Integrated processes for the utilization of synthesized and stored methanol

Abstract

This disclosure relates to an integrated process for the production, storage, and use of methanol. In one aspect, this disclosure provides a process for producing an H2 / CO stream. This process includes, in a first step, the synthesis of methanol by hydrogenation of CO2 and the production of CO and H2 by decomposition of a second feed stream containing methanol. The second step also includes the production of CO and H2 by decomposition of a third feed stream containing storage methanol. The synthesized methanol fraction in the second feed stream is substantially greater than the synthesized methanol fraction in the third feed stream.

Description

Cross-references to related applications

[0001] This application claims priority to European Patent Application No. 23182233.9, filed on 28 June 2023, which is incorporated herein by reference in its entirety. [Technical Field]

[0002] This disclosure relates to an integrated process for the synthesis and storage utilization of methane in synthesis gas production and other applications. [Background technology]

[0003] The technology of converting synthesis gas into hydrocarbons using the Fischer-Tropsch process has been known for many years. Amidst the growing importance of alternative energy sources, interest in the Fischer-Tropsch (FT) process, which enables alternative routes to high-quality fuels and feedstock chemicals by utilizing bio-based carbon sources, is once again on the rise.

[0004] The FT process is typically used to produce linear hydrocarbons used in fuel production, as well as oxygen compounds that are not only useful in fuel production but also function as valuable supply chemicals.

[0005] In reactions that convert synthesis gas to hydrocarbons and their oxygenated derivatives, various transition metals have been confirmed to exhibit catalytic activity. Cobalt, nickel, and iron, in particular, are subjects of research, and these are often used in combination with support materials, the most common of which are alumina, silica, and carbon.

[0006] Syngas is composed of carbon monoxide and hydrogen. While hydrogen is traditionally produced from natural gas and other fossil fuel sources, it can also be produced by the electrolysis of water using electricity generated from renewable energy sources, resulting in hydrogen products with potentially lower carbon dioxide emissions. However, renewable energy sources such as wind and solar power are highly volatile, making their integration into steady-state processes like Fischer-Tropsch synthesis difficult.

[0007] Therefore, there remains a need to develop processes that utilize renewable energy sources more efficiently in the production of synthesis gas. [Overview of the project] [Problems that the invention aims to solve]

[0008] The inventors have developed an integrated process for the production and storage of methanol. This methanol is then decomposed to produce synthesis gas. An advantage is that these processes can incorporate hydrogen produced using renewable energy sources, which helps to smooth out the intermittent energy supply associated with the use of renewable energy sources. This improves the consistency of methanol supply and, consequently, the consistency of synthesis gas production. [Means for solving the problem]

[0009] Therefore, in one aspect, this disclosure provides a process for producing an H2 / CO stream containing hydrogen and carbon monoxide, the process is In the first step, A first supply stream containing hydrogen and CO2 is supplied, The first feed stream is brought into contact with a hydrogenation catalyst (for example, in a hydrogenation reactor) to form a first product stream containing synthesized methanol. A second feed stream is supplied, containing at least a portion of the synthetic methanol from the first product stream. The second feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol and form a second product stream containing CO and H2. At least a portion of the CO and H2 from the second product stream is supplied to the H2 / CO stream. In the second step, Supply a storage methanol source, A third feed stream containing stored methanol is supplied, The third feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol and form a third product stream consisting of CO and H2. At least a portion of the CO and H2 from the third product stream is supplied to the H2 / CO stream. Here, the process involves the fact that the synthetic methanol fraction of the second feed stream is greater than the synthetic methanol fraction of the third feed stream.

[0010] In another aspect, the present disclosure provides a hydrocarbon production process, which involves preparing H2 / CO vapor by the method described herein, and carrying out a Fischer-Tropsch reaction by contacting at least a portion of the H2 / CO fluid with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reactor) by the method separately described herein, to obtain a Fischer-Tropsch product stream containing hydrocarbons, water, and optionally oxygenated hydrocarbons.

[0011] Other aspects of this specification will become apparent to those skilled in the art in light of the following description. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 shows a schematic diagram of a process according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0013] Energy obtained from renewable energy sources is subject to significant fluctuations associated with the availability of the source and is often unstable. For example, solar energy can produce energy that is only available during the day, and wind energy only works during strong wind times. However, many industrial processes require operation in a steady state to operate efficiently, and frequent process interruptions lead to an increase in energy consumption, a decrease in product production volume and / or quality, and / or an increase in wear of process machinery, which may lead to a decrease in the lifespan of capital equipment. Furthermore, effective large-scale energy storage methods are often prohibitively expensive or inefficient. The present disclosure provides a method for managing energy-related intermittency, such as the intermittency of hydrogen produced by electrolysis from renewable energy sources. Advantageously, the inventors recognized that methanol can function as a storage medium for syngas. This is because methanol can be easily transported and stored as a liquid. Therefore, the stored methanol can function as a buffer for intermittent syngas production.

[0014] Thus, in one aspect, the present disclosure provides a process for producing a H2 / CO stream comprising hydrogen and carbon monoxide, the process comprising In a first step, Supplying a first feed stream comprising hydrogen and CO2, Contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthetic methanol, Supplying a second feed stream comprising at least a portion of the synthetic methanol of the first product stream, Contacting the second feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reactor) to decompose at least a portion of the methanol to form a second product stream comprising CO and H2, Supplying at least a portion of the CO and H2 of the second product stream to a H2 / CO stream, In a second step, Supplying a source of stored methanol, Supply a third feed stream containing stored methanol, Contact the third feed stream with a methanol decomposition catalyst (e.g., in a methanol decomposition reactor) to decompose at least a portion of the methanol to form a third product stream consisting of CO and H2, Supply at least a portion of the CO and H2 of the third product stream to the H2 / CO stream, where the synthetic methanol fraction of the second feed stream is greater than the synthetic methanol fraction of the third feed stream.

