Production of hydrogen using methanol

Abstract

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

Description

PRODUCTION OF HYDROGEN USING METHANOLBACKGROUND OF THE DISCLOSUREFIELD

[0001] The present disclosure relates to integrated processes for the production of hydrogen through a methanol intermediate.TECHNICAL BACKGROUND

[0002] Molecular hydrogen is highly relevant compound, both as a source of energy and as a key feedstock in a variety of industrial processes such as Fischer-Tropsch synthesis and the Haber-Bosch process. The growing importance of renewable energy has resulted in 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 electrolysis of water using energy from renewable resources, for example, solar or wind power. Thus, hydrogen represents a fuel / reagent that can be considered as environmentally friendly in both its production and consumption.

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

[0004] While it is possible to store hydrogen for use during an intermission in renewable production of hydrogen, this, too, has significant drawbacks. Hydrogen suffers from poor handling properties compared to other fuels such as liquid hydrocarbons. H2molecules are small, and thus can leak through a variety of dense materials and may cause issues such as hydrogen embrittlement, wherein the ductility of a metal is reduced due to absorbed hydrogen. Additionally, as a gas H2is difficult to transport, as it must be transported in the low-density vapor phase or liquefied under high pressure.

[0005] Accordingly, there exists a need to develop improved protocols for the production and handling of hydrogen.SUMMARY

[0006] The inventors have identified processes to efficiently store and transport hydrogen through the intermediacy of methanol (MeOH). Advantageously, the intermediacy of methanol allows hydrogen produced using renewable energy to be transported and stored in the form of liquid methanol. Additionally, these processes advantageously allow formethanol to be converted back into hydrogen through a variety of processes (e.g., methanol cracking or methanol electrolysis).

[0007] Thus, in one aspect, the present disclosure provides a process for producing hydrogen, the method comprising: providing a first feed stream comprising H2 and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2and CO2, the dehydrogenation having a carbon product selectivity of at least 40% for CO2.

[0008] In another aspect, the present disclosure provides a process for performing an integrated hydrogenation, the method comprising: providing a first feed stream comprising H2and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2and CO2, the dehydrogenation having a carbon product selectivity of at least 40% for CO2; providing a third feed stream comprising at least a portion of H2 of the second product stream; in a hydrogen reaction zone, reacting hydrogen of the third feed stream with one or more co-reactants to provide a third product stream comprising one or more products including reacted hydrogen atoms from hydrogen of the third feed stream.

[0009] Other aspects of the disclosure will be apparent to those skilled in the art in view of the description that follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIGS. 1-4 provide process schematics according to example embodiments of the disclosure.DETAILED DESCRIPTION

[0011] The present disclosure relates generally to techniques for using methanol as an intermediary for hydrogen, especially for the transport and storage thereof. Energy derived from renewable resources often suffer from intermittency in availability. For example, solar energy can only produce usable energy during daytime, and wind energy is only effective during windy periods. As such, a stream of hydrogen produced using such energy sources can likewise be intermittent.

[0012] However, many industrial processes require substantially continuous operation in order to run efficiently (from both a process standpoint and a cost standpoint), and frequent process interruptions can lead to increased energy usage, diminished product output and / or quality, and / or increased wear on the process machinery, potentially leading to lower utilization of and lower lifetimes of capital equipment. Furthermore, effective large-scale energy storage methods are often prohibitively expensive or inefficient. And transport and storage of hydrogen itself present a number of complications.

[0013] Advantageously, the present inventors have recognized that methanol can serve as a storage and transport vehicle for hydrogen, as methanol can be easily transported and stored as a liquid. Thus, stored methanol can serve as a buffer against intermittent hydrogen production, and can help to manage energy-associated intermittency, for example the intermittency of hydrogen produced through the use of electrolysis powered by renewable sources of energy.

[0014] Carbon dioxide is a widely available gas (currently present in the atmosphere at about 400 ppm) that is inert to many transformations. Additionally, the tendency of carbon dioxide to absorb infrared radiation has led to its designation as a greenhouse gas. Thus, there is a need to develop economical processes that utilize carbon dioxide, especially waste carbon dioxide that would otherwise be added to the concentration of carbon dioxide in the atmosphere. Carbon dioxide is produced by many industries where it can be captured as a point source to be used as a feedstock, for example from facilities involved in steel production, fossil fuel power generation, cement production, fermentation processes or fertilizer production. Carbon dioxide may also be sourced from direct air capture projects. One productive way to use captured carbon dioxide is to transform carbon dioxide and hydrogen into methanol. Methanol, being a liquid at ambient temperatures and pressures, may optionally be transported through low-pressure pipelines, ships or trucks, and thusgenerally allows for increased transportation efficiency as a liquid. Methanol in combination with water may then be subjected to a dehydrogenation step in order to regenerate H2, along with CO2.

[0015] Hydrogen has wide-ranging utility as a fuel and as a chemical feedstock. There are methods known in the art for separating H2 from other gases (e.g., CO2) for use in subsequent hydrogen-consuming processes. Alternatively, as CO2 is inert to many transformations, and indeed a co-reactant in others, separation of CO2 from H2 may not be necessary prior to utilization of H2.

[0016] Of course, the net reaction of the hydrogenation step and the dehydrogenation step is conversion of hydrogen and carbon dioxide to hydrogen and carbon dioxide. But, critically, the methanol intermediate between these steps is far more convenient to store and transport than is hydrogen.

[0017] Accordingly, in one aspect, the present disclosure provides an integrated process for producing hydrogen, the method comprising: providing a first feed stream comprising H2and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2 and CO2, the dehydrogenation having a carbon product selectivity of at least 40% for CO2.

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

[0019] Advantageously, the process as described herein can be substantially symmetrical in nature, where the streams entering CO2 hydrogenation and leaving methanol dehydrogenation have similar carbon makeup. As most of the reactions described herein are equilibrium processes, they naturally lend themselves to being integrated symmetrically.

[0020] The first feed stream comprises H2 and CO2 for subsequent contacting with a hydrogenation catalyst for the production of methanol. Accordingly, in various embodiments as otherwise described herein, the first feed stream includes at least 10 mol% H2. For example, in various embodiments, the first feed stream includes at least 20 mol% H2, e.g., at least 30 mol% H2. In various embodiments as otherwise described herein, the first feed stream includes at least 5 mol% CO2. For example, in various embodiments, the first feed stream includes at least 10 mol% CO2, e.g., at least 15 mol% CO2.

[0021] In general, CO2 hydrogenation to produce methanol proceeds according to the reaction: CO2 + 3 H2— > CH3OH + H2O. Accordingly, in various embodiments as otherwise described herein, the ratio of H2:CC>2 of the first feed stream is at least 1 :1 , e.g., at least 1.5:1 , on a molar basis. For example, in various embodiments as otherwise described herein, the ratio of H2:CO2 of the first feed stream is at least 2:1 , e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1 , or at least 6:1 , or at least 8:1. In particular embodiments, the ratio of H2:CC>2 of the first feed stream is no more than 25:1 , e.g., 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 comprises other gases in addition to CO2 and H2. For example, in various embodiments, the first feed stream further comprises one or more of CO, CH4, and N2. For example, in particular embodiments, the first feed stream comprises other gases in addition to CO2 and H2 (e.g., one or more of CO, CH4, and N2) in an amount up to 70 mol%. In various embodiments, the first feed stream comprises 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 comprises no more than 20 mol% CO, e.g., 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 a hydrogenation catalyst. The hydrogenation catalyst may be selected by the person of ordinary skill in the art; various catalysts for hydrogenation of CO2 to methanol are known by the person of ordinary skill in the art. Examples of suitable catalysts include Cu / ZnO catalysts, for example, supported on aluminum oxide or zirconium oxide.

[0024] Advantageously, the CO2 hydrogenation reaction may be performed at a relatively low temperature, leading to increased energy efficiency of the overall process. Forexample, in various embodiments as otherwise described herein, the contacting of the first feed stream with the hydrogenation catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C. In various embodiments, the contacting of the first feed stream with the hydrogenation catalyst is performed at a pressure of no more than 100 barg, for example, no more than 80 barg, or no more than 60 barg.

[0025] As described herein, the hydrogenation of CO2 advantageously produces methanol with relatively high selectivity. Accordingly, in various embodiments as otherwise described herein, the hydrogenation of CO2 is performed with a carbon selectivity of at least 50% for methanol, e.g., at least 55%, or at least 60%. For example, in particular embodiments, the hydrogenation of CO2 is performed with a carbon selectivity of at least 65% for methanol (e.g., at least 70%, or at least 75%, or at least 80% for methanol). Advantageously, the hydrogenation of CO2 can be performed with a low selectivity for methane. In various embodiments as otherwise described herein, the hydrogenation of CO2 is performed with a carbon selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane. As the person of ordinary skill in the art will understand, “carbon selectivity” (sometimes referred to in context merely as “selectivity”) for a given species is the fraction of the carbon-containing reactant that reacts that is converted to that species, i.e. , not counting unreacted material.

[0026] Importantly, the CO2 hydrogenation reaction as described herein is not a reverse water-gas shift reaction. As known in the art, the reverse water-gas shift reaction transforms CO2 and H2 into CO and H2O. Accordingly, in various embodiments as otherwise described herein, the hydrogenation of CO2 is performed with a carbon selectivity of no more than 20% for CO, e.g., no more than 10%, or no more than 5% for CO. In particular embodiments, the hydrogenation of CO2 is performed with a carbon selectivity of no more than 2% for CO, or 1% for CO.

[0027] During the CO2 hydrogenation reaction, at least a portion of the CO2 is hydrogenated to form MeOH and H2O. Advantageously, this process may be performed with a relatively high conversion of CO2. Accordingly, in various embodiments as otherwise described herein, the hydrogenation of CO2 is performed with a conversion of CO2 of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%.

[0028] The person of ordinary skill in the art will be familiar with catalytic methods for the hydrogenation of carbon dioxide to methanol. Various examples of catalysts and catalytic processes are described in R.Guil-Lopez et al., Materials, 12, 3902 (2019); Xiao et al., In:Aresta et al. (eds) An Economy Based on Carbon Dioxide and Water (2019); Marlin et al., Front. Chem. (2018); Rodriguez et al., ACS Cat. 5(11), 6696 (2015); Choundhury, Chem. Cat. Chem. 4(5), 609 (2012), each of which is hereby incorporated herein by reference in its entirety.

[0029] The CO2 hydrogenation produces a first product stream. In various embodiments as otherwise described herein, the first product stream includes at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol. As described herein, the CO2 hydrogenation also has advantageously low selectivity for other products such as methane and / or carbon monoxide. Accordingly, in various embodiments as otherwise described herein, the first product stream includes no more than 10 mol% methane, e.g., no more than 5 mol% methane, or no more than 2 mol% methane. In various embodiments as otherwise described herein, the first product stream includes no more than 10 mol% CO, e.g., no more than 5 mol% CO, or no more than 2 mol% CO. Of course, in some embodiments, there may be more methane and / or CO present, for example, when provided as part of the first feed stream. As would be understood by the skilled person, the composition of the first product stream as disclosed herein is calculated exclusive of inert gas or unreacted CO2 and / or H2.

[0030] As described herein, the CO2 hydrogenation step produces both methanol and water. While an equivalent of water is generally necessary in the methanol dehydrogenation process step, in some embodiments, the formed water can be undesirable in subsequent industrial processes in which the hydrogen released by dehydrogenation is to be used. For example, in the context of Fischer-Tropsch synthesis, excess water present in the methanol dehydrogenation product stream can undesirably cause CO to be converted back to CO2 through the water-gas shift reaction. Moreover, separating water from the methanol avoids the need to store and transport the additional volume and mass of water; in some cases, it may be more cost-efficient overall to separate water from the methanol and reintroduce a desired amount of water for the methanol dehydrogenation. Accordingly, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of water from the first product stream. For example, in particular embodiments, the process further comprises separating at least 50%, or at least 75%, or at least 90% of the water in the first product stream. In various embodiments as otherwise described herein, the portion of the first product stream that is included in the second feed stream has a water content of no more than 10 mol%, e.g., no more than 2 mol%, or no more than 1 mol%, or no more than 0.5 mol%.

[0031] In embodiments in which 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 electrolysis reactor for theformation of H2 gas, e.g., for use in this process or in other processes. In certain embodiments, the separated water is subjected to a purification step before introduction into the electrolysis reactor.

