, aromatic compounds, and heteroaromatic compounds.

[0263] Implementation Scheme 131. The method according to Implementation Scheme 129 or Implementation Scheme 130, wherein the hydrogenation catalyst comprises ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum or rhenium.

[0264] Implementation Scheme 132. The method according to any one of Implementation Schemes 129-131, wherein the third feed stream contains less than 10 mol% of CO, CO2, O2 and H2O, for example less than 5 mol% of CO, CO2, O2 and H2O, or less than 1 mol% of CO, CO2, O2 and H2O, or substantially free of CO, CO2, O2 and H2O.

[0265] Implementation Scheme 133. The method according to any one of Implementation Schemes 79-84, wherein the reaction with hydrogen is carried out by contacting the third feed stream with a hydrotreating catalyst, wherein the one or more co-reactants comprise hydrocarbon feed, and wherein one or more products comprising reacted hydrogen atoms from the third feed stream hydrogen comprise hydrotreating hydrocarbon feed.

[0266] Implementation Scheme 134. The method according to Implementation Scheme 133, wherein the one or more co-reactants comprise petroleum-derived hydrocarbon feedstocks.

[0267] Implementation Scheme 135. The method according to Implementation Scheme 133, wherein the one or more co-reactants comprise a renewablely derived hydrocarbon feed.

[0268] Implementation Scheme 136. The method according to any one of Implementation Schemes 133-135, wherein the one or more co-reactants comprise sulfur, oxygen and / or nitrogen in an amount from 0.05 wt% to 20 wt%, for example, 0.05-10 wt%, or in the range of 0.05-5 wt%.

[0269] Implementation Scheme 137. The method according to any one of Implementation Schemes 133-136, wherein the degree of unsaturation of said one or more co-reactants is in the range of 0.05-20 atomic%, for example 0.05-10 wt%, or 0.05-5 wt% unsaturation.

[0270] Implementation Scheme 138. The method according to any one of Implementation Schemes 133-137, wherein the third feed stream is contacted with the hydrotreating catalyst at a temperature in the range of 300-600°C, for example, 300-550°C, or 300-500°C, or 350-550°C, or 350-500°C, or 300-450°C, or 350-450°C.

[0271] Implementation Scheme 139. The method according to any one of Implementation Schemes 133-138, wherein the third feed stream is contacted with the hydrotreating catalyst at a pressure in the range of 30 to 200 barg, for example 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg, or 80 to 160 barg.

[0272] Implementation Scheme 140. The method according to any one of Implementation Schemes 79-84, wherein the reaction of hydrogen is a reaction of hydrogen with oxygen, wherein the one or more co-reactants are oxygen, and wherein one or more products comprising the reacted hydrogen atoms from the third feed stream of hydrogen are water.

[0273] Implementation Scheme 141. The method according to Implementation Scheme 140, wherein the method further comprises storing at least a portion of the hydrogen in the second product stream in a hydrogen fuel tank before being provided to the third feed stream.

[0274] Implementation Scheme 142. The method according to Implementation Scheme 140 or Implementation Scheme 141, wherein the hydrogen reaction zone is a hydrogen fuel cell.

[0275] Implementation Scheme 143. The method according to Implementation Scheme 142, wherein the hydrogen fuel cell is in a vehicle, such as a bus or car.

[0276] Implementation Scheme 144. The method according to Implementation Scheme 142, wherein the hydrogen fuel cell is located in a power plant.

[0277] Implementation Scheme 145. The method according to Implementation Scheme 141, wherein the portion of hydrogen in the second product stream in the hydrogen fuel tank is cooled to a temperature not exceeding -252.8°C, and wherein the hydrogen reaction zone is a hydrogen combustion engine in a rocket.

[0278] Implementation Scheme 146. The method according to any one of Implementation Schemes 1-145, wherein at least a portion of the CO2 in the first feed stream originates from a renewable source.

[0279] Implementation Scheme 147. The method according to any one of Implementation Schemes 1-146, wherein at least a portion of the CO2 in the first feed stream is derived from direct air capture.

[0280] Implementation Scheme 148. The method according to any one of Implementation Schemes 1-147, wherein at least a portion of the CO2 in the first feed stream is captured from a manufacturing plant, such as a bioethanol plant, steel plant, or cement plant.

[0281] Implementation Scheme 149. The method according to any one of Implementation Schemes 1-148, wherein at least a portion of H2 in the first feed stream originates from a renewable source.