[0015] As used herein, the term "feed stream" means the total material input to a process step (e.g., CO2 hydrogenation, methanol decomposition, or Fischer-Tropsch reaction), whether provided as a single physical fluid or as multiple physical fluids, and whether provided through a single inlet or multiple inlets. For example, the H2 and CO2 of the first feed stream can be supplied to the hydrogenation reactor as a single physical stream (e.g., a single pipe to the reactor) or as multiple physical streams (e.g., separate inlets for CO2 and H2, or an inlet for fresh CO2 and H and a separate inlet for recycled CO2 and / or H2). Similarly, the "product stream" refers to the total material output from a process step such as the hydrogenation of carbon dioxide, methanol decomposition, or Fischer-Tropsch reaction, whether provided as a single physical stream or as multiple physical streams, and whether provided from a single reactor outlet or multiple reactor outlets.

[0016] Hydrogen can be classified based on its production process. Therefore, in various embodiments described elsewhere herein, at least a portion of the hydrogen in the first feed stream (e.g., at least 50%, at least 75%, at least 90%, or at least 95%) is one of the following: gray hydrogen (produced conventionally by steam reforming using natural gas or methane as a feed source, without recovering associated greenhouse gases), brown or black hydrogen (hydrogen produced using lignite or brown coal), green hydrogen (produced by water electrolysis using electricity from renewable energy sources), pink hydrogen (produced by electrolysis using nuclear energy), turquoise hydrogen (producing hydrogen and solid carbon by methane pyrolysis), blue hydrogen (produced by steam reforming of natural gas, with the resulting carbon dioxide recovered), yellow hydrogen (produced by electrolysis using solar power), or orange hydrogen (produced by electrolysis using wind power). In certain embodiments, at least a portion of the hydrogen in the first feed stream is one or more of green hydrogen, pink hydrogen, or blue hydrogen (e.g., green hydrogen or blue hydrogen). Those skilled in the art are familiar with the classification of various types of hydrogen by color. Biomass gasification can also be used for hydrogen production.

[0017] Advantageously, processes otherwise described herein can incorporate hydrogen gas prepared by electrolysis. Therefore, in various embodiments, the process further includes the steps of electrolyzing water to form an electrolytic product stream containing hydrogen, and supplying the hydrogen obtained from the electrolytic product stream to a first feed stream. In various embodiments otherwise described herein, the hydrogen in the first feed stream contains green hydrogen. For example, in certain embodiments, the process further includes the step of electrolyzing water using electricity from a renewable energy source to form an electrolytic product stream containing hydrogen. Electrolysis is an attractive source of hydrogen gas because it can be driven primarily by renewable energy sources. Therefore, in various embodiments, the electrolysis otherwise described herein is carried out using renewable power sources. Examples of renewable power sources include photovoltaic power (including photovoltaic and solar thermal power), hydroelectric power (e.g., tidal energy), wind power, and geothermal power. Other examples include biomass-derived power. Numerous electrolytic methods are known in the art. For example, it is possible to electrolyze water to produce a gas stream containing hydrogen gas. In certain embodiments, hydrogen is produced through the electrolysis of an aqueous solution (e.g., pure water). Electrolysis of water is further described in U.S. Patents 4,312,720, 4,021,323, and 4,094,751, each of which is incorporated by reference as a whole.

[0018] In various embodiments described herein, methanol synthesis by hydrogenation is carried out by the reaction of hydrogen with carbon dioxide. In particular, carbon dioxide is a common waste gas that can act as a greenhouse gas when released into the atmosphere. In various specific embodiments, the first feed stream contains 10% by volume or less of CO (e.g., 5% by volume or less, 3% by volume or less, 2% by volume or less, 1% by volume or less, or 0.1% by volume or less of CO). In some embodiments, the first feed stream is substantially free of CO.

[0019] Optionally, the first feed stream may contain one or more additional gases. In certain embodiments, the first feed stream contains an inert carrier gas, which includes one or more CH4 or N2, for example, N2. In various embodiments otherwise described herein, at least 50 volume percent of the first feed stream consists of a combination of hydrogen, carbon dioxide, and nitrogen. For example, at least 60 volume percent, at least 70 volume percent, at least 80 volume percent, or at least 90 volume percent.

[0020] Carbon dioxide is a common waste and is often preferable to remove from waste streams rather than release into the atmosphere. Capture of such carbon dioxide is crucial in many initiatives because it can be a means of reducing carbon emissions from related processes. An advantage is that the carbon dioxide used in the processes described herein may be captured from the atmosphere or would have been emitted from combustion or other industrial processes (e.g., unavoidable release into the atmosphere). Carbon dioxide may be captured or absorbed after emissions from industrial processes, or it may be directly captured from the atmosphere. Methods of carbon dioxide capture are well known to those skilled in the art. In various embodiments, at least a portion of the CO2 in the first feed stream is captured directly from the atmosphere. Furthermore, or alternatively, carbon dioxide is often leached from industrial wastewater, particularly processes that generate large amounts of carbon dioxide as byproducts.

[0021] In various embodiments otherwise described herein, the carbon dioxide of the first feed stream includes recovered carbon dioxide and / or carbon dioxide derived from biomass gasification, for example, at least 50%, at least 75%, at least 90%, or at least 95% of recovered carbon dioxide and / or carbon dioxide derived from biomass gasification.

[0022] One source of biomass is agricultural products cultivated as energy crops. Examples include switchgrass, miscanthus, bamboo, sorghum, tall fescue, kochia, wheatgrass, poplar, willow, silver maple, eastern cottonwood, green ash, black walnut, sweet gum, and sycamore. Another source is agricultural waste or crop residue. Traditional agricultural activities (including the production of food, feed, fiber, and forest products) generate large amounts of plant waste. Examples include corn stalks and leaves, wheat straw, oat straw, barley straw, sorghum stubble, and rice straw. A third source of biomass is forestry residue left after logging. Biomass also exists in the form of commercial waste, industrial waste, sewage sludge, and municipal waste (commercial and household waste including garden pruning, paper and cardboard, plastics, rubber, leather, textiles, and food waste). Accordingly, in various embodiments described elsewhere herein, at least a portion of the CO2 in the first feed stream (e.g., at least 20%, at least 50%, at least 75%, at least 90%, or at least 95%) originates from biomass gasification, such as agricultural biomass or municipal waste biomass. The additional source of agricultural biomass is determined by local availability, economics, and process suitability, which will be apparent to those skilled in the art.