[0032] However, water is a reactant in many dehydrogenation processes that provide substantial amounts of CO2 in combination with hydrogen. And there is typically cost and / or energy involved to separate water from the first product stream and then reintroduce water into the second feed stream, and in some cases, the cost and energy consumed may be substantially more than the cost and energy involved in storage and transport of the water along with the methanol. As such, in various embodiments as otherwise described herein, water is not separated from the first product stream. For example, in various embodiments, the portion of the first product stream that is included in the second feed stream has a water content of at least 10 mol%, e.g., at least 20 mol%, or at least 30 mol%. In various embodiments, the portion of the first product stream that is included in the second feed stream has at least 75% of the water content of the first product stream, e.g., at least 85%, or at least 90%, or at least 95%.

[0033] In various embodiments as otherwise described herein, not all H2 gas input to the CO2 hydrogenation is reacted. Accordingly, in such embodiments, the process may further comprise separating at least a portion of H2from the first product stream. For example, in particular embodiments as otherwise described herein, the process further comprises separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2in the first product stream. The separated H2may be optionally purified, and then optionally recycled. In various embodiments, the 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 processes described herein may be integrated for increased efficiency. For example, in various embodiments as otherwise described herein, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed in the same plant. As would be appreciated by the person of ordinary skill in the art, the “same plant” signifies that the two processes occur within a small geographical area or property, so that it would be economical to directly connect the two without a significant intervening transportation step. Similarly, in various embodiments, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed within 1 km of one another. For example, inparticular embodiments as otherwise described herein, at least a portion of methanol of the first product stream may be provided directly to the second feed stream.

[0035] As described herein, there are a number of uses of hydrogen from the first product stream. Any or all of them may be exploited in a particular real-world process. Notably, the inventors recognize that the presence of hydrogen in the second feed stream may work against the conversion of methanol to carbon monoxide (i.e., because hydrogen is a co-product in that reaction, presence of hydrogen in the second feed stream would force equilibrium in the undesired reverse direction). Accordingly, in various embodiments, the portion of the first product stream that is provided to the second feed stream includes no more than 50% of the hydrogen of the first product stream, e.g., no more than 25%, no more than 10%, or no more than 5% of the hydrogen of the first product stream.

[0036] The portion of the first product stream that is provided to the second feed stream may be advantageously be at elevated temperature and / or pressure. This may reduce capital costs by mitigating the heating and / or pressurization needs of the second feed stream. Accordingly, in various embodiments as otherwise described herein (e.g., when the methanol dehydrogenation is a methanol cracking), the portion of the first product stream that is provided to the second feed stream has a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 C, or 300-400 °C. In other embodiments (e.g., when the methanol dehydrogenation is a methanol electrolysis), the portion of the first product stream that is provided to the second feed stream has a temperature in the range of 0-200 °C, e.g., 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. In particular embodiments, the portion of the first product stream that is provided to the second feed stream is at a pressure of 0 to 50 barg, e.g., 1 to 50 barg.

[0037] Compared to gaseous compositions, compositions that are liquid at ambient temperature and pressure generally possess lower capital expenditure for handling due to their increased density and decreased need for high pressures and / or low temperatures. The present inventors have noted that the methanol product of the CO2 hydrogenation can be simply stored and / or transported. Accordingly, in various embodiments as otherwise described herein, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed in different plants. As used herein, a different “plant” is not merely a different catalyst bed or different vessel, but rather a different facility than the facility in which the carbon dioxide hydrogenation is performed. In various embodiments, the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed more than 1 km from one another. In varioussuch embodiments, the methanol from the first product stream may be stored and / or transported before provision to the second feed stream.

[0038] In various embodiments, regardless of whether the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed in the same or different plants, or near or far from one another, at least a portion of the methanol of the first product stream is stored (e.g., in one or more tanks) before provision to the second feed stream. The storage may be for any suitable time. In various embodiments, the stored portion of the methanol of the first product stream is stored at least one day, e.g., at least two days, or at least three days, or at least 1 week. In particular embodiments, the stored portion of the methanol is transported at least 1 km during storage, e.g., at least 2 km, or at least 10 km. In some embodiments, the methanol may be transported via pipeline. Storage of methanol within a single plant can, for example, allow for stored methanol to be dehydrogenated when provision of hydrogen (e.g., via electrolysis with renewable energy) is not sufficient for process continuity. And storage with transport can allow for a convenient vehicle for the provision of hydrogen to sites remote from a water electrolysis.

[0039] The second feed stream introduces methanol for dehydrogenation to provide CO2 and H2. Methanol dehydrogenation is a distinct process from methanol decomposition. In methanol decomposition, methanol and water are reacted to produce CO and H2. Accordingly, in various embodiments as otherwise described herein, methanol decomposition is not utilized. For example, in particular embodiments, no more than 10% of the H2is derived from methanol decomposition (e.g., no more than 5%, or no more than 1%).

[0040] The water-gas shift reaction is a method to generate H2by reacting carbon monoxide with water. The reaction is reversible as well, where carbon dioxide may be reacted with hydrogen to form carbon monoxide and water. Both of these reactions are conventionally used in the art. Advantageously, the presently disclosed processes can be performed in the absence of substantial use of the water-gas shift reaction, the reverse water-gas shift reaction, or both. Accordingly, in various embodiments as otherwise described herein, less than 10% (e.g., less than 5%, or less than 2%) of each of the H2and CO2of the process are generated by the water-gas shift reaction. In various embodiments as otherwise described herein, less than 10% (e.g., less than 5%, or less than 2%) of each of the CO of the process is generated by the reverse water-gas shift reaction, as appropriate. In various processes as disclosed herein, there is no use of a dedicated water- gas shift reactor or reverse water-gas shift reactor (however, as would be appreciated by theperson of ordinary skill in the art, the water-gas shift reaction or reverse water-gas shift reaction can operate to a minor degree as a side reaction during certain processes).

[0041] Of course, in other processes, water-gas shift or reverse water-gas shift can be used in tandem with the methanol dehydrogenation processes described herein.

[0042] As described herein, methanol dehydrogenation is utilized to form a product stream that includes CO2 and H2. Accordingly, in various embodiments as otherwise described herein, the second feed stream comprises at least 5 mol% methanol. For example, in particular embodiments, the second feed stream comprises at least 7.5% methanol, e.g., at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0043] Typically, methanol dehydrogenation to produce H2 and CO2 proceeds according to the reaction: CH3OH + H2O — > CO2 + 3 H2. Accordingly, in various embodiments as otherwise described herein, the second feed stream comprises water. For example, in some embodiments as described herein, the second feed stream has a concentration of water of at least 5 mol%, e.g., 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 molar ratio of water to methanol of at least 0.75, e.g., at least 0.85, or at least 0.95, or at least 1. In various embodiments as otherwise described herein, the second feed stream has a molar ratio of water to methanol in the range of 0.75-2, e.g., 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 comprise one or more additional gases, which may be inert or reactive. In such embodiments, the second feed stream may further comprise one or more of H2, CO, CH4, CO2, and N2. In particular embodiments, the second feed stream comprises an inert carrier gas, wherein the inert carrier gas includes one or more of CH4and N2. Additionally or alternatively, H2and / or CO2 may be added to the second feed stream in order to tune the methanol reaction. In such embodiments, the second feed stream further comprises H2 and / or CO2. In various embodiments as otherwise described herein, one or more of H2, CO, CH4, CO2, and N2 are be present in second feed stream an amount in the range of up to 50 mol%, e.g., up to 40 mol%, or up to 30 mol%. The person of ordinary skill in the art can select particular additional gases in the second feed stream based, e.g., on the use to which the hydrogen generated will be put, and the process tolerance of the dehydrogenation method used.

[0045] In various embodiments as otherwise described herein, methanol dehydrogenation is performed by the thermocatalytic conversion of methanol and water into H2 and CO2. Such processes are known in the art variously as methanol cracking, methanolreforming, and methanol steam reforming; the present disclosure generally uses the term “methanol cracking” to refer to this process step. In various embodiments as otherwise described herein, the methanol dehydrogenation is a methanol cracking performed by contacting the second feed stream with a methanol cracking catalyst. Any suitable methanol cracking catalyst may be used; a variety are known in the art. For example, the methanol cracking catalyst may include a transition metal, for example, one or more transition metals selected from Groups 8-12 of the periodic table. In particular embodiments, the methanol cracking catalysts comprises one or more of Cr, Ni, Cu, Zn, Pt, or mixtures thereof. In some embodiments, the methanol cracking catalyst may comprise an intermetallic or alloy. For example, the catalyst may further comprise one or more of Sc, Y, Ti, Zr, Ce, B, Al, Ga, In, Si, Ge, Sn, or Sb. The methanol cracking catalyst may be a supported catalyst, wherein the support is a refractory oxide, such as oxidized diamond, silica, zirconia, ceria, titania, alumina, lanthanum oxide, or magnesia. In some embodiments, the methanol cracking catalyst is a copper / zinc oxide catalyst, e.g., on alumina.

[0046] The person of ordinary skill in the art will be familiar with catalytic methods for the cracking of methanol to CO2 and H2. Various examples of catalysts and catalytic processes are described in U.S. Patent no. 9,174,199, JP 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 hereby incorporated herein by reference in its entirety.

[0047] The contacting of the second feed stream with the methanol cracking catalyst occurs at a temperature suitable to effect efficient methanol cracking. In various embodiments as otherwise described herein, the contacting of the second feed stream with the methanol cracking catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C. The contacting may be performed at a variety of suitable pressures. For example, in various embodiments as described herein, the contacting of the second feed with the methanol cracking catalyst is performed at a pressure in the range of 0 to 50 barg, e.g., 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, the contacting of the second feed stream with the methanol cracking catalyst may be performed in the same plant as the contacting of the first feed stream with the hydrogenation catalyst. In such examples, it may be advantageous to coordinate the temperatures of the methanol cracking reaction and the hydrogenation reaction in order to avoid excessive heating and cooling capital costs and energy costs. Accordingly, in particular embodiments as otherwise described herein, the contacting of the second feed stream with the methanol cracking catalyst is performed at a temperature within75 °C of a temperature of the contacting of the first feed stream with the hydrogenation catalyst, e.g., within 50 °C.

[0049] In various embodiments as otherwise described herein, methanol dehydrogenation is performed by the electrolytic conversion of methanol and water to H2 and CO2. For example, in various embodiments as otherwise described herein, the methanol dehydrogenation is a methanol electrolysis performed by electrolyzing at least a portion of the methanol of the second feed stream by contact with an anode in a methanol electrolysis reaction zone, the methanol electrolysis reaction zone having disposed therein a cathode, and a voltage source placing an electrical potential between the cathode and the anode.

[0050] The electrolysis of aqueous methanol can require a lower operating voltage compared to the electrolysis of water. Thus, it can be desirable to electrolyze methanol as a solution in water. In various examples as described herein, the second feed stream has a concentration of water of at least 75 mol%, e.g., at least 80 mol%, or at least 90 mol%. Electrolysis is generally carried out on a feed stream in a liquid phase rather than a vapor phase. As such, the second feed stream has temperature such that the methanol and water of the second feed stream remain substantially in the liquid phase. In various embodiments as described herein, the second feed stream has a temperature no greater than 100 °C, e.g., no greater than 80 °C, or no greater than 65 °C, or no greater than 45 °C. Pressure can be used to operate at temperatures above 65 °C.

[0051] There are various methods known in the art for methanol electrolysis, and thus, the contacting of the second feed stream with the anode is not particularly limited. In various embodiments as described herein, the anode comprises platinum and ruthenium. As described above, electrolysis is generally carried out on a feed stream in a liquid phase rather than a vapor phase. Thus, in various embodiments as described herein, the contacting of the second feed stream with the anode is performed at a temperature no greater than 100 °C, e.g., no greater than 80 °C, or no greater than 65 °C, or no greater than 45 °C.

[0052] As described above, the electrolysis of aqueous methanol can require a lower operating voltage compared to the electrolysis of water. Thus, there is sufficient electrical potential between the anode and cathode such that the aqueous methanol is electrolyzed. For example, in various embodiments as described herein, the contacting of the second feed stream with the anode is performed at an electrical potential between the cathode and the anode greater than 0.02 V, e.g., 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 can require a lower operating voltage compared to the electrolysis ofwater, it can be desirable to apply an electrical potential between the cathode and anode such that the water of the second feed stream is not electrolyzed. As such, in various embodiments as otherwise described herein, the contacting of the second feed stream with the anode is performed at an electrical potential between the cathode and the anode in the range of 0.02 to 2.0 V, e.g., 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 electrolytes disposed between the cathode and anode in order to pass direct electric current between the cathode and the anode. Proton exchange membranes (PEM) are used to conduct protons from the anode to the cathode to generate H2. In various embodiments as described herein, the methanol electrolysis reaction zone has disposed therein a proton exchange membrane disposed between the anode and cathode. In certain embodiments, the proton exchange membrane is Nation. The composition of the cathode is not particularly limiting, and can depend on the composition of the anode. In certain embodiments as described herein, the cathode comprises platinum or palladium.