[0282] Implementation Scheme 150. The method according to any one of Implementation Schemes 1-149, wherein at least a portion of the hydrogen in the first feed stream is green hydrogen.

[0283] Implementation Scheme 151. The method according to any one of Implementation Schemes 1-150, wherein at least a portion of the hydrogen in the first feed stream is blue hydrogen.

[0284] Implementation Scheme 152. The method according to any one of Implementation Schemes 1-151, wherein at least a portion of the hydrogen in the first feed stream is gray hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen and / or white hydrogen.

[0285] Implementation Scheme 153. The method according to any one of Implementation Schemes 1-152 further includes providing at least a portion of H2 to the first feed stream by electrolysis of water.

[0286] Implementation Scheme 154. The method according to Implementation Scheme 153, wherein the electrolysis of water is carried out using electricity derived at least partially from a renewable source.

[0287] The details shown herein are merely illustrative and intended only to illustrate various embodiments of this disclosure, and are presented to provide the most useful and readily understood description of the principles and concepts of the various embodiments of this disclosure. In this regard, no attempt is made to show details related to the methods of this disclosure in more detail than is necessary for a basic understanding of the methods described herein, and the specification, together with the embodiments, enables those skilled in the art to understand how certain forms of the methods of this disclosure manifest in practice. Therefore, it should be understood that the aspects described herein are not limited to particular embodiments, apparatuses, or configurations before the description of the disclosed methods and apparatus, and thus can certainly be varied. It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting unless specifically defined herein.

[0288] The terms “a,” “an,” “the,” and similar designations used in the context of describing the methods of this disclosure (especially in the context of the following embodiments and claims) should be interpreted to cover both the singular and the plural, unless otherwise indicated herein or the context clearly contradicts them.

[0289] All methods described herein may be performed in any suitable order of steps unless otherwise indicated herein or the context expressly contradicts it. The use of any and all instances or exemplary language (e.g., “for example”) provided herein is intended only to better illustrate the methods of this disclosure and does not constitute a limitation on the scope of this disclosure. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the methods of this disclosure.

[0290] Unless the context explicitly requires otherwise, throughout the specification and claims, the words “comprising,” “including,” etc., 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.” The use of singular or plural forms also includes both singular and plural forms, respectively. Furthermore, the words “this article,” “above,” and “below,” as well as words with similar meanings, should refer to the entire application and not any particular part of it when used in this application.

[0291] As will be understood by those skilled in the art, each embodiment disclosed herein may comprise, consist substantially of, or be composed of the elements, steps, ingredients, or components specifically stated herein. As used herein, the transitional terms “comprising” or “including” mean, but are not limited to, and allow the inclusion of unspecified elements, steps, ingredients, or components, even in substantial quantities. The transitional phrase “consisting of” excludes any unspecified elements, steps, ingredients, or components. The transitional phrase “consisting substantially of” limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiment.

[0292] All percentages, ratios and proportions in this document are by weight unless otherwise specified.

[0293] Although the numerical ranges and parameters described in this disclosure are approximate, the values ​​illustrated in the specific embodiments are reported as precisely as possible. However, any numerical value inherently contains various errors that are necessarily caused by the standard deviation present in its respective test measurement.

[0294] The grouping of alternative elements or embodiments in this disclosure should not be construed as limiting. Each member of a group may be referenced and claimed individually or in any combination with other members of that group or other elements found herein. One or more members of a contemplated group may be included in or removed from the group for convenience and / or patentability reasons. When any such inclusion or removal occurs, this specification is deemed to contain the group as so modified to satisfy the written description of all Markush groups used in the appended claims.

[0295] This document describes several embodiments of various aspects of this disclosure, including the best mode known to the inventors for carrying out the methods described herein. Of course, variations of these embodiments will become apparent to those skilled in the art upon reading the foregoing description. Those skilled in the art will employ such variations as appropriate, and thus the methods of this disclosure can be implemented in ways other than those specifically described herein. Therefore, the scope of this disclosure includes all modifications and equivalents of the subject matter described in the appended claims to the extent permitted by applicable law. Furthermore, unless otherwise indicated herein or the context clearly contradicts it, any combination of the foregoing elements in all possible variations is covered by this disclosure.

[0296] As used in this article, the phrase “at least a part” is used to indicate that at least a part of the quantity is required, up to the entire possible quantity.