[0023] To produce carbon dioxide from carbon-containing materials (such as biomass), gasification is typically performed. Gasification is a process in which a material is heated under controlled conditions to produce gaseous streams of carbon monoxide, hydrogen, and carbon dioxide. The process can be adjusted by adding other reactants, such as oxygen or water vapor, in controlled amounts. Gasification conditions are adjusted according to the carbon-containing material being gasified to efficiently produce gaseous products. Biomass can be obtained from any of the sources described above, or from a combination of multiple sources.

[0024] In some embodiments, biomass gasification can produce a gas mixture of carbon dioxide and other gases such as methane and / or hydrogen sulfide. Therefore, in various embodiments, the first feed stream contains carbon dioxide derived from the biogas. For example, it may also contain contaminating methane. Thus, in various embodiments, the first feed stream further contains methane. However, in some embodiments, a relatively low methane concentration is desirable, for example, 50 mol% or less of the carbon-containing compound, e.g., 30 mol% or less, 20 mol% or less, 10 mol% or less, or 5 mol% or less. Hydrogen sulfide is a common component of biogas. However, in various embodiments, hydrogen sulfide may have adverse effects on certain catalysts in the processes disclosed herein. Therefore, in various embodiments otherwise described herein, the biogas further includes a washing step to remove at least a portion of the hydrogen sulfide.

[0025] Carbon derived from renewable resources such as biomass gasification can be distinguished from fossil-derived carbon using known techniques such as carbon isotope analysis.

[0026] In various embodiments, the first feed stream contains H2 and CO2 so that it can be contacted with the hydrogenation catalyst and reacted to produce methanol. Therefore, in various embodiments described elsewhere herein, the first feed stream contains at least 10 mol% H2. For example, in various embodiments, the first feed stream contains at least 20 mol% H2, for example, at least 30 mol% H2. In various embodiments described elsewhere herein, the first feed stream contains at least 5 mol% CO2. For example, in various embodiments, the first feed stream contains at least 10 mol% CO2, for example, at least 15 mol% CO2.

[0027] Generally, the hydrogenation of CO2 to produce methanol proceeds according to the following reaction: CO2 + 3H2 → CH3OH + H2O. Therefore, in various embodiments otherwise described herein, the H2:CO2 ratio of the first feed stream is at least 1:1 on a molar basis, for example, at least 1.5:1. For example, in various embodiments otherwise described herein, the H2:CO2 ratio of the first feed stream is at least 2:1, for example, at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 8:1. In certain embodiments, the H2:CO2 ratio of the first feed stream is 25:1 or less, for example, 20:1 or less, 15:1 or less, or 12:1 or less.

[0028] In some embodiments, the first feed stream contains other gases in addition to CO2 and H2. For example, in various embodiments, the first feed stream further contains one or more of CO, CH4, and N2. For example, in certain embodiments, the first feed stream contains other gases (e.g., one or more of CO, CH4, and N2) in amounts up to 70 mol% in addition to CO2 and H2. In various embodiments, the first feed stream contains 1% or less O2, for example, 0.1% or less O2, or 0.01% or less O2, or substantially no O2.

[0029] As otherwise described herein, the first feed stream is brought into contact with a hydrogenation catalyst. The hydrogenation catalyst can be selected by those skilled in the art. Examples of suitable catalysts include, for example, a Cu / ZnO catalyst supported on aluminum oxide or zirconium oxide.

[0030] Advantageously, the CO2 hydrogenation reaction can be carried out at relatively low temperatures, which improves energy efficiency and integrates the overall process. For example, in various embodiments otherwise described herein, contact between the first feed stream and the hydrogenation catalyst is carried out at temperatures 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, contact between the first feed stream and the hydrogenation catalyst is carried out at pressures of, for example, 100 bar or less, 80 bar or less, or 60 bar or less.

[0031] The hydrogenation reaction of CO2, resulting from contacting a first feed stream with a hydrogenation catalyst, produces a first product stream. As described herein, the production of the first product stream has the advantage of producing methanol with high selectivity. Thus, in various embodiments otherwise described herein, the production of the first product stream is carried out with a selectivity of at least 50%, e.g., at least 55%, or at least 60%, for methanol. For example, in certain embodiments, the production of the first product stream is carried out with a selectivity of at least 65% (e.g., at least 70%, at least 75%, or at least 80%) for methanol. Advantageously, the production of the first product stream can be carried out with low selectivity for methane. In various embodiments otherwise described herein, the production of the first product stream is carried out with a selectivity for methane of 20% or less, e.g., 10% or less, or 5% or less. As those skilled in the art will understand, “selectivity” for a particular substance means the proportion of the reacted carbon-containing reactants converted to that substance, and does not include unreacted substances.

[0032] Importantly, the CO2 hydrogenation reaction used to form the first product stream as described herein is not a reverse water-gas shift reaction. As is well known to those skilled in the art, a reverse water-gas shift reaction converts CO2 and H2 to CO and H2O. Therefore, in various embodiments described elsewhere herein, the generation of the first product stream is carried out with a selectivity for CO of 20% or less, for example, 10% or less, or 5% or less. In certain embodiments, the generation of the first product stream is carried out with a selectivity for CO of 2% or less, or 1% or less.

[0033] In the CO2 hydrogenation reaction used to form the initial product stream, at least a portion of the CO2 is hydrogenated to methyl alcohol (MeOH) and water (H2O). Advantageously, this process can be carried out with a relatively high CO2 conversion rate. Therefore, in various embodiments otherwise described herein, the generation of the first product stream is carried out with a CO2 conversion rate of at least 25%, for example, at least 35%, for example, at least 45%, or at least 50%.