[0054] One advantage of using electrolysis for methanol dehydrogenation is that the H2 and CO2 produced from methanol electrolysis can be separated as they are produced. CO2 is produced when methanol is oxidized by the anode, and CO2 cannot permeate through the proton exchange membrane to the cathode. Only protons can permeate through the proton exchange membrane to the cathode, wherein they are reduced after contacting the cathode to form H2gas. As such, CO2 can be produced only on the anode side of the methanol electrolysis reaction zone, and H2 can be produced only on the cathode side of the methanol electrolysis reaction zone. For example, in various embodiments as described herein, the second product stream is provided to a plurality of outlets that are distal from one another. In some embodiments, a first portion of the product stream is provided to a first outlet, wherein the first outlet is placed 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, e.g., at least 95 mol% H2, or at least 99 mol% H2, or substantially all H2. Further, in some embodiments, a second portion of the second product stream is provided to a second outlet, wherein the second outlet is placed such that the anode is disposed between the membrane and the second outlet, wherein the second portion of the second product stream is no greater than 10 mol% H2, e.g., no greater than 5 mol% H2, or no greater than 1 mol% H2. For example, in certain embodiments, the second portion of the second product stream is at least 90 mol% CO2, e.g., at least 95 mol% CO2, or at least 99 mol% CO2.

[0055] The methanol dehydrogenation reaction, whether via a thermolytic method or an electrolytic method, generates CO2 and H2, ideally with CO2 as the main carbon product.Accordingly, in various embodiments as otherwise described herein, the dehydrogenation of methanol is performed with a carbon product selectivity of at least 50% for CO2, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90% for CO2. Advantageously, in various embodiments, the methanol dehydrogenation is performed with a selectivity of no more than 20% for CO, e.g., no more than 15%, or no more than 10%, or no more than 5%.

[0056] The main hydrogen product of the methanol dehydrogenation is desirably H2. Accordingly, in various desirable embodiments as otherwise described herein, the dehydrogenation of methanol is performed with a hydrogen product selectivity of at least 50% for H2, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%. As used herein, the hydrogen product selectivity for H2 is calculated as(moles H2 in second product stream - moles H2 in second feed stream) divided by[(moles of H2O in second feed stream - moles H2O in second product stream) + 2x(moles of CH3OH in second feed stream - moles of CH3OH in second product stream)].

[0057] In various embodiments as otherwise described herein, the methanol dehydrogenation is performed with a conversion of methanol of at least 30%, e.g., at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0058] As described herein, the methanol dehydrogenation generates CO2 and H2. Accordingly, in various embodiments as otherwise described herein, the second product stream comprises at least 20 mol% total of CO2 and H2, e.g., at least 35 mol%, or at least 50 mol%, or at least 65 mol%. Without wishing to be bound by theory, methanol dehydrogenation under these conditions is expected to generate 3 moles of H2 per mole of CO2. Accordingly, in various embodiments as otherwise described herein, the second product stream has a molar ratio of hydrogen to carbon dioxide in the range of 0.5:1 to 6:1, e.g., 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 be different, e.g., as a consequence of inclusion of H2 or CO2 in the second feed stream.

[0059] In various embodiments, the second product stream comprises no more than 20 mol% CO, e.g., 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 (for example, any CO present in the second feed stream, is excluded).

[0060] Advantageously, a proportion of methanol is consumed during the methanol dehydrogenation reaction. Accordingly, in various embodiments as otherwise described herein, the second product stream includes no more than 75 mol% methanol, e.g., no morethan 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 includes no more than 15 mol% methanol, e.g., no more than 10 mol% methanol, or no more than 5 mol% methanol, or no more than 2 mol% methanol.

[0061] In some embodiments, further removal of methanol from the second product stream is desired. For example, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of methanol from the second product stream, e.g., separating at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the second product stream. Advantageously, methanol of the second product stream, e.g., at least a portion of the methanol separated from the second product stream, may be transferred or recycled to other processes. For example, in various embodiments as otherwise described herein, the process further comprises recycling to the second feed stream at least a portion of the methanol separated from the second product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol of 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 for subsequent processes. And, notably, hydrogen may already be present in the second feed stream, further increasing the hydrogen content in the second product stream. Accordingly, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of H2from 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] Methods for separating hydrogen from the second product stream are not particularly limited, and a variety of methods for separating hydrogen from a gaseous mixture are known in the art. In various embodiments as described herein, at least a portion of the hydrogen separated from the second product stream is separated using a H2 permeable membrane, or using pressure-swing adsorption. Hydrogen separated from the second product stream in this manner can be substantially pure. In some embodiments as described herein, the portion of separated from the second product stream is greater than 90 mol% H2, e.g., greater than 95 mol% H2, or greater than 99 mol% H2, or substantially all H2.

[0064] The separated H2 may be suitable for a variety of processes. For example, in particular embodiments, at least a portion of the separated H2 from the second product stream is provided to the first feed stream. Additionally or alternatively, in various embodiments as otherwise described herein, the process further comprises activating themethanol cracking catalyst using at least a portion of the H2 separated from the second product stream.

[0065] As described above, the methanol dehydrogenation reaction generates CO2 and H2, ideally with CO2 as a primary carbon product. As such, it may be desirable to separate CO2 from the second product stream instead of separating H2. In various embodiments as otherwise described herein, the process further comprises separating at least a portion of the CO2 from the second product stream. For example, in particular embodiments, at least a portion of the CO2 separated from the second product stream using amine scrubbers. In some embodiments as otherwise described herein, at least a portion of the CO2 is separated from the second product stream by cooling the second product stream to a temperature less than -78.5 °C, e.g., less than -90.0 °C, or less than -100.0 °C.

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

[0067] Of course, in many downstream uses of the generated hydrogen, CO2 is merely inert. And in others, such as iron-based Fischer-Tropsch syntheses, CO2 is a desirable coreactant. Accordingly, in various embodiments the CO2 can remain in admixture with the hydrogen generated in the methanol dehydrogenation.

[0068] The methanol dehydrogenation can be performed to provide hydrogen to a downstream process, e.g., a reaction of hydrogen. Accordingly, in another aspect, the present disclosure provides a process for performing an integrated hydrogenation, the method comprising: providing a first feed stream comprising F^ and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2 and CO2, the dehydrogenation having a carbon product selectivity of at least 40% for CO2; providing a third feed stream comprising at least a portion of H2 of the second product stream;in a hydrogen reaction zone, reacting hydrogen of the third feed stream with one or more co-reactants to provide a third product stream comprising one or more products including reacted hydrogen atoms from hydrogen of the third feed stream.

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

[0070] In various embodiments as described herein, at least a portion of the H2 of the second product stream is provided to the third feed stream. For example, in various embodiments, at least 50% of H2 of the second product stream is provided to the third feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%. In various embodiments, substantially all of the H2 of the second product stream is provided to the third feed stream. Additionally or alternatively, in various embodiments as otherwise described herein, the H2of the third feed stream may be supplied at least in part from a hydrogen source other than the second product stream.

[0071] In various embodiments as otherwise described herein, the third feed stream may include other gases, for example, CO2, CH4, or N2. Other gases, in embodiments where they are included, may be contained in the second product stream and carried through to the third feed stream. But in other embodiments, one or more other gases (e.g., one or more of CO2, CH4, N2) is provided to the third feed stream from a source thereof other than the second product stream.

[0072] In certain embodiments as otherwise described herein, the reaction of hydrogen in the hydrogen reaction zone is a Fischer-Tropsch reaction performed by contacting the third feed steam with a Fischer-Tropsch catalyst, and wherein one or more co-reactants includes one or more of CO and CO2. The person of ordinary skill in the art is familiar with a variety of Fischer-Tropsch processes, and can select particular FT reaction systems and parameters for use in the methods of the disclosure.

[0073] Accordingly, in various embodiments as otherwise described herein, the third feed steam has a molar H2:CO appropriate for Fischer-Tropsch synthesis. For example, in various embodiments, the third feed stream has a molar H2:CO ratio in the range of 0.5:1 to 5:1 , e.g., in the range of 1 :1 to 2.5:1. In particular embodiments, 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 may be selected by the person of ordinary skill in the art. In various embodiments as otherwise described herein, the Fischer-Tropsch catalystcomprises cobalt, iron, rhodium, ruthenium, or a combination thereof (e.g., comprises cobalt or iron). In particular embodiments, the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 2 to 30 wt%, e.g., in the range of 5 to 25 wt%, or in the range of 8 to 20 wt%, calculated as Co(0). In particular embodiments, the Fischer-Tropsch catalyst comprises iron in an amount in the range of 15 to 95 wt%, e.g., 25 to 95 wt%, or 30 to 90 wt%, calculated as Fe(0). In various embodiments as otherwise described herein, the Fischer-Tropsch catalyst further comprises manganese (e.g., comprises manganese in the amount of 0.1 to 15 wt%, or 1 to 10 wt%). As the person of ordinary skill in the art will appreciate, cobalt-based catalysts are especially suitable for use with third feed streams in which a substantial fraction of the carbon oxides are CO, e.g., at least 50 mol%, at least 75 mol%, or at least 90 mol%. Iron-based catalysts are especially suitable for use with third feed streams in which a substantial fraction of the carbon oxides are CO2, e.g., at least 50 mol%, at least 75 mol%, or at least 90 mol%.

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

[0076] Prior to use, certain catalysts require activation. In various embodiments as otherwise described herein, the Fischer-Tropsch catalyst is activated in a reductive atmosphere. In various embodiments, the catalyst is substantially reduced to generate a reduced catalyst material that is used in the catalysis of the Fischer-Tropsch reaction. In embodiments wherein the Fischer-Tropsch catalyst comprises cobalt, this process results in at least portion of the cobalt being transformed into cobalt metal. Desirably, the reduction results in at least 50% of the cobalt being provided as cobalt(O). The person of ordinary skill in the art can use conventional methods to reduce cobalt catalyst materials (e.g., cobalt oxide- or cobalt hydroxide-based materials) to metallic form. In various embodiments as otherwise described herein, the first reducing agent is hydrogen gas, H2. The hydrogen gas may be mixed with other gases, such as an inert carrier gas. Examples of such inert carrier gasses include nitrogen, carbon dioxide, argon, or helium. The hydrogen gas may also be mixed with carbon monoxide, with or without one or more additional carrier gasses. In various embodiments, the reduction is effected by contacting the first catalyst material with a first reducing gas, wherein the first reducing gas comprises the first reducing agent, whereinthe first reducing gas comprises 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 essentially 100 vol% H2). In certain embodiments as described herein, H2 for reduction can come from the second product stream. H2 can also be separated and recycled from the third product stream for use in reducing the Fischer-Tropsch catalyst.

[0077] The temperature of the Fischer-Tropsch synthesis can suitably be in the range of 200-400 °C, such as 200-300 °C, or 210-400 °C, or 210-300 °C, or 220-400 °C, or 220-300 °C. In various embodiments as otherwise described herein, the temperature of the Fischer- Tropsch synthesis is in the range of 200-250 °C, e.g., or 200-240 °C, or 200-230 °C, or 200- 220 °C, or 210-250 °C, or 210-240 °C, or 210-230 °C, or 220-250 °C, or 220-240 °C, or 230- 250 °C. The pressure of the reaction may suitably be in the range from 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. In particular embodiments, the contacting of the third feed stream with the Fischer-Tropsch catalyst is performed at a pressure in the range of 20-40 barg.

[0078] Subject to the limitations described herein, the person of ordinary skill in the art can adapt conventional Fischer-T ropsch catalysts and processes to arrive at the processes of the disclosure. Suitable techniques for catalyst preparation and hydrocarbon synthesis, especially with regard to the synthesis of C5+ hydrocarbons and / or oxygenates, are well- known in the art, for example, described in International Patent Application Publication No. 2019 / 154885, which is hereby incorporated by reference herein in its entirety.

[0079] Advantageously, in various embodiments as otherwise described herein, the contacting of the third feed stream with the Fischer-Tropsch catalyst and the methanol dehydrogenation of the second feed stream may be performed in the same plant. This can be, e.g., within different beds in the same reactor, or in different reactors. In such embodiments, the two processes may be integrated together to provide efficient transformation of methanol to hydrocarbons.