[0297] Finally, it should be understood that the various embodiments described herein are illustrative of the methods of this disclosure. Other modifications that may be adopted are within the scope of this disclosure. Therefore, alternative configurations of the methods can be utilized in accordance with the teachings of this document, rather than as examples or limitations. Thus, the methods of this disclosure are not limited to those exactly as shown and described.

Claims

1. A method for producing H2, the method comprising: Provide the first feed flow containing H2 and CO2; The first feed stream is brought into contact 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 containing methanol. Storing at least a portion of the methanol in the first product stream; Provide a second feed stream that includes at least a portion of the stored methanol; In the methanol dehydrogenation reaction zone, at least a portion of the methanol in the second feed stream is dehydrogenated to form a second product stream containing H2 and CO2. Provide a third feed stream that includes at least a portion of H2 of the second product stream; In the hydrogen reaction zone, hydrogen from the third feed stream is reacted with one or more co-reactants to provide a third product stream comprising one or more products, the products including reacted hydrogen atoms from the hydrogen in the third feed stream.

2. The method according to claim 1, wherein the first feed stream comprises at least 20 mol% H2 and at least 10 mol% CO2.

3. The method according to claim 1 or claim 2, wherein the hydrogenation of CO2 is carried out with a carbon selectivity of at least 65% for methanol.

4. The method according to any one of claims 1-3, wherein the hydrogenation of CO2 is carried out with a CO2 conversion rate of at least 45%, and the carbon selectivity for methane is not more than 10%, and the carbon selectivity for CO is not more than 10%.

5. The method according to any one of claims 1-4, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are carried out at intervals of more than 1 km from each other.

6. The method according to any one of claims 1-5, wherein the second feed stream is provided and dehydrogenated during intermittent periods of hydrogen generation from renewable resources.

7. The method according to any one of claims 1-6, wherein the stored portion of methanol in the first product stream is stored for at least one day, for example, at least two days or at least one week.

8. The method according to any one of claims 1-7, wherein the second feed stream comprises at least 20 mol% methanol.

9. The method according to any one of claims 1-8, wherein the molar ratio of water to methanol in the second feed stream is at least 0.

85.

10. The method according to any one of claims 1-9, wherein the methanol dehydrogenation is carried out by contacting the second feed stream with a methanol cracking catalyst disposed in the methanol dehydrogenation reaction zone.

11. The method according to any one of claims 1-9, wherein the methanol dehydrogenation is performed by electrolysis of methanol by contacting at least a portion of the methanol in the second feed stream with an anode in a methanol electrolysis reaction zone, wherein a cathode and a voltage source are provided in the methanol electrolysis reaction zone, the voltage source being arranged to apply a potential between the anode and the cathode.

12. The method according to any one of claims 1-11, wherein the methanol dehydrogenation is carried out with a methanol conversion rate of at least 50%, a carbon product selectivity for CO2 of at least 50%, and a hydrogen product selectivity for H2 of at least 50%.

13. The method according to any one of claims 1-12, wherein the methanol dehydrogenation is carried out with a selectivity for carbon products of CO not exceeding 10%.

14. The method according to any one of claims 1-13, wherein the hydrogen reaction in the hydrogen reaction zone is The Fischer-Tropsch reaction is carried out by contacting the third feed stream with a Fischer-Tropsch catalyst, wherein one or more co-reactants comprise one or more of CO and CO2, and one or more products comprising reacted hydrogen atoms from hydrogen gas from the third feed stream contain C. 5+ hydrocarbon; Ammonia synthesis is carried out by contacting the third feed stream with an ammonia synthesis catalyst, wherein one or more co-reactants comprise N2, and one or more products comprising reacted hydrogen atoms from hydrogen gas from the third feed stream contain ammonia. Hydrogenation of an unsaturated organic compound, which is carried out by contacting the third feed stream with a hydrogenation catalyst, wherein one or more co-reactants include the unsaturated organic compound, and one or more products comprising reacted hydrogen atoms from hydrogen gas from the third feed stream are hydrogenated organic compounds. Hydrotreating is carried out by contacting the third feed stream with a hydrotreating catalyst, wherein one or more co-reactants comprise hydrocarbon feed, and one or more products comprising reacted hydrogen atoms from hydrogen in the third feed stream contain hydrotreated hydrocarbon feed; or The reaction of hydrogen with oxygen, wherein one or more co-reactants are oxygen, and one or more products comprising the reacted hydrogen atoms from the third feed stream are water.

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