[0034] Those skilled in the art are familiar with catalytic methods in the hydrogenation reaction 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); and Choundhury, Chem. Cat. Chem. 4(5), 609 (2012), each of which is incorporated herein by reference in its entirety.

[0035] In various embodiments described separately herein, the first product stream contains at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol. As described herein, CO2 hydrogenation also has advantageously low selectivity for other products such as methane and / or carbon monoxide. Therefore, in various embodiments described separately herein, the first product stream contains 10 mol% or less methane, e.g., 5 mol% or less methane, or 2 mol% or less methane. In various embodiments described separately herein, the first product stream contains 10 mol% or less CO, e.g., 5 mol% or less CO, or 2 mol% or less CO. Of course, in some embodiments, more methane and / or carbon monoxide may be present, for example, when one or both are supplied as part of the first feed stream, e.g., as recycled from the Fischer-Tropsch output.

[0036] As described above, in the CO2 hydrogenation reaction, both methanol and water are produced by contact between the first feed stream and the hydrogenation catalyst. The water produced can sometimes be detrimental to subsequent processes. For example, if there is excess water in the subsequent methanol decomposition process, it can cause an undesirable phenomenon in which CO is reverse-converted to CO2 by a water-gas shift reaction. Therefore, in various embodiments described separately herein, the process further includes a step of separating at least some of the water from the first product stream. For example, in certain embodiments, the process further includes separating at least 50%, or at least 75%, or at least 90%, or at least 95%, or at least 99%, or at least 99.5% of the water in the first product stream. In various embodiments described separately herein, the portion of the first product stream contained in the second feed stream has a water content of 10 mol% or less, for example, 2 mol% or less, or 1 mol% or less, or 0.5 mol% or less.

[0037] In embodiments where water is separated from the first product stream, the water is either disposed of as waste or reused in another process. For example, in various embodiments, the separated water is led to an electrolytic reactor for the production of H2 gas, for example, for use in this integrated process or in another process. In various embodiments, the separated water undergoes a purification process before being introduced into the electrolytic reactor.

[0038] In various embodiments described elsewhere herein, not all of the H2 gas introduced into the CO2 hydrogenation process reacts. Therefore, in such embodiments, the process may further include a step of separating at least a portion of the H2 from the first product stream. For example, in certain embodiments described elsewhere herein, the process further includes separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 in the first product stream. The separated H2 can optionally be purified and then optionally recycled. In various embodiments, at least a portion of the separated H2 can be recycled into a first feed stream and / or led to another reactor. For example, in various embodiments, at least a portion of the separated H2 is led to a feed stream of a Fischer-Tropsch reactor (e.g., at least a portion of the H2 separated from the first product stream is supplied to a third feed stream). In certain embodiments, the process further includes activating a Fischer-Tropsch catalyst using at least a portion of the H2 separated from the first product stream. In addition, or alternatively, at least a portion of the H2 separated from the first product stream may be used to activate the methanol decomposition catalyst.

[0039] Compared to gaseous compositions, compositions that are liquid at room temperature and pressure generally have lower handling capital expenditures because they have a higher density and do not require high pressure and / or low temperature. The inventors have confirmed that methanol products from the CO2 hydrogenation reaction are simply storable and / or transportable. Therefore, in various embodiments described separately herein, the contact of the second feed stream and / or third feed stream with the methanol decomposition catalyst, and the contact of the first feed stream with the hydrogenation catalyst, may be carried out in different plants. For example, in some embodiments, the contact of the second feed stream and / or third feed stream with the methanol decomposition catalyst, and the contact of the first feed stream with the hydrogenation catalyst are carried out in different plants. Hereinafter, different “plants” means facilities different from the facility where carbon dioxide hydrogenation takes place, rather than simply referring to different catalyst layers or different containers. In such embodiments, the plant in which the second feed stream and / or third feed stream contact the methanol decomposition catalyst may be, for example, at least 1 km away from the plant in which the first feed stream contacts the hydrogenation catalyst.

[0040] In various embodiments described herein, the synthetic methanol fraction of the second feed stream is substantially greater than the synthetic methanol fraction of the third feed stream. In this specification, “synthetic methanol” means methanol supplied substantially directly to methanol decomposition without undergoing storage that significantly delays its use. “Synthetic methanol” is methanol synthesized from CO2 hydrogenation, as described herein, and then contacted with a methanol decomposition catalyst under methanol decomposition conditions in the first step. Synthetic methanol may be transported from the CO2 hydrogenation reactor to the methanol decomposition reactor via, for example, pipelines, rail vehicles, or trucks. “Synthetic methanol fraction” in the feed stream refers to the fraction of methanol in the feed stream that is “synthetic methanol” as described above. In this specification, “storage methanol” refers to methanol produced by CO2 hydrogenation as described herein, and which, after synthesis from CO2 hydrogenation, is contacted with a methanol decomposition catalyst under methanol decomposition conditions only after a predetermined first step has elapsed. “Storage methanol fraction” in the feed stream refers to the fraction of methanol in the feed stream that is “storage methanol” as described above.