[0080] The Fischer-Tropsch process is typically used to make C5+ hydrocarbons, for example, unsubstituted C5+ hydrocarbons (e.g., alkanes and alkenes) and oxygenated C5+ hydrocarbons (e.g., C5+ alcohols, aldehydes, ketones, carboxylic acids). The Fischer- Tropsch reaction as described herein is desirably operated with a high selectivity for hydrocarbons. For example, in various embodiments as otherwise described herein, the contacting of the Fischer-Tropsch catalyst with the third feed stream is performed with a C5+ selectivity of at least 30%, e.g., at least 50%, or at least 70%. The hydrocarbon composition of the third product stream can vary depending on identify of catalyst and process conditions as known in the art. In various embodiments, the hydrocarbon composition compriseshydrocarbons (e.g., linear hydrocarbons, branched hydrocarbons, saturated or unsaturated hydrocarbons) and oxygenated derivatives thereof. In various embodiments as otherwise described herein, the hydrocarbon composition comprises at least one of alkanes, alkenes, and alcohols.

[0081] In general, longer-chain hydrocarbons are more desirable compared to shorter- chain hydrocarbons. Accordingly, in various embodiments as otherwise described herein, the third product stream comprises C1-C4 hydrocarbons, and the process further comprises separating at least a portion of the C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream. In particular embodiments, the process further comprises oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the third feed stream. For example, catalytic partial oxidation of hydrocarbon feedstocks is described in European Patent Application Publication no.0303438 A1 , which is hereby incorporated herein by reference in its entirety. Additionally or alternatively, in particular embodiments, 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 included, at least in part, in the third feed stream as otherwise described herein.

[0082] The light hydrocarbon stream comprises numerous components, including shortchain (e.g., C1-C4) saturated hydrocarbons, short-chain olefins, and short-chain oxygenates. In particular, olefins (e.g., ethene, propene, butene) and alcohols, may also be recycled to the Fischer-Tropsch reactor in order to generate additional C5+ hydrocarbons. Accordingly, in various embodiments as otherwise described herein, the process further comprises including at least a portion of the light hydrocarbon stream in the third feed stream.Additionally or alternatively, at least a portion of the light hydrocarbon stream can be included in the second feed stream, to be passed through to the third feed stream.

[0083] In various embodiments, the third product stream may comprise unreacted H2. In various embodiments as otherwise described herein, the process further comprises separating at least a portion of H2 of the third product stream. The separated H2 may then be directed to a process in need thereof. For example, in particular embodiments, 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 H2 separated from the third product stream can be used to activate the Fischer-T ropsch catalyst.

[0084] In various embodiments, the third product stream may comprise unreacted CO. In various embodiments as otherwise described herein, the process further comprisesseparating at least a portion of CO of the third product stream. The separated CO may then be directed to a process in need thereof. For example, in particular embodiments, 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 comprise CO2. Accordingly, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of CO2 from the third product stream. The separated CO2 may then be directed to a process in need thereof.

[0086] It can be desirable to provide from the third product stream a C5+ hydrocarbon product stream, i.e. , that contains at least 70 wt% C5+ hydrocarbons, e.g., at least 80 wt% C5+ hydrocarbons, or at least 85 wt% C5+ hydrocarbons. As the person of ordinary skill in the art will appreciate, this can be performed by separating out at least a portion of other components, such as C1-C4 hydrocarbons, CO, CO2 and H2, e.g., as described above.

[0087] Moreover, it can be desirable in some cases to perform further transformations on the C5+ hydrocarbon product stream. Hydroprocessing, i.e., contacting the C5+ hydrocarbon product stream with hydrogen and a hydroprocessing catalyst, can be used for this purpose. Accordingly, in various embodiments, a process as otherwise described herein includes hydroprocessing the C5+ hydrocarbon product stream by contacting the C5+ hydrocarbon product stream with hydrogen and a hydroprocessing catalyst. A variety of hydroprocessing process steps may be used. For example hydrocracking can be used to provide products with lower molecular weight, e.g., to convert higher molecular weight waxes to lower molecular weight products for use as fuels such as aviation fuel, diesel fuel or gasoline. Hydrodeoxygenation can be used to convert oxygenates to non-oxygenated hydrocarbons. Hydroprocessing can also be used to convert olefins to alkanes.Hydroisomerization may be used to alter the mix of hydrocarbon isomers. At least a portion of the H2 used in the hydroprocessing can be H2 provided from one or both of the second and third product streams as described above.

[0088] As the person of ordinary skill in the art will appreciate, the Fischer-Tropsch processes described herein can be used to provide a variety of end products. For example, in various embodiments as otherwise described herein, one or more products are provided from at least a portion of C5+ hydrocarbons of the third product stream. The one or more products can be, for example, one or more of a fuel (e.g., a diesel fuel, a gasoline, or an aviation fuel), a wax or an oil (e.g., for use in lubrication or metalworking).

[0089] The processes described herein can be performed with high throughputs. For example, in various embodiments as otherwise described herein, the CO2 hydrogenation,MeOH dehydrogenation, and / or Fischer-Tropsch synthesis is conducted at a GHSV in the range of 2000 hr1to 20,000 hr1. For example, in various such embodiments the contacting is conducted at a GHSV in the range of 4000 hr1to 18,000 hr1, or 6000 hr1to 16,000 hr1, or 8000 hr1to 12,000 hr1, or 2000 hr1to 12,000 hr1, or 4000 hr1to 10,000 hr1, or 6000 hr1to 10,000 hr1, or 2000 hr1to 8,000 hr1, or 4000 hr1to 8,000 hr1, or 2000 hr1to 6000 hr1. Of course, depending on the system, higher and lower space velocities may also be used.

[0090] Hydrogen gas may be added to the third feed stream in order to increase the H2:COXratio. Conventional H2 gas is most commonly derived from natural gas, often through steam reforming of methane, hydrocarbon partial oxidation, and / or coal gasification. However, each of these methods, as conventionally performed, release significant amounts of CO2 into the atmosphere and rely on fossil fuels as a starting material and / or energy source. In contrast, other sources of H2are known which are preferable from an environmental standpoint. Accordingly, in various embodiments as otherwise described herein, at least a portion of the H2of the second feed stream and / or the third feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) is from a renewable resource.

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

[0092] The Haber-Bosch process is another industrial process that relies on hydrogen, that includes an ammonia synthesis step in which hydrogen and nitrogen are combined to make ammonia. Ammonia serves as a precursor to other nitrogen-containing compounds, such nitrates and ureas, many of which are useful as fertilizers. Accordingly, in various embodiments as otherwise described herein, the reaction of hydrogen is an ammonia synthesis performed by contacting the third feed stream with an ammonia synthesis catalyst, wherein the one or more co-reactants includes N2.

[0093] As described above, the third feed stream can include N2, either carried over from the methanol dehydrogenation reaction or added from another source prior to conduction to the hydrogen reaction zone. Thus, in various embodiments as described herein, the N2 coreactant of the ammonia synthesis is provided by the third feed stream. The third feed stream can comprise sufficient N2 to carry out ammonia synthesis. For example, in various embodiments as described herein, the third feed stream comprises N2 in the range of 10-50 mol%, e.g., 15-45 mol%, or 20-40 mol%, or 25-35 mol%. Ammonia synthesis occurs according to the equation: N2+ 3 H2-> 2 NH3, and as such, the third feed stream cancontain both H2 and N2 in appropriate amounts to synthesize ammonia. For example, in various embodiments as described herein, the third feed stream has a H2:N2 ratio in the range of 1 :2 to 10:1 , e.g., 1 :1 to 5:1 , or 2:1 to 4:1 or 2.5:1 to 3.5:1.

[0094] Oxygen containing molecules, e.g., CO, CO2, and H2O, are known in the art to be ammonia synthesis catalyst poisons. Thus, it can be desirable to limit the amount CO, CO2, and H2O, in the third feed stream. For example, in various embodiments as described herein, the third feed stream comprises less than 10 mol% of CO, CO2, and H2O, e.g., less than 5 mol% CO, CO2, and H2O, or less than 1 mol% CO, CO2, and H2O, or is substantially free of CO, CO2, and H2O.

[0095] Any suitable ammonia synthesis catalyst may be used; a variety are known in the art. For example, the ammonia synthesis catalyst may include a transition metal, for example, iron or ruthenium. In particular embodiments, the ammonia synthesis catalyst comprises 5-25 wt% of Fe, on an elemental basis. In some embodiments, the ammonia synthesis catalyst may further comprise a promoter. For example, in certain embodiments, the ammonia synthesis is a promoted catalyst, further comprising alkali metals, alkali 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, zirconia, ceria, titania, alumina, lanthanum oxide, or magnesia.

[0096] The person of ordinary skill in the art will be familiar with catalysts and catalytic methods for the synthesis of ammonia from H2and N2. Various examples of catalysts and catalytic processes are described in U.S. Patent no. 9,150,423, U.S. Patent no. 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 hereby incorporated herein by reference in its entirety.

[0097] The contacting of the third feed stream with the ammonia synthesis catalyst can be performed under a temperature and pressure sufficient to provide ammonia in the third product stream. The reaction conditions for achieving this are not particularly limiting. For example, in various embodiments as described herein, the contacting of the third feed stream with the ammonia synthesis catalyst is performed at a temperature in the range of 200-600 °C, e.g., 200-550 °C, or 200-500 °C, or 250-550 °C, or 250-500 °C, or 200-450 °C, or 250-450 °C. In various embodiments as otherwise described herein, the contacting of the third feed stream with the ammonia synthesis catalyst is performed at a pressure in the range of 30 to 200 barg, e.g., 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg.

[0098] In certain situations, it can be desirable to integrate the methanol dehydrogenation and the ammonia synthesis for increased efficiency. As such, in variousembodiments as described herein, the contacting of the third feed stream with the ammonia synthesis catalyst and the methanol dehydrogenation are performed in the same plant.

[0099] Ammonia synthesis combines H2 and N2 provide ammonia, ideally with minimal other products. For example, in various embodiments as described herein, the third product stream comprises ammonia in an amount greater than 30 mol%, e.g., greater than 50 mol%, or greater than 75 mol%, or greater than 90 mol%.

[0100] As described above, ammonia is an important precursor to nitrogenous fertilizers. Nitrogenous fertilizers can be provided in many forms, e.g., as ammonia, as an ammonium salt, as a nitrate, or as a urea. In certain embodiments as described herein, the process further comprises converting at least a portion of the ammonia of the third product stream into a nitrate or a urea.

[0101] The hydrogenation of unsaturated organic molecules are an established process in both the chemical and petroleum refining industries. Unsaturated organic molecules, e.g., organic molecules containing at least one double bond and / or triple bond, and / or aromatic molecules, can undergo hydrogenation, wherein the pair of hydrogen atoms of hydrogen are incorporated into the organic molecule, for example, reducing one or more multiple bonds (i.e., double bonds or triple bonds), or breaking of aromaticity. The scope of the hydrogenation of unsaturated organic molecules is not particularly limited, e.g., hydrogenating unsaturated molecules obtained from petroleum refining or hydrogenating complex unsaturated small molecules. In various embodiments as described herein, the reaction of hydrogen is a hydrogenation of an unsaturated organic compound performed by contacting the third feed stream with a hydrogenation catalyst, wherein the one or more coreactants includes the unsaturated organic compound and the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises a hydrogenated organic compound. The unsaturated organic compound being hydrogenated is not particularly limiting. For example, in various embodiments as described herein, the unsaturated organic compound contains one or more of a carbonyl functionality, an imine functionality, a nitro functionality, an alkene functionality, an alkyne functionality, an aromatic functionality, and a heteroaromatic functionality.

[0102] The identity and nature of the hydrogenation catalyst is not particularly limited; and a variety of hydrogenation catalysts are known in the art. For example, the hydrogenation catalyst may include a metal. In various embodiments as described herein, the hydrogenation catalyst comprises ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, rhenium, or a combination thereof. The hydrogenation catalyst can be a heterogeneous hydrogenation catalyst. Alternatively, the hydrogenation catalyst can be ahomogenous hydrogenation catalyst, wherein the metal comprising the hydrogenation catalyst is in the form of single molecules, optionally supported by ligands. In certain embodiments as otherwise described herein, the hydrogenation catalyst is a supported catalyst, wherein the support is a refractory oxide, such as silica, zirconia, ceria, titania, alumina, lanthana, or magnesia.

[0103] Oxygen-containing molecules, e.g., CO, CO2, O2, and H2O, are known in the art to be potential hydrogenation catalyst poisons. Thus, it can be desirable to limit the amount CO, CO2, O2, and H2O, in the third feed stream. For example, in various embodiments as described herein, the third feed stream comprises less than 10 mol% of CO, CO2, O2, and H2O, e.g., less than 5 mol% CO, CO2, O2, and H2O, or less than 1 mol% CO, CO2, O2, and H2O, or is substantially free of CO, CO2, O2, and H2O.

[0104] Hydroprocessing is a term known in the art that encompasses catalytic processes for treating hydrocarbon feeds. These catalytic processes, e.g., hydrotreating and hydrocracking, sulfur, oxygen, nitrogen, and metals from hydrocarbon feeds by replacing heteroatoms (i.e. , sulfur, oxygen and nitrogen) with hydrogen atoms. Additionally, these catalytic processes saturate olefins in the hydrocarbon-based feed. Hydroprocessing is important for reducing emissions when using hydrocarbons as fuels, as the removal of sulfur and nitrogen reduces SOXand NOXemissions when hydrocarbon fuels are combusted. Hydroprocessing can also improve the handling of hydrocarbon-based feeds for other refinery-related processes, as the removal of sulfur prevents downstream reformer catalysts from being poisoned. Thus, in various embodiments as described herein, the reaction with hydrogen is a hydroprocessing conducted by contacting the third feed stream with a hydroprocessing catalyst, wherein the one or more co-reactants includes a petroleum- derived hydrocarbon feed or a renewable-derived hydrocarbon feed, and the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises a hydroprocessed hydrocarbon feed.

[0105] Hydroprocessing of hydrocarbon feeds is discussed in U.S. Patent no. 8,143,438, which is herein incorporated by reference in its entirety.

[0106] As discussed above, hydroprocessing is generally used to remove sulfur, oxygen, nitrogen, and metals from hydrocarbon feeds and to saturate olefins in hydrocarbon feeds. As such, the hydrocarbon feed co-reactants for the hydroprocessing as described herein will comprise sulfur, oxygen, nitrogen, and olefins. For example, in various embodiments as described herein, the hydrocarbon feed comprises sulfur, oxygen, and / or nitrogen in an amount in the range of 0.05 wt% to 20 wt%, e.g., 0.05 wt% to 10 wt%, or 0.05 to 5 wt%. In various embodiments as otherwise described herein, the hydrocarbon feed is unsaturated toa degree in the range of 0.05 to 20 atom% unsaturation, e.g., 0.05 to 10 atom% unsaturation, or 0.05-5 wt% unsaturation.

[0107] Conditions, e.g., temperature and pressure, for hydroprocessing can vary as known in the art. The hydroprocessing is conducted at a temperature and pressure sufficient to provide a hydroprocessed hydrocarbon. For example, in various embodiments as described herein, the contacting of the third feed stream with the hydroprocessing catalyst is performed at a temperature in the range of 300-600 °C, e.g., 300-550 °C, or 350- 550 °C, or 350-500 °C, or 300-450 °C, or 350-450 °C. In various embodiments as otherwise described herein, the contacting of the third feed stream with the hydroprocessing catalyst is performed at a pressure in the range of 30 to 200 barg, e.g., 40 to 190 barg, or 50 to 180 barg, or 80 to 160 barg. Hydroprocessing of hydrocarbon feeds is discussed in U.S. Patent no. 9,187,702, which is herein incorporated by reference in its entirety.

[0108] Hydrogen is not only highly relevant as a reagent in a variety of industrial processes, but also as a fuel. The growing importance of environmentally-responsible, renewable energy has resulted in renewed interest in hydrogen. As a fuel, hydrogen is ideal since it can cleanly react with oxygen in hydrogen fuel cells to provide energy, forming water as the only byproduct. Thus, in various embodiments as otherwise described herein, the reaction of hydrogen is a reaction of hydrogen with oxygen to produce energy, wherein the one or more co-reactants includes oxygen, and wherein the one or more products includes water.

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

[0110] Hydrogen is also used as a fuel for rockets, wherein hydrogen is burned with oxygen in a combustion engine to make steam as a propellant. Hydrogen as rocket fuel is typically stored as a liquid prior to use. Thus, in particular embodiments as described herein, the hydrogen reaction zone is a hydrogen combustion engine in a rocket. Further, in particular embodiments as described herein, at least a portion of the hydrogen of the second product stream is stored in a hydrogen fuel tank prior to being provided to the hydrogencombustion engine in the third feed stream, wherein the portion of hydrogen of the second product stream and the hydrogen fuel tank are cooled to a temperature no more than -252.8 °C.

[0111] The present inventors have noted that carbon dioxide is a chief input of carbon to the processes described herein, and that carbon dioxide can advantageously be provided by a variety of sources. Importantly, at least part of the carbon dioxide of the first feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) can come from a renewable source.

[0112] Carbon dioxide is a common waste material, and often desirable to be removed from waste streams rather than be vented to the atmosphere. Advantageously, the carbon dioxide utilized in the processes described herein may be carbon dioxide collected from the atmosphere or that would otherwise have been released into the atmosphere, e.g., from a combustion or other industrial process. The carbon dioxide may be captured, where it is collected or absorbed after release from an industrial process, or harvested directly from the atmosphere. Methods of carbon dioxide capture are known to those of skill in the art. In various embodiments, at least a portion of the CO2 of the first feed stream is from direct air capture. Additionally or alternatively, carbon dioxide is often scrubbed from industrial effluent, especially processes that generate large amounts of carbon dioxide as a byproduct. Accordingly, in various embodiments as otherwise described herein, at least part of the CO2 of the first feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) is captured from a manufacturing plant, e.g., a bioethanol plant, a steel plant or a cement plant.

[0113] As noted above, renewable sources can be used to provide CO2 to the claimed processes. For example, biomass is an attractive source of renewable carbon dioxide for use in the processes 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 biomass source is agricultural waste or agricultural crop residue. Conventional agricultural activities, including the production of food, feed, fiber, and forest products, generate large amounts of waste plant material. Examples of such materials include corn stover, wheat straw, oat straw, barley straw, sorghum stubble, and rice straw. A third biomass source is through forestry residues left after timber operations. Biomass may also be in the form of commercial waste, industrial waste, sewage sludge, and municipal waste, which includes commercial and residential garbage, including yard trimmings, paper and paperboard, plastics, rubber, leather, textiles, and food waste. Accordingly, in various embodiments as otherwise described herein, the at least a portion of the CO2 of the first feed stream is derived from a renewable source. Forexample, in particular embodiments, at least a portion (e.g., at least 50%, at least 75%, at least 90% or at least 95%) of the CO2 of the first feed stream is derived from biomass, for example, agricultural biomass or municipal waste biomass. Additional sources of agricultural biomass will be apparent to one of skill in the art as dictated by local availability, economics, and process compatibility.

[0114] To generate carbon dioxide from a carbon-containing material, such as biomass, the material is typically subjected to gasification. Gasification involves heating the material under controlled conditions to generate gaseous streams of carbon monoxide, hydrogen, and carbon dioxide. Controlled amounts of other reactants, such as oxygen and / or steam, may be used to tune the process. Gasification conditions are tuned in accordance with the carbon-containing material being gasified in order to efficiently produce gaseous products. In various embodiments, the carbon dioxide of the first feed stream includes carbon dioxide from gasification of biomass, e.g., at least 50%, at least 75%, at least 90% or at least 95% of the carbon dioxide is from gasification of biomass. The biomass may be any source as described above, or from multiple sources may be combined.

[0115] Conventional H2 gas is most commonly derived from natural gas, often through steam reforming of methane, hydrocarbon partial oxidation, and / or coal gasification. However, each of these methods, as conventionally performed, release significant amounts of CO2 into the atmosphere and rely on fossil fuels as a starting material and / or energy source. In contrast, other sources of H2are known which are preferable from an environmental standpoint. Accordingly, in various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream and / or the second feed stream (e.g., at least 50%, at least 75%, at least 90% or at least 95%) is from a renewable resource.

[0116] As known in the art, hydrogen can be provided with color-based names according to its source of production. Examples of types of hydrogen include green hydrogen, blue hydrogen, grey 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. Numerous methods of electrolysis are known in the art. For example, electrolysis may be performed on pure water to produce hydrogen gas and oxygen gas, or on other solutions, such as saline solution, to produce hydrogen gas and another product (e.g., chlorine gas). In particular embodiments, the hydrogen is formed through the electrolysis of a saline solution. Water electrolysis is described further in U.S. Patent No. 4,312,720, U.S. Patent No. 4,021 ,323, and U.S. Patent No. 4,094,751, each of which is incorporated by reference in their entirety.

[0118] To qualify as green hydrogen, the electrical power used for the water electrolysis must be from a renewable source, that is, a source that does not depend on fossil fuel combustion. Example sources of renewable power include solar power through photovoltaic capture or solar thermal technology, wind power, geothermal energy capture, hydroelectric energy, or other renewable sources. Hydrogen that uses solar power for water electrolysis is sometimes called yellow hydrogen. Appropriate renewable energy sources are known to those of skill in the art, and may optionally be selected through certification by an appropriate agency. Accordingly, in various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream is green hydrogen and / or yellow hydrogen. For example, in particular embodiments, the process further comprises providing at least a portion of the H2 of the first feed stream by electrolysis of water. In various embodiments, the electrolysis of water is performed using electricity at least partially derived from a renewable source.

[0119] Blue hydrogen is defined as hydrogen gas produced with some reliance on fossil fuels, but in a process that is overall carbon neutral (i.e. , does not result in any net introduction of carbon dioxide into the atmosphere). In various embodiments as otherwise described herein, the hydrogen utilized in the processes as otherwise described herein comprises blue hydrogen. An example of blue hydrogen is hydrogen gas produced from fossil fuel-derived hydrocarbons such as methane gas, wherein the resulting carbon product is captured or otherwise utilized. For example, steam reforming of methane may be conducted to produce three moles of hydrogen gas and one mole of carbon monoxide for each mole of methane. Methane steam reforming is highly endothermic, requiring significant energy input. Of course, the energy required to perform these processes must be sources from renewable sources, or sources with adequate carbon capture technology. Accordingly, in various embodiments as otherwise 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 through the steam reforming of methane. Steam reforming of methane to produce hydrogen is discussed in International Patent Application Publication no. 2004 / 022480, which is herein incorporated by reference in its entirety. Accordingly, in various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream is blue hydrogen.

[0120] Grey hydrogen is the source of most conventional H2. Grey hydrogen is created from natural gas / methane through steam reforming, but, in contrast to blue hydrogen, none of the resulting greenhouse gases (e.g., CO2) is captured. In various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream is grey hydrogen.

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

[0122] Pink hydrogen is generated through water electrolysis where the required energy for the electrolysis is generated by nuclear power. In various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream is pink hydrogen. Pink hydrogen is also known as purple hydrogen or red hydrogen.

[0123] Turquoise hydrogen is generated by methane pyrolysis, where the byproducts are hydrogen gas and solid elemental carbon. In various embodiments as otherwise described herein, at least a portion of the H2 of the first feed stream is turquoise hydrogen.

[0124] White hydrogen is naturally-occurring hydrogen which can be released through fracking. In various embodiments as otherwise described herein, at least a portion of the H2of the first feed stream is white hydrogen.

[0125] As described herein, the disclosed process, in various embodiments, includes two central reactions: the hydrogenation of CO2 and methanol dehydrogenation. As described herein, these reactions may be advantageously carried out in different spatial arrangements relative to each other. As known in the art, reaction zones are comprised of one or more catalyst beds, and one or more reaction zones may be within the same plant. Different plants are typically geographically separated so that feedstocks cannot be transferred between them without an intervening transportation and storage step.Accordingly, in various embodiments as otherwise described herein, the first reaction zone comprises a first reactor in which the hydrogenation catalyst is disposed, and the second reaction zone comprises a second reactor in which the methanol cracking catalyst is disposed. In various embodiments as otherwise described herein, the first reaction zone comprises a first catalyst bed in which the hydrogenation catalyst is disposed, and the second reaction zone comprises a second catalyst bed in which the methanol cracking catalyst is disposed. In particular embodiments, the first reactor is located in a first plant, and the second reactor is located in a second plant.

[0126] As described herein, in some embodiments, various catalyst beds may be located in different reactors. Locating catalyst beds in separate reactors can have various process advantages. For example, such separation allows individual units to experience reactor downtime (e.g., for maintenance) independently of one another. Further, reactors may be kept at different temperatures to maximize individual process selectivity and efficiency. Exothermic and endothermic chemical reactions require temperature control tomaintain a stable operating temperature. Separate processes occurring in separate reactors leads to simplified temperature control, as different catalysts will change in activity at different rates over time. Accordingly, in certain embodiments as otherwise described herein, the first catalyst bed and the second catalyst bed are not co-mingled. Co-mingling of catalysts occurs when catalysts for different processes share the same catalyst bed. As used herein, two distinct catalyst beds within one reactor are not co-mingled. In certain embodiments as otherwise described herein, the first catalyst bed and the second catalyst bed are disposed within separate reactors.