[0041] The first step is a value that distinguishes the substantially immediate use of methanol by CO2 hydrogenation from the long-term storage of such methanol. This value can be selected by those skilled in the art according to this specification, taking into account various factors such as the size of the plant, the distance between the CO2 hydrogenation reactor and the methanol decomposition reactor, and the possibility of intermittent hydrogen supply for methanol synthesis. In various embodiments otherwise described herein, the first step is in the range of 30 minutes to 4 hours. For example, in various embodiments, the first step is in the range of 30 minutes to 3.5 hours, e.g., 30 minutes to 3 hours, or 30 minutes to 2.5 hours, or 30 minutes to 2 hours, or 30 minutes to 1.5 hours, or 30 minutes to 1 hour. In various embodiments otherwise described herein, the first step is in the range of 1 to 4 hours, e.g., 1 to 3.5 hours, or 1 to 3 hours, or 1 to 2.5 hours, or 1 to 2 hours, or 1 to 1.5 hours. In various embodiments described elsewhere in this specification, the first step is in the range of 1.5 to 4 hours, for example 1.5 to 3.5 hours, or 1.5 to 3 hours, or 1.5 to 2.5 hours, or 1.5 to 2 hours. In various embodiments described elsewhere in this specification, the first step is in the range of 2 to 4 hours, for example 2 to 3.5 hours, or 2 to 3 hours, or 2 to 2.5 hours. In various embodiments described elsewhere in this specification, the first step is in the range of 2.5 to 4 hours, for example 2.5 to 3.5 hours, or 2.5 to 3 hours. In various embodiments described elsewhere in this specification, the first step is in the range of 3 to 4 hours, for example 3 to 3.5 hours, or 3.5 to 4 hours. In various embodiments described elsewhere in this specification, the first characteristic process step is 30 minutes. In various embodiments described elsewhere in this specification, the first step is 1 hour. In various embodiments described elsewhere in this specification, the first step is 1.5 hours. In various embodiments described separately herein, the first step is 2 hours. In various embodiments described separately herein, the first step is 2.5 hours. In various embodiments described separately herein, the first step is 3 hours. In various embodiments described separately herein, the first step is 3.5 hours. In various embodiments described separately herein, the first step is 4 hours.

[0042] The synthetic methanol fraction in the feed stream is measured at the point of contact with the methanol decomposition catalyst and represents the proportion of synthetic methanol in the total methanol. Therefore, if the feed stream contains 10 kg of methanol supplied directly from carbon dioxide hydrogenation (e.g., within the first step, such as 2 hours) and 40 kg of storage methanol produced by carbon dioxide hydrogenation much earlier, the synthetic methanol fraction will be 0.20.

[0043] As described above, the inventors recognized that methanol can function as a storage medium for CO and H2 because it can be easily transported and stored as a liquid. Therefore, stored methanol can function as a buffer for intermittent synthesis gas production. Thus, methanol is synthesized (e.g. by CO2 hydrogenation) or supplied by other means, stored for later use, and essentially functions as a reserve of stored CO and H2. During times of high hydrogen production (e.g., during the first step in some embodiments), a portion of the methanol produced by CO2 hydrogenation can be stored for later use. Therefore, in various embodiments described separately herein, the method further includes storing at least a portion of the methanol in the first product stream during the first step. In various embodiments described separately herein, at least a portion of the methanol stored during the first step is supplied to a third feed stream during the second step.

[0044] For example, in various embodiments otherwise described herein, the process further includes storing at least a portion of the methanol in the first product stream to provide stored methanol. The methanol can be stored, for example, in various embodiments otherwise described herein, in a storage tank, a railway vehicle, a pipeline under stagnant flow conditions, or other suitable storage container.

[0045] In various embodiments described elsewhere herein, hydrogen is abundantly produced in the first step, making it possible to directly synthesize methanol, then decompose it to produce an H2 / CO stream, and / or divert it to storage for later use. In various embodiments, the production of H2 by electrolysis, and consequently methanol, may vary depending on the availability of renewable energy sources such as wind or solar power. For example, in various embodiments, the synthetic methanol in the first product stream is distributed between a second feed stream and a storage stream, the storage stream transferring the synthetic methanol to a storage facility. During periods of high methanol production, the synthetic methanol is supplied to both the second feed stream and the storage stream. When methanol production is moderate (e.g., to meet the demand of downstream processes such as hydrocarbon production by the Fischer-Tropsch process), the synthetic methanol is supplied to the second feed stream and substantially not to the storage stream. In embodiments of low methanol production (e.g., below the demand of downstream processes such as hydrocarbon production by the Fischer-Tropsch process), the synthetic methanol may be supplied to the second feed stream. For example, total synthetic methanol may be supplied to a second feed stream. In such embodiments, storage methanol may also be supplied to the second feed stream. For example, enough storage methanol may be supplied to meet the demands of downstream processes when supplied in combination with synthetic methanol. In embodiments where methanol production is substantially zero, synthetic methanol may not be supplied to the second feed stream, and storage methanol may be supplied to the second feed stream instead.

[0046] Therefore, in various embodiments otherwise described herein, substantially all of the methanol in the second feed stream is synthetic methanol. For example, in various embodiments, the synthetic methanol fraction of the second feed stream is at least 95%, e.g., at least 98%, or at least 99%. However, in some embodiments, the second feed stream may contain a substantial amount of methanol other than synthetic methanol. For example, in various embodiments, the second feed stream has a synthetic methanol fraction of at least 50%, e.g., at least 65%, or at least 75%. In various embodiments, the second feed stream has a synthetic methanol fraction of at least 80%, e.g., at least 85%, or at least 90%.

[0047] In various embodiments described elsewhere herein, a third feed stream containing stored methanol is supplied to the methanol decomposition catalyst during the second step. Advantageously, the stored methanol can be used during times when the hydrogen supply is relatively low compared to the first step, for example, when the amount of electricity generated from renewable energy sources is low. During such times, the output of the synthetic methanol can be reduced, and the stored methanol can be used to continue a relatively stable methanol supply to the methanol decomposition catalyst, thereby maintaining the production of the desired H2 / CO stream. Accordingly, in various embodiments described elsewhere herein, the synthetic methanol fraction of the third feed stream is 90% or less, for example, 85% or less, or 80% or less. In various embodiments, the synthetic methanol fraction of the third feed stream is 75% or less, for example, 70% or less, or 65% by weight or less. In various embodiments, the synthetic methanol fraction of the third feed stream is 60% by weight or less, for example, 55% by weight or less, or 50% by weight or less. In various embodiments, the synthetic methanol fraction of the third feed stream is 45% or less, for example, 40% or less, or 35% or less. In various embodiments, the third feed stream has a synthetic methanol fraction of 30% or less, for example, 25% or less, or 20% or less. In various embodiments, the third feed stream has a synthetic methanol fraction of 15% or less, for example, 10% or less, or 5% or less.