[0127] An example embodiment is shown in schematic view in FIG. 1 , which depicts a process 100 that is contained within a single plant 141. First feed stream 111 comprising H2 and CO2 is conducted to hydrogenation reaction zone 110 (here, a hydrogenation reactor), and is contacted therein with a hydrogenation catalyst 113, under conditions appropriate to generate first product stream 112 comprising methanol. The first product stream will typically contain other substances as well. For example, in the embodiment of FIG. 1 , the first product stream includes 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 recycle 114. Similarly, the first product stream can include H2(e.g., unreacted H2) and / or CO. Here, at least a portion of H2and / or CO is separated from the first product stream and recycled to the first feed stream 111 via H2and / or CO recycle stream 115. Any water present can be optionally removed from the first product stream 112 by water separation stream 116 prior to the second feed stream (121). Additionally, the water feed stream 116 can optionally be fed to an electrolysis reactor 160.

[0128] In the embodiment of FIG. 1 , the remaining portions of the first product stream 112 (i.e., after the separations described above) are provided to the second feed stream 121. Second feed stream 121 includes at least a portion of the methanol of the first product stream and may be augmented through the introduction of other gases, such as CO2 and / or H2 and / or water through an augmenting feed 118. Second feed stream 121 is conducted to the methanol dehydrogenation reaction zone 120 (here, a methanol dehydrogenation reactor), in which it is contacted with methanol cracking catalyst 123 to decompose at least a portion of the methanol to form a second product stream 122 comprising CO2 and H2. At least a portion of CO2 can be separated from the second product stream via CO2 recycle 124 and recycled to the first feed stream 111 via CO2 recycle 114. Alternatively and / or additionally, at least a portion of H2 from 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 by electrolysis H2 stream 117.

[0129] As noted above, methanol can be formed via hydrogenation of carbon dioxide in a first plant, then transported (e.g., via vehicle or pipeline) to a second plant where the methanol is dehydrogenated and the resulting H2 and / or CO2 are utilized in downstream processes. An example of such an embodiment is shown in schematic view in FIG. 2. Here, the carbon dioxide hydrogenation step of process 200 is performed in a first plant 241. A first feed stream 211 comprising carbon dioxide and hydrogen is conducted to a hydrogenation reaction zone 210 (here, a hydrogenation reactor) containing CO2 hydrogenation catalyst 213. The first feed stream 211 is contacted with the CO2 hydrogenation catalyst 213 to hydrogenate at least a portion of the CO2 to generate a first product stream 212 that includes methanol. First product steam 212 can be subjected to various separations as described herein, not shown, and then methanol of the first product stream can be stored for later use, and / or or transported to another plant. For example, in the embodiment of FIG. 2, at least a portion of the first product stream 212, the portion comprising methanol, is loaded into storage tank 217, then transported to second plant 242, here, by truck 218. The portion of the first product stream is provided to second feed stream 221, which is conducted to methanol dehydrogenation reaction zone 220, in which it is contacted with methanol cracking catalyst 223 to generate second product stream 222 comprising CO2 and H2.

[0130] Another example embodiment is shown in schematic view in FIG. 3. Here, in process 300, first feed stream 311 is conducted to first reaction zone 310 and contacted with CO2 hydrogenation catalyst 313 to hydrogenate at least a portion of CO2of the first feed stream to form first product stream 312 comprising methanol. First product stream 312 is conducted from the first reaction zone 310 and additional gas stream 324 is added, and the resulting mixture is provided as second feed stream 321. Second feed stream 321 conducted to methanol dehydrogenation reaction zone 320 in which with methanol cracking catalyst 323 to provide second product stream 322. Here, second product stream 322 is conducted 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 is recycled to the second feed stream 321 via methanol recycle 325. Notably, at least a portion of H2of the second product stream 322 can be separated and recycled to the first feed stream 311 via H2recycle 326. At least a portion of H2of the second product stream 322 may also or alternatively be provided to an external reactor or process through H2stream 327.

[0131] Another example embodiment, wherein the methanol dehydrogenation is a methanol electrolysis, is shown in schematic view in FIG 4. Here, in process 400, first feed stream 411 is conducted to first reaction zone 410 and contacted with CO2 hydrogenationcatalyst 413 to hydrogenate at least a portion of CO2 of the first feed stream to form first product stream 412 comprising methanol. First product stream 412 is conducted from the first reaction zone 410 and additional water stream 424 is added, and the resulting mixture is provided as second feed stream 421. Second feed stream 421 is conducted to the methanol electrolysis reaction zone, wherein anode 423a, cathode 423b, and proton exchange membrane 423c are disposed. Second feed stream 421 is contacted with anode 423a to provide the second product stream as two separate streams, CO2 product stream 422a and H2 product stream 422b. At least a portion of CO2 product stream 422a can be separated and recycled back to first feed stream 411 via CO2 recycle 425.

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

[0133] Embodiment 1. A process for producing H2, the process comprising: providing a first feed stream comprising H2and CO2; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reaction zone) to hydrogenate at least a portion of the CO2 to form a first product stream comprising methanol; providing a second feed stream comprising at least a portion of the methanol of the first product stream; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2 and CO2,

[0134] Embodiment 2. The process according to embodiment 1, wherein the first feed stream includes at least 10 mol% H2, e.g., at least 20 mol% H2, or at least 30 mol% H2.

[0135] Embodiment s. The process according to embodiment 1 or embodiment 2, wherein the first feed stream includes at least 5 mol% CO2, e.g., at least 10 mol% CO2, or at least 15 mol% CO2.

[0136] Embodiment 4. The process according to any of embodiments 1-3, wherein a ratio of H2:CO2 of the first feed stream is at least 1:1, e.g. at least 1.5:1 , at least 2:1 , at least 2.5:1 , at least 3:1, or at least 4:1 , or at least 5:1, or at least 6:1 , or at least 8:1.

[0137] Embodiment 5. The process according to any of embodiments 1-4, wherein a ratio of H2:CO2 of the first feed stream is no more than 25:1, e.g., no more than 20:1 , or no more than 15:1 , or no more than 12:1.

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

[0139] Embodiment 7. The process according to any of embodiments 1-6, wherein the first feed stream comprises 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] Embodiment 8. The process according to any of embodiment 1-7, wherein the first feed stream comprises no more than 20 mol% CO, e.g., no more than 15 mol% CO, or no more than 10 mol% CO, or no more than 5 mol% CO.

[0141] Embodiment 9. The process according to any of embodiments 1-8, wherein the hydrogenation catalyst is a copper / zinc oxide catalyst, e.g., supported on aluminum oxide or zirconium oxide.

[0142] Embodiment 10. The process according to any of embodiments 1-9, wherein the contacting of the first feed stream with the hydrogenation catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C.

[0143] Embodiment 11 . The process according to any of embodiments 1-10, wherein the hydrogenation of CO2 is performed with a carbon selectivity of at least 50% for methanol, e.g., at least 65% or at least 80%.

[0144] Embodiment 12. The process according to any of embodiments 1-11 , wherein the hydrogenation of CO2 is performed with a carbon selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5%.

[0145] Embodiment 13. The process according to any of embodiments 1-12, wherein the hydrogenation of CO2 is performed with a carbon selectivity of no more than 20% for CO, e.g., no more than 10%, or no more than 5%.

[0146] Embodiment 14. The process according to any of embodiments 1-13, wherein the hydrogenation of CO2 is performed with a conversion of CO2 of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%.

[0147] Embodiment 15. The process according to any of embodiments 1-14, wherein the first product stream includes at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol.

[0148] Embodiment 16. The process according to any of embodiments 1-15, wherein the first product stream includes no more than 10 mol% methane, e.g., no more than 5 mol% methane, or no more than 2 mol% methane.

[0149] Embodiment 17. The process according to any of embodiments 1-16, wherein the first product stream includes no more than 10 mol% CO, e.g., no more than 5 mol% CO, or no more than 2 mol% CO.

[0150] Embodiment 18. The process according to any of embodiments 1-17, further comprising separating at least a portion of water from the first product stream (e.g., at least 50%, at least 75%, or at least 90% of water in the first product stream).

[0151] Embodiment 19. The process of any of embodiments 1-18, wherein the portion of the first product stream that is included in the second feed stream has a water content of at least 10 mol%, e.g., or at least 20 mol%, or at least 30 mol%.

[0152] Embodiment 20. The process of any of embodiments 1-19, wherein the portion of the first product stream that is included in the second feed stream has at least 75% of the water content of the first product stream, e.g., at least 85%, or at least 90%, or at least 95%.

[0153] Embodiment 21. The process according to any of embodiments 1-20, further comprising separating at least a portion of H2from 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 H2in the first product stream).

[0154] Embodiment 22. The process of embodiment 21, further comprising recycling to the first feed stream at least a portion of the H2separated from the first product stream.

[0155] Embodiment 23. The process of any of embodiments 1-22, wherein the portion of the first product stream that is provided to the second feed stream includes no more than 50% of the hydrogen of the first product stream, e.g., no more than 25%, no more than 10%, or no more than 5% of the hydrogen of the first product stream.

[0156] Embodiment 24. The process of any of embodiments 1-23, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed in the same plant.

[0157] Embodiment 25. The process of any of embodiments 1-24, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed within 1 km of each other.

[0158] Embodiment 26. The process according to any of embodiments 1-25, wherein at least a portion of methanol of the first product stream is provided directly to the second feed stream.

[0159] Embodiment 27. The process according to embodiment 26 wherein the portion of the first product stream that is provided to the second feed stream has a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 C, or 300-400 °C.

[0160] Embodiment 28. The process according to embodiment 26, wherein the portion of the first product stream that is provided to the second feed stream has a temperature in the range of 0-200 °C, e.g., 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] Embodiment 29. The process according to any of embodiments 1-28, wherein the dehydrogenation and the contacting of the first feed stream with the hydrogenation catalyst are performed in different plants.

[0162] Embodiment 30. The process according to any of embodiments 1-29, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed more than 1 km from one another

[0163] Embodiment 31. The process according to any of embodiments 1-30, wherein at least a portion of methanol of the first product stream is stored (e.g., in one or more tanks) before provision to the second feed stream.

[0164] Embodiment 32. The process according to embodiment 31, wherein the stored portion of the methanol of the first product stream is stored for at least one day, e.g., at least two days or at least a week.

[0165] Embodiment 33. The process according to embodiment 31 or embodiment 32, wherein the stored portion of the methanol is transported at least 1 km during storage, e.g., at least 2 km or at least 10 km.

[0166] Embodiment 34. The process according to any of embodiments 31-33, wherein the second feed stream is provided and dehydrogenated during a period of intermittency in hydrogen generation using energy from a renewable resource (e.g., via electrolysis with renewable energy).

[0167] Embodiment 35. The process according to any of embodiments 1-34, wherein the second feed stream comprises at least 5 mol% methanol, e.g., 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] Embodiment 36. The process according to any of embodiments 1-35, wherein the second feed stream further comprises H2O, and one or more of H2, CO, CH4, CO2 and N2.

[0169] Embodiment 37. The process according to any of embodiments 1-30, wherein the second feed stream has a concentration of water of at least 5 mol%, e.g., e.g., at least 7.5 mol%, or at least 10 mol%, or at least 15%, or at least 20%, or at least 25 mol%.

[0170] Embodiment 38. The process according to any of embodiments 1-36, wherein a molar ratio of water to methanol of the second feed stream is at least 0.75, e.g., at least 0.85, or at least 0.95, or at least 1.

[0171] Embodiment 39. The process according to any of embodiments 1-38, wherein a molar ratio of water to methanol of the second feed stream is in the range of 0.75-2, e.g., 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] Embodiment 40. The process according to any of embodiments 1-39, wherein the methanol dehydrogenation is a methanol cracking performed by contacting the second feed stream with a methanol cracking catalyst disposed in the methanol dehydrogenation reaction zone

[0173] Embodiment 41. The process of embodiment 40, the method further comprising activating the methanol cracking catalyst using at least a portion of the H2separated from the first product stream.

[0174] Embodiment 42. The process according embodiments 40 or embodiment 41 , wherein the methanol cracking catalyst comprises copper, e.g., on an alumina carrier.

[0175] Embodiment 43. The process according to any of embodiments 40-42, wherein the contacting of the second feed stream with the methanol cracking catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C.

[0176] Embodiment 44. The process according to any of embodiments 40-43, wherein the contacting of the second feed stream with the methanol cracking catalyst is performed at a pressure in the range of 1-50 barg, e.g., 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] Embodiment 45. The process according to any of embodiments 40-44, wherein the contacting of the second feed stream with the methanol cracking catalyst is performed at a temperature within 75 °C of a temperature of the contacting of the first feed stream with the hydrogenation catalyst, e.g., within 50 °C.

[0178] Embodiment 46. The process according to any of embodiments 1-39, wherein the methanol dehydrogenation is a methanol electrolysis performed by electrolyzing at least a portion of the methanol of the second feed stream by contact with an anode in an methanol electrolysis reaction zone, the methanol electrolysis reaction zone having disposed therein a cathode, and a voltage source arranged to place an electrical potential between the anode and the cathode.

[0179] Embodiment 47. The process of embodiment 46, wherein the second feed stream has a concentration of water of at least 75 mol%, e.g., at least 80 mol%, or at least 90 mol%.

[0180] Embodiment 48. The process of embodiment 46 or embodiment 47, wherein second feed stream has a temperature no greater than 100 °C, e.g., no greater than 80 °C, or no greater than 60 °C, or no greater than 40 °C.

[0181] Embodiment 49. The process of any of embodiments 46-48, wherein the anode comprises platinum and ruthenium.

[0182] Embodiment 50. The process of any of embodiments 46-49, wherein the contacting of the second feed stream with the anode is performed at a temperature no greater than 100 °C, e.g., no greater than 80 °C, or no greater than 65 °C, or no greater than 45 °C.

[0183] Embodiment 51. The process of any of embodiments 46-50, wherein the contacting of the second feed stream with the anode is performed at an electrical potential between the cathode and the anode in the range of 0.02 to 2.0 V, e.g., 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 O.3-1.4 V, or 0.3-1.0 V.

[0184] Embodiment 52. The process of any of embodiments 46-51 , wherein the methanol electrolysis reaction zone has disposed therein a membrane disposed between the anode and the cathode.

[0185] Embodiment 53. The process of embodiment 52, wherein the membrane is proton permeable.

[0186] Embodiment 54. The process of embodiment 52 or embodiment 53, wherein the cathode comprises platinum or palladium.

[0187] Embodiment 55. The process of any of embodiments 52-54, wherein the second product stream is provided to a plurality of outlets that are distal from one another.

[0188] Embodiment 56. The process of embodiment 55, wherein a first portion of the second product stream provided to a first outlet, wherein the first outlet is placed 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, e.g., at least 95 mol% H2, or at least 99 mol% H2, or substantially all H2.

[0189] Embodiment 57. The process of embodiment 55 or embodiment 56, wherein a second portion of the second product stream provided to a second outlet, wherein the second outlet is placed such that the anode is disposed between the membrane and the second outlet, wherein the second portion of the second product stream is no greater than 10 mol% H2, e.g., no greater than 5 mol% H2, or no greater than 1 mol% H2, or substantially free H2.

[0190] Embodiment 58. The process of embodiment 57, wherein the second portion of the second product stream is at least 90 mol% CO2, e.g., at least 95 mol% CO2, or at least 99 mol% CO2.

[0191] Embodiment 59. The process according to any of embodiments 1-58, wherein the dehydrogenation of methanol is performed with a carbon product selectivity of at least 50% for CO2, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0192] Embodiment 60. The process according to any of embodiments 1-59, wherein the dehydrogenation of methanol is performed with a carbon product selectivity of no more than 20% for CO, e.g., no more than 15%, no more than 10%, or no more than 5%.

[0193] Embodiment 61 . The process according to any of embodiments 1-60, wherein the dehydrogenation of methanol is performed with a hydrogen product selectivity of at least 50% for H2, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%.

[0194] Embodiment 62. The process according to any of embodiments 1-61 , wherein the dehydrogenation of methanol is performed with a conversion of methanol of at least 30%, e.g. at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0195] Embodiment 63. The process according to any of embodiments 1-62, wherein the second product stream includes at least 20 mol% total of CO2 and H2, e.g., at least 35 mol%, or at least 50 mol%, or at least 65 mol%.

[0196] Embodiment 64. The process of any of embodiments 1-63, wherein the second product stream comprises no more than 20 mol% CO, e.g., no more than 15 mol% CO, orno more than 10 mol% CO, or no more than 5 mol% CO, excluding CO not derived from methanol dehydrogenation.

[0197] Embodiment 65. The process according to any of embodiments 1-64, wherein the second product stream has a molar ratio of hydrogen to carbon dioxide in the range of 0.5:1 to 6:1, e.g., 1:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 3.5:1.

[0198] Embodiment 66. The process according to any of embodiments 1-65, wherein the second product stream includes no more than 75 mol% methanol, e.g., no more than 60 mol% methanol, or no more than 50 mol% methanol, or no more than 25 mol% methanol.

[0199] Embodiment 67. The process according to any of embodiments 1-65, wherein the second product stream includes no more than 15 mol% methanol, e.g., no more than 10 mol% methanol, or no more than 5 mol% methanol, or no more than 2 mol% methanol.

[0200] Embodiment 68. The process according to any of embodiments 1-67, further comprising 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 methanol in the second product stream).

[0201] Embodiment 69. The process of embodiment 68, further comprising recycling to the second feed stream at least a portion of the methanol separated from the second product stream, e.g., at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol of the second product stream.

[0202] Embodiment 70. The process of any of embodiments 1-69, further comprising separating at least a portion of H2from the second product stream (e.g., at least 50 %, or at least 75%, or at least 90% of the H2in the second product stream).

[0203] Embodiment 71. The process of embodiment 70, wherein at least a portion of H2is separated from the second product stream using an H2permeable membrane.

[0204] Embodiment 72. The process of embodiment 70, wherein at least a portion of H2is separated from the second product stream using pressure-swing adsorption.

[0205] Embodiment 73. The process of any of embodiments 70-72, wherein the portion separated from the second product stream is greater than 90 mol% H2, e.g., greater than 95 mol% H2, or greater than 99 mol%, or substantially all H2.

[0206] Embodiment 74. The process of embodiment 73, further comprising providing at least a portion of the H2separated from the second product stream to the first feed stream.

[0207] Embodiment 75. The process of any of embodiments 1-74, further comprising separating at least a portion of the CO2from the second product stream.

[0208] Embodiment 76. The process of embodiment 75, wherein at least a portion of the CO2 is separated from the second product stream using amine scrubbing.

[0209] Embodiment 77. The process of embodiment 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 less than -78.5 °C, e.g., less than -90.0 °C, less than -100.0 °C.

[0210] Embodiment 78. The process of any of embodiments 75-77, further comprising providing at least a portion of the CO2 separated from the second product stream to the first feed stream.

[0211] Embodiment 79. The process of any of embodiments 1-78, the method further comprising: providing a third feed stream comprising at least a portion of H2 of the second product stream; in a hydrogen reaction zone, reacting hydrogen of the third feed stream with one or more co-reactants to provide a third product stream comprising one or more products including reacted hydrogen atoms from hydrogen of the third feed stream.

[0212] Embodiment 80. The process of embodiment 79, wherein at least 50% of H2of the second product stream is provided to the third feed stream, e.g., at least 75%, or at least 90%, or at least 95%, or at least 99%.

[0213] Embodiment 81 . The process of embodiment 79 or embodiment 80, wherein H2is provided to the third feed stream from a hydrogen source other than the second product stream.

[0214] Embodiment 82. The process of any of embodiments 79-81 , wherein CO is provided to the third feed stream from a CO source other than the second product stream.

[0215] Embodiment 83. The process of any of embodiments 79-82, wherein CO2 is provided to the third feed stream from a CO2 source other than the second product stream.

[0216] Embodiment 84. The process of any of embodiments 79-83, wherein one or more of CH4 and N2 is provided to the third feed stream from a source thereof other than the second product stream.

[0217] Embodiment 85. The process of any of embodiments 79-84, wherein the reaction of hydrogen in the hydrogen reaction zone is a Fischer-Tropsch reaction performed by contacting the third feed stream with a Fischer-Tropsch catalyst, wherein the one or more co-reactants includes one or more of CO and CO2, and wherein the one or more productsincluding reacted hydrogen atoms from hydrogen of the third feed stream comprises C5+ hydrocarbons.

[0218] Embodiment 86. The process of embodiment 85, wherein the third feed stream has a molar H2:COXratio in the range of 0.5: 1 to 5: 1.

[0219] Embodiment 87. The process of embodiment 85, wherein the third feed stream has a molar H2:COXratio in the range of 1 : 1 to 2.5: 1.

[0220] Embodiment 88. The process of embodiment 85, wherein the third feed stream has a molar H2:COXratio of at least 1.2:1, e.g., in the range of 1.2:1 - 2.5:1.

[0221] Embodiment 89. The process of any of embodiments 85-88, wherein the Fischer-Tropsch catalyst comprises cobalt, iron, rhodium, ruthenium, or a combination thereof.

[0222] Embodiment 90. The process of any of embodiments 85-88, wherein the Fischer-Tropsch catalyst comprises cobalt in an amount in the range of 5-25 wt%, calculated as Co(0).

[0223] Embodiment 91. The process of any of embodiments 85-88, wherein the Fischer-Tropsch catalyst comprises iron in an amount in the range of 25-95 wt%, calculated as Fe(0).

[0224] Embodiment 92. The process of any of embodiments 89-91 , wherein the Fischer-Tropsch catalyst further comprises manganese.

[0225] Embodiment 93. The process of any of embodiments 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, magnesium oxide, silicon oxide and zinc oxide.

[0226] Embodiment 94. The process of any of embodiments 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support comprises at least one of titanium oxide, aluminum oxide, and silicon oxide.

[0227] Embodiment 95. The process of any of embodiments 89-92, wherein the Fischer-Tropsch catalyst is a supported catalyst, wherein the support is a titanium dioxide support.

[0228] Embodiment 96. The process of any of embodiments 89-95, wherein the Fischer-Tropsch catalyst is activated in a reductive atmosphere.

[0229] Embodiment 97. The process of embodiment 96, wherein the reductive atmosphere comprises at least a portion of hydrogen from the second product stream.

[0230] Embodiment 98. The process of any of embodiments 85-97, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst is performed 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 200-300 °C, or 200-250 °C, or 250-400 °C, or 250-350 °C, or 250-300 °C, or 300-400 °C).

[0231] Embodiment 99. The process of any of embodiments 85-97, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst is performed at a temperature in the range of 200-350 °C.

[0232] Embodiment 100. The process of any of embodiments 85-99, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst is performed 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] Embodiment 101. The process of any of embodiments 84-98, wherein the contacting of the third feed stream with the Fischer-Tropsch catalyst is performed at a pressure in the range of 20-40 barg.

[0234] Embodiment 102. The process of any of embodiments 85-101, wherein the contacting of third feed stream with the Fischer-Tropsch catalyst and the dehydrogenization of the second feed stream are performed in the same plant.

[0235] Embodiment 103. The process of any of embodiments 85-102, wherein the contacting of the Fischer-Tropsch catalyst with the third feed stream is performed with a C5+ selectivity of at least 30%, e.g., at least 50%, or at least 70%.

[0236] Embodiment 104. The process of any of embodiments 85-103, wherein the C5+ hydrocarbons of the third product stream comprise C5+ oxygenates.

[0237] Embodiment 105. The process of any of embodiments 85-104, further comprising separating at least a portion of C1-C4 hydrocarbons from the third product stream to provide a light hydrocarbon stream.

[0238] Embodiment 106. The process of embodiment 105, further comprising oxidizing at least a portion of the light hydrocarbon stream in a partial oxidation reactor to provide a pOX stream comprising CO and / or CO2, and including at least a portion of the pOX stream in the third feed stream.

[0239] Embodiment 107. The process of embodiment 105 or embodiment 106, further comprising including at least a portion of the light hydrocarbon stream in the third feed stream.

[0240] Embodiment 108. The process of any of embodiments 85-107, further comprising separating at least a portion of H2 of the third product stream.

[0241] Embodiment 109. The process of embodiment 108, wherein at least a portion of the H2 separated from the third product stream is recycled to the third feed stream.

[0242] Embodiment 110. The process of embodiment 108 or embodiment 109, wherein at least a portion of the H2 separated from the third product stream is used to activate the Fischer-T ropsch catalyst.

[0243] Embodiment 111. The process of any of embodiments 85-110, further comprising separating at least a portion of CO of the third product stream.

[0244] Embodiment 112. The process of embodiment 111 , wherein at least a portion of the CO separated from the third product stream is provided to the third feed stream.

[0245] Embodiment 113. The process of any of embodiments 85-112, further comprising providing from the third product stream a C5+ hydrocarbon product stream comprising at least 80 wt% C5+ hydrocarbons, e.g., at least 90 wt% C5+ hydrocarbons.