[0048] The majority of methanol in the third feed stream may be supplied by storage methanol. For example, in various embodiments, substantially all of the methanol in the third feed stream is storage methanol. However, the amount may vary. In various embodiments, the storage methanol fraction of the third feed stream is at least 5%, e.g., at least 10%, or at least 15%. In various embodiments, the third feed stream has a storage methanol fraction of at least 20%, e.g., at least 25%, or at least 30%. In various embodiments, the third feed stream has a storage methanol fraction of at least 35%, e.g., at least 40%, or at least 45%. In various embodiments, the third feed stream has a storage methanol fraction of at least 50%, e.g., at least 55%, or at least 60%. In various embodiments, the third feed stream has a storage methanol fraction of at least 65%, e.g., at least 70%, or at least 75%. In various embodiments, the third feed stream has a storage methanol fraction of at least 80%, for example, at least 85%, or at least 90%. In various embodiments, the third feed stream has a storage methanol fraction of at least 95%, for example, at least 98%, or at least 99%.

[0049] Stored methanol can be easily stored for long periods. The storage time of a methanol mass is the weight-average storage time for the entire mass. For example, in a sample containing 1 kg of methanol stored for 5 hours and 1 kg of methanol stored for 25 hours, the storage time would be 15 hours. For this purpose, we assume that the storage tank is homogeneously mixed.

[0050] In various embodiments described separately herein, the storage time for the stored methanol in the third feed stream is at least 3 hours, for example, at least 5 hours, or at least 8 hours. In various embodiments, the storage time for the stored methanol in the third feed stream is at least 12 hours, for example, at least 18 hours, or at least 24 hours. In various embodiments, the storage time for the stored methanol is at least 36 hours, for example, at least 3 days, or at least 7 days.

[0051] Of course, it may be desirable to store methanol in case methanol production from CO2 hydrogenation decreases, but it is also desirable to avoid excessive methanol stockpiling. Therefore, especially when the decrease in methanol production is a cyclical phenomenon (for example, when dependent on solar or tidal power), it is desirable to use the stored methanol moderately and regularly to avoid excessive stockpiling. Accordingly, in various embodiments, the storage period for the stored methanol in the third feed stream is 30 days or less, for example, 21 days or less, 14 days or less, or 7 days or less. In various embodiments, the storage period for the stored methanol in the third feed stream is 3 days or less, for example, 2 days or less, or 1 day or less.

[0052] In a preferred embodiment, the second feed stream and / or third feed stream consist substantially of synthetic methanol and storage methanol. For example, in various embodiments, the second feed stream and / or third feed stream have a combined synthetic methanol fraction and storage methanol fraction of at least 95%, e.g., at least 98%, or at least 99%. However, since the methanol in the second feed stream and / or third feed stream may also be supplied from other sources, in some cases the combined synthetic methanol fraction of the second feed stream and / or third feed stream may be substantially less than 100%.

[0053] Stored methanol can be preserved for a long period of time.

[0054] As described herein, in various embodiments, the synthetic methanol fraction of the second feed stream is substantially greater than the synthetic methanol fraction of the third feed stream. For example, in various embodiments, the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 5%, e.g., at least 10%, or at least 15%. In various embodiments, the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 20%, e.g., at least 25%, or at least 30%. In various embodiments, the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 35%, e.g., at least 40%, or at least 45%. In various embodiments, the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 50%, e.g., at least 55%, or at least 60%. In various embodiments, the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 65%, for example, at least 70%, or at least 75%.

[0055] The processes described herein are particularly useful in addressing the intermittent loss of hydrogen used for methanol production by CO2 hydrogenation, for example, due to the intermittent reduction or loss of renewable energy sources used for hydrogen production. This may occur, for example, due to the loss of solar power during nighttime or cloudy days, the loss of wind power, the loss of tidal power, etc. In such cases, stored methanol can be used to sustain the methanol decomposition process, for example, during the second step. In various embodiments, the second step is in the range of 30 minutes to 24 hours (e.g., 30 minutes to 18 hours, or 30 minutes to 12 hours, or 1 to 24 hours, or 1 to 18 hours, or 1 to 12 hours, or 3 to 24 hours, or 3 to 18 hours, or 3 to 12 hours, or 6 to 24 hours, or 6 to 18 hours, or 6 to 12 hours) and occurs after the first step.

[0056] After the second step, once the renewable energy source is restored, the use of stored methanol can be reduced or stopped. Therefore, in various embodiments, another first step follows the second step (i.e., the synthetic methanol fraction in the second feed stream is substantially greater than the synthetic methanol fraction in the third feed stream used during the second step), which is substantially greater than 20% (e.g., 10%) of the synthesis / storage ratio in the first step.

[0057] In various embodiments, for example, particularly when the loss of renewable energy sources is due to periodic phenomena such as sunset or tidal patterns, the process includes a plurality of alternating first and second steps.

[0058] In various embodiments described separately herein, at least a portion of the second product stream can be recycled to the first feed stream. For example, in some embodiments where the methanol supply is small, it may be advantageous to maintain operation of the methanol synthesis reactor.

[0059] As described herein, an advantage of this disclosure is the ability to store and use intermittently produced methanol. One advantage of methanol storage is that, being a liquid at ambient temperature and atmospheric pressure, it can be stored and transported more easily and at higher densities, such as through low-pressure pipelines. Therefore, liquid methanol can often be stored more efficiently than many gaseous feedstock components, such as hydrogen (and / or carbon monoxide or carbon dioxide). Thus, the ability to store methanol and subsequently generate an H2 / CO stream from methanol decomposition avoids the need to store hydrogen gas (and / or carbon monoxide or carbon dioxide) during periods of low production. Therefore, in various embodiments described elsewhere herein, hydrogen produced by electrolysis is not stored for a considerable amount of time. For example, in certain embodiments, hydrogen produced by electrolysis is not stored for more than 6 hours. For example, not for more than 3 hours, more than 1 hour, or more than 30 minutes. For example, hydrogen is often stored in high-pressure tanks or other containers, but this can be advantageously avoided.