[0246] Embodiment 114. The process of embodiment 113, further comprising hydroprocessing at least a portion of the C5+ hydrocarbon product stream by contacting the C5+ hydrocarbon product stream with hydrogen and a hydroprocessing catalyst.

[0247] Embodiment 115. The process of embodiment 114, wherein at least a portion of the hydrogen used in the hydroprocessing is provided from the second product stream or the third product stream.

[0248] Embodiment 116. The process of any of embodiments 84-115, wherein one or more products are provided from at least a portion of C5+ hydrocarbons of the third product stream, the one or more products being one or more of a fuel, a wax, or an oil.

[0249] Embodiment 117. The process of any of embodiments 84-116, wherein at least part of the H2of the third feed stream is from a renewable source.

[0250] Embodiment 118. A process of any of embodiments 79-84, wherein the reaction of hydrogen is an ammonia synthesis performed by contacting the third feed stream with an ammonia synthesis catalyst, wherein the one or more co-reactants includes N2, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises ammonia.

[0251] Embodiment 119. A process of embodiment 118, wherein the third feed stream comprises N2 in the range of 10-50 mol%, e.g., 15-45 mol%, or 20-40 mol%, or 25-35 mol%.

[0252] Embodiment 120. A process of embodiment 118 or embodiment 119, wherein the third feed stream has a H2:N2 ratio in the range of 1:2 to 10:1 , e.g., 1 :1 to 5:1, or 2:1 to 4:1 or 2.5:1 to 3.5:1.

[0253] Embodiment 121. A process of embodiment 120, wherein the third feed stream comprises less than 10 mol% of CO, CO2, and H2O, e.g., less than 5 mol% CO, CO2, and H2O, or less than 1 mol% CO, CO2, and H2O, or is substantially free of CO, CO2, and H2O.

[0254] Embodiment 122. A process of any of embodiments 118-121, wherein the ammonia synthesis catalyst comprises 5-25 wt% Fe, on an elemental basis.

[0255] Embodiment 123. A process of embodiment 122, wherein the ammonia synthesis catalyst is a promoted catalyst, further comprising aluminum, potassium, calcium, molybdenum, and / or magnesium.

[0256] Embodiment 124. A process of any of embodiments 118-123, wherein the contacting of the third feed stream with the ammonia synthesis catalyst is performed at a temperature in the range of 200-600 °C, e.g., 200-550 °C, or 200-500 °C, or 250-550 °C, or 250-500 °C, or 200-450 °C, or 250-450 °C.

[0257] Embodiment 125. A process of any of embodiments 118-124, wherein the contacting of the third feed stream with the ammonia synthesis catalyst is performed at a pressure in the range of 30 to 200 barg, e.g., 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg.

[0258] Embodiment 126. The process of any of embodiments 118-125, wherein the contacting of third feed stream with the ammonia synthesis catalyst and the methanol dehydrogenation step are performed in the same plant.

[0259] Embodiment 127. The process of any of embodiments 118-126, wherein the third product stream comprises ammonia in an amount greater than 30 mol%, e.g., greater than 50 mol%, or greater than 75 mol%, or greater than 90 mol%.

[0260] Embodiment 128. The process of any of embodiments 118-127, wherein the ammonia is further converted to a urea or a nitrate.

[0261] Embodiment 129. A process of any of embodiments 79-83, wherein the reaction of hydrogen is a hydrogenation of an unsaturated organic compound performed by contacting the third feed stream with a hydrogenation catalyst, wherein the one or more coreactants includes the unsaturated organic compound, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream is a hydrogenated organic compound.

[0262] Embodiment 130. A process of embodiment 129, wherein the unsaturated organic compound is one or more of a carbonyl-containing compound, an imine-containing compound, an alkene-containing compound, an alkyne-containing compound, a nitro compound, an aromatic compound, and a heteroaromatic compound.

[0263] Embodiment 131. A process of embodiment 129 or embodiment 130, wherein the hydrogenation catalyst comprises ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, or rhenium.

[0264] Embodiment 132. A process of any of embodiments 129-131 , wherein the third feed stream comprises less than 10 mol% of CO, CO2, O2, and H2O, e.g., less than 5 mol% CO, CO2, O2, and H2O, or less than 1 mol% CO, CO2, O2, and H2O, or is substantially free of CO, CO2, O2, and H2O.

[0265] Embodiment 133. A process of any of embodiments 79-84, wherein the reaction with hydrogen is a hydroprocessing conducted by contacting the third feed stream with a hydroprocessing catalyst, wherein the one or more co-reactants includes a hydrocarbon feed, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises a hydroprocessed hydrocarbon feed.

[0266] Embodiment 134. A process of embodiment 133, wherein the one or more coreactants includes a petroleum-derived hydrocarbon feed.

[0267] Embodiment 135. A process of embodiment 133, wherein the one or more coreactants includes a renewable-derived hydrocarbon feed.

[0268] Embodiment 136. A process of any of embodiments 133-135, wherein the one or more co-reactants comprise sulfur, oxygen, and / or nitrogen in an amount in the range of 0.05 wt% to 20 wt%, e.g., 0.05-10 wt%, or 0.05-5 wt%

[0269] Embodiment 137. A process of any of embodiments 133-136, wherein the one or more co-reactants are unsaturated to a degree in the range of 0.05-20 atom% unsaturation, e.g., 0.05-10 wt%, or 0.05-5 wt%.

[0270] Embodiment 138. A process of any of embodiments 133-137, wherein the contacting of the third feed stream with the hydroprocessing catalyst is performed at a temperature in the range of 300-600 °C, e.g., 300-550 °C, or 300-500 °C, or 350-550 °C, or 350-500 °C, or 300-450 °C, or 350-450 °C.

[0271] Embodiment 139. A process of any of embodiments 133-138, wherein the contacting of the third feed stream with the hydroprocessing catalyst is performed at a pressure in the range of 30 to 200 barg, e.g., 40 to 190 barg, or 50 to 180 barg, or 60 to 180 barg, or 80 to 160 barg.

[0272] Embodiment 140. A process of any of embodiments 79-84, wherein the reaction of hydrogen is reaction of hydrogen with oxygen, wherein the one or more co-reactants is oxygen, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream is water.

[0273] Embodiment 141. The process of embodiment 140, wherein the process further comprises storing at least a portion of the hydrogen of the second product stream in a hydrogen fuel tank prior to being provided to the third feed stream.

[0274] Embodiment 142. The process of embodiment 140 or embodiment 141 , wherein the hydrogen reaction zone is a hydrogen fuel cell.

[0275] Embodiment 143. The process of embodiment 142, wherein the hydrogen fuel cell is in a vehicle, e.g., a bus or a car.

[0276] Embodiment 144. The process of embodiment 142, wherein the hydrogen fuel cell is in a power plant.

[0277] Embodiment 145. The process of embodiment 141 , wherein the portion of the hydrogen of the second product stream in a hydrogen fuel tank is cooled to a temperature no more than -252.8 °C, and wherein the hydrogen reaction zone is a hydrogen combustion engine in a rocket.

[0278] Embodiment 146. The process of any of embodiments 1-145, wherein at least part of the CO2 of the first feed stream is from a renewable source.

[0279] Embodiment 147. The process of any of embodiments 1-146, wherein at least part of the CO2 of the first feed stream is from direct air capture.

[0280] Embodiment 148. The process of any of embodiments 1-147 wherein at least part of the CO2 of the first feed stream is captured from a manufacturing plant, e.g., a bioethanol plant, a steel plant or a cement plant.

[0281] Embodiment 149. The process of any of embodiments 1-148, wherein at least part of the H2 of the first feed stream is from a renewable source.

[0282] Embodiment 150. The process of any of embodiment 1-149, wherein at least a portion of the hydrogen of the first feed stream is green hydrogen.

[0283] Embodiment 151. The process of any of embodiment 1-150, wherein at least a portion of the hydrogen of the first feed stream is blue hydrogen.

[0284] Embodiment 152. The process of any of embodiment 1-151 , wherein at least a portion of the hydrogen of the first feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0285] Embodiment 153. The process of any of embodiments 1-152, further comprising providing at least a portion of H2 to the first feed stream by electrolysis of water.

[0286] Embodiment 154. The process of embodiment 153, wherein the electrolysis of water is performed using electricity at least partially derived from a renewable source.

[0287] The particulars shown herein are by way of example and for purposes of illustrative discussion of various embodiments of the present disclosure only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the disclosure. In this regard, no attempt is made to show details associated with the methods of the disclosure in more detail than is necessary for the fundamental understanding of the methods described herein, the description taken with the examples making apparent to those skilled in the art how the several forms of the methods of the disclosure may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatus, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0288] The terms “a,” “an,” “the” and similar referents used in the context of describing the methods of the disclosure (especially in the context of the following embodiments and claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0289] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the methods of the disclosure and does not pose a limitation on the scope of the disclosure. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the methods of the disclosure.

[0290] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0291] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of” excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

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

[0293] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains various errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0294] Groupings of alternative elements or embodiments of the disclosure are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0295] Some embodiments of various aspects of the disclosure are described herein, including the best mode known to the inventors for carrying out the methods described herein. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The skilled artisan will employ such variations as appropriate, and as such the methods of the disclosure can be practiced otherwise than specifically described herein. Accordingly, the scope of the disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.

[0296] The phrase “at least a portion” as used herein is used to signify that, at least, a fractional amount is required, up to the entire possible amount.

[0297] In closing, it is to be understood that the various embodiments herein are illustrative of the methods of the disclosures. Other modifications that may be employed are within the scope of the disclosure. Thus, by way of example, but not of limitation, alternative configurations of the methods may be utilized in accordance with the teachings herein.Accordingly, the methods of the present disclosure are not limited to that precisely as shown and described.

Claims

What is claimed is:

1. A process for producing H2, the process 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; in a methanol dehydrogenation reaction zone, dehydrogenating at least a portion of the methanol of the second feed stream to form a second product stream comprising H2 and CO2, providing a third feed stream comprising at least a portion of H2of the second product stream; in a hydrogen reaction zone, reacting hydrogen of the third feed stream with one or more co-reactants to provide a third product stream comprising one or more products including reacted hydrogen atoms from hydrogen of the third feed stream.

2. The process according to claim 1, wherein the first feed stream includes at least 20 mol% H2and at least 10 mol% CO2.

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

4. The process according to any of claims 1-3, wherein the hydrogenation of CO2 is performed with a conversion of CO2 of at least 45%, and a carbon selectivity of no more than 10% for methane, and no more than 10% for CO.

5. The process according to any of claims 1-4, wherein the methanol dehydrogenation step and the contacting of the first feed stream with the hydrogenation catalyst are performed more than 1 km from one another.

6. The process according to any of claims 1-5, wherein the second feed stream is provided and dehydrogenated during a period of intermittency in hydrogen generation from a renewable resource.

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

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

9. The process according to any of claims 1-8, wherein a molar ratio of water to methanol of the second feed stream is at least 0.85.

10. The process according to any of claims 1-9, wherein the methanol dehydrogenation is a methanol cracking performed by contacting the second feed stream with a methanol cracking catalyst disposed in the methanol dehydrogenation reaction zone11. The process according to any of claims 1-9, wherein the methanol dehydrogenation is a methanol electrolysis performed by electrolyzing at least a portion of the methanol of the second feed stream by contact with an anode in an methanol electrolysis reaction zone, the methanol electrolysis reaction zone having disposed therein a cathode, and a voltage source arranged to place an electrical potential between the anode and the cathode.

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

13. The process according to any of claims 1-12, wherein the dehydrogenation of methanol is performed with a carbon product selectivity of no more than 10% for CO.

14. The process according to any of claims 1-13, wherein the reaction of hydrogen in the hydrogen reaction zone is a Fischer-Tropsch reaction performed by contacting the third feed stream with a Fischer-Tropsch catalyst, wherein the one or more co-reactants includes one or more of CO and CO2, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises C5+ hydrocarbons; an ammonia synthesis performed by contacting the third feed stream with an ammonia synthesis catalyst, wherein the one or more co-reactants includes N2,and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises ammonia; a hydrogenation of an unsaturated organic compound performed by contacting the third feed stream with a hydrogenation catalyst, wherein the one or more coreactants includes the unsaturated organic compound, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream is a hydrogenated organic compound; a hydroprocessing conducted by contacting the third feed stream with a hydroprocessing catalyst, wherein the one or more co-reactants includes a hydrocarbon feed, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream comprises a hydroprocessed hydrocarbon feed; or reaction of hydrogen with oxygen, wherein the one or more co-reactants is oxygen, and wherein the one or more products including reacted hydrogen atoms from hydrogen of the third feed stream is water.

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