[0060] During periods of high hydrogen production, for example, when the production of related renewable energy sources is abundant, it may be desirable to bypass the hydrogenation reaction and supply some of the hydrogen to the H2 / CO stream. Therefore, in various embodiments otherwise described herein, for example, during the first step, the process further includes supplying at least some of the hydrogen to the H2 / CO stream. For example, in various embodiments, for example, during the first step, the H2 / CO stream further includes at least some of the hydrogen not derived from methanol decomposition. In some embodiments, the proportion of hydrogen not derived from methanol decomposition may include at least one of green hydrogen and / or blue hydrogen. In certain embodiments, the proportion of hydrogen not derived from methanol decomposition may include gray hydrogen. For example, hydrogen from sources other than methanol decomposition can be added to adjust the synthesis gas composition for use in further processes (e.g., Fischer-Tropsch hydrocarbon synthesis).

[0061] As described herein, carbon monoxide can be used in methanol synthesis by hydrogenation. However, in various embodiments, the carbon monoxide in the first feed stream is limited, for example, to 10% by volume or less. Therefore, in various embodiments described separately herein, carbon monoxide is supplied in the form of an H2 / CO stream. For example, in various embodiments, the H2 / CO stream further contains at least a portion of carbon monoxide not derived from methanol decomposition. In some embodiments, carbon monoxide from sources other than methanol decomposition can be added to adjust the composition of the synthesis gas for use in further processes (e.g., Fischer-Tropsch hydrocarbon synthesis).

[0062] In various embodiments described separately herein, a second feed stream and / or a third feed stream introduce methanol into a methanol decomposition catalyst, which decomposes it into CO and H2. Methanol decomposition is a different process from methanol reforming, in which methanol and water react to produce CO2 and H2. Therefore, methanol reforming is not utilized in various embodiments described separately herein. For example, in certain embodiments, less than 10% of the H2 is derived from methanol reforming (e.g., less than 5%, or less than 1%).

[0063] The water-gas shift reaction is another method of producing H2 by reacting carbon monoxide with water. This reaction is also reversible, and it is possible to produce carbon monoxide and water by reacting carbon dioxide with hydrogen. An advantage is that, in various embodiments, the processes of this disclosure can be used to avoid the use of both water-gas shift reactions and reverse water-gas shift reactions. Therefore, in the various embodiments described separately herein, the proportion of each component of the process—H2, CO, and CO2—produced by either a water-gas shift reaction or a reverse water-gas shift reaction (whichever is appropriate) is 10% or less (e.g., 5% or less, or 2% or less). In the various processes disclosed herein, no dedicated water-gas shift reactor or reverse water-gas shift reactor is used (however, as those skilled in the art will understand, trace amounts of water-gas shift reactions or reverse water-gas shift reactions may occur as side reactions during certain processes).

[0064] As described herein, methanol decomposition is utilized to form an H2 / CO stream containing CO and H2. Thus, in various embodiments separately described herein, the second feed stream contains at least 5 mol% methanol. For example, in certain embodiments, the second feed stream contains 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. When the methanol supply is intermittent, it may be desirable to keep the process running. Therefore, in various embodiments, the method further includes contacting at least a portion of the H2 / CO stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor).

[0065] Optionally, the second feed stream and / or third feed stream may contain one or more additional gases. In such embodiments, the second feed stream may further contain one or more of H2, CO, CH4, CO2, and N2. In certain embodiments, the second feed stream contains an inert carrier gas, which contains one or more of CH4, CO2, and N2. Furthermore, or instead, H2 and / or CO may be added to the second feed stream to adjust the decomposition reaction and / or provide a desired second product stream for use in the Fischer-Tropsch process. In such embodiments, the second feed stream further contains H2 and / or CO. In various embodiments otherwise described herein, one or more of H2, CO, CH4, CO2, and N2 are present in the second feed stream in amounts ranging from 50 mol percent or less, for example, 40 mol% or less, or 30 mol% or less.

[0066] In various embodiments, the second feed stream and / or third feed stream have a low water content. The present water can react with CO via a water-gas shift reaction to be converted at least partially to CO2 and H2. The water can also react with methanol via a reforming reaction to produce H2 and CO2. The produced H2 inhibits the decomposition of methanol to CO and H2, according to the reaction equilibrium of methanol decomposition. Therefore, in various embodiments otherwise described herein, the water concentration of the second feed stream is 5 mol% or less, for example, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.3 mol% or less, 0.2 mol% or less, or 0.1 mol% or less.

[0067] In certain embodiments, the second feed stream and / or third feed stream may be supplied at a high temperature. For example, in various embodiments otherwise described herein, the temperature of the second feed stream is in the range of 200 to 500°C, e.g., 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C.

[0068] As described herein, a second feed stream and / or a third feed stream are contacted with a methanol decomposition catalyst. Any suitable decomposition catalyst can be used, and a variety of them are known in the art. For example, the decomposition catalyst may include transition metals, such as Ni, Co, Rh, Ir, Cu, Pt, Ru, or mixtures thereof. The decomposition catalyst is a supported catalyst, and the support is a refractory oxide such as diamond oxide, silica, zirconia, ceria, titania, alumina, or magnesia. In some embodiments, the methanol decomposition catalyst is, for example, a copper / zinc oxide catalyst on alumina.

[0069] Contact between the second feed stream and / or third feed stream and the methanol decomposition catalyst is carried out at a temperature suitable for effective and efficient methanol decomposition. In various embodiments described separately herein, contact between the second feed stream and the methanol decomposition catalyst is carried out in the range of 200 to 500°C, for example, 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C. Contact may be carried out at various suitable pressures, for example, in the range of 0 to 50 bar (barg), where barg is a unit of gauge pressure, representing pressure above ambient pressure or atmospheric pressure in bar units. In various embodiments otherwise described herein, contact with the methanol decomposition catalyst can be integrated with a Fischer-Tropsch reactor. Thus, in such embodiments, contact with the methanol decomposition catalyst can be carried out at relatively high pressures, for example, in the range of up to 50 bar (e.g., 20-40 bar).

[0070] As described herein, contact between a second feed stream and / or a third feed stream and a methanol decomposition catalyst can be carried out in the same plant as contact between a first feed stream and a hydrogenation catalyst. In such examples, it may be advantageous to adjust the temperatures of the methanol decomposition and hydrogenation reactions to avoid excessive heating and cooling equipment and energy costs. Therefore, in certain embodiments described separately herein, contact between a second feed stream and a methanol decomposition catalyst is carried out within a temperature range of 75°C above the contact temperature between the first feed stream and the hydrogenation catalyst, for example, within 50°C.

[0071] The decomposition reaction of methanol produces CO and H2, ideally minimizing other products. Therefore, in various embodiments otherwise described herein, the decomposition of methanol is carried out such that the carbon product selectivity for CO is at least 50%, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90%. Advantageously, in various embodiments, the decomposition of methanol is carried out with a selectivity for CO2 of 20% or less, e.g., 15% or less, 10% or less, or 5% or less. In various embodiments otherwise described herein, the decomposition of methanol is carried out with a methanol conversion rate 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%.

[0072] As described herein, when methanol is decomposed by contacting a second feed stream and / or a third feed stream with a methanol decomposition catalyst, CO and H2 are produced. Therefore, in the various embodiments described separately herein, the second product stream contains a total of at least 20 mol%, e.g., at least 35 mol%, or at least 50 mol%, or at least 65 mol%, of CO and H2. While not intended to be bound by theory, methanol decomposition under these conditions is expected to produce 2 moles of H2 per mole of CO. Therefore, in the various embodiments described separately herein, the molar ratio of hydrogen to carbon monoxide in the second product stream is in the range of 0.5:1 to 5:1, e.g., 1:1 to 3:1, or 1.5:1 to 2.5:1, or 1.5:1 to 3.5:1. Of course, in other embodiments, this molar ratio may differ, for example, as a result of the inclusion of H2 and / or CO in the second feed stream and / or third feed stream.

[0073] Advantageously, some methanol is consumed during the methanol decomposition reaction. Therefore, in various embodiments otherwise described herein, the second product stream contains methanol in an amount of 75 mol% or less, for example, 60 mol% or less, 50 mol% or less, or 25 mol% or less.

[0074] In some embodiments, further removal of methanol from the second product stream is desirable. For example, in various embodiments described separately herein, the process further includes a step of separating at least a portion of methanol from the second product stream. For example, separating at least 50%, or at least 75%, or at least 90%, or at least 95% of methanol from the second product stream. Advantageously, the methanol in the second product stream, for example, at least a portion of the methanol separated from the second product stream, can be transferred to other processes or recycled. For example, in various embodiments described separately herein, the process further includes recycling at least a portion of the methanol separated from the second product stream to a second feed stream. In other embodiments, the process further includes storing at least a portion of the methanol from the second product stream to form recycled / stored methanol, and then feeding at least a portion of the recycled / stored methanol to a third feed stream.

[0075] Those skilled in the art are familiar with catalytic methods for decomposing methanol into CO and H2. Examples of various catalysts and catalytic processes are described in U.S. Patents 6,541,142, 9,883,773, and 4,716,859, each of which is incorporated herein by reference in its entirety.

[0076] Methanol is a valuable feedstock in various chemical processes. Furthermore, when produced from renewable carbon dioxide using the processes described herein (e.g., recovery from the atmosphere, other chemical processes, or biomass conversion), it can be favorably considered a carrier of renewable carbon. Similarly, when produced using green hydrogen and / or blue hydrogen using the methods described herein (e.g., hydrogen produced from the electrolysis or steam reforming of water), methanol can be considered a carrier of hydrogen from such sources.

[0077] The methanol decomposition reaction theoretically produces CO and H2 in a 2:1 molar ratio, but the actual reaction product ratio can vary in various embodiments. This can result in excess hydrogen useful for subsequent processes, depending on the desired ratio. In particular, the presence of hydrogen in the second feed stream can further increase the amount of hydrogen in the second product stream. Therefore, in various embodiments described separately herein, the process further includes a step of separating at least some of the H2 from the second product stream. The separated H2 is suitable for various processes. For example, in certain embodiments, at least some of the H2 separated from the second product stream is supplied to the first feed stream. Furthermore, or alternatively, in various embodiments described separately herein, the process further includes activating a methanol decomposition catalyst or a Fischer-Tropsch catalyst using at least some of the H2 separated from the second product stream.

[0078] As described herein, in various embodiments, methanol decomposition yields a product with a hydrogen gas to carbon monoxide molar ratio of 2:1. However, this ratio may not be ideal for downstream processes. For example, in hydrocarbon synthesis by the Fischer-Tropsch process (C 5+In processes such as hydrocarbon production, a hydrogen-to-carbon monoxide molar ratio typically requires a ratio ranging from 1.8:1 to 4:1. Therefore, in various embodiments described separately herein, the process further includes a step of preparing the synthesis gas to provide an H2 / CO stream with an H2:CO ratio ranging from 1.5:1 to 3:1.

[0079] Adjustment can be achieved by various means or a combination thereof. For example, in various embodiments, adjustment includes subjecting at least a portion of the H2 / CO stream to a water-gas shift reaction (e.g., in a water-gas shift reactor). In various embodiments, adjustment includes adding hydrogen gas to the H2 / CO stream. For example, the process includes electrolyzing water to produce a hydrogen gas-containing fluid (e.g., as otherwise described herein) and using at least a portion of the hydrogen gas-containing fluid in the adjustment step. In various embodiments, adjustment includes removing carbon monoxide from the H2 / CO stream.

[0080] As described herein, one aspect of the present disclosure is the production of synthesis gas. In various embodiments, the production of synthesis gas proceeds through the production of methanol from carbon dioxide, followed by the decomposition of methanol to produce carbon monoxide and hydrogen. Thus, synthesis gas may further contain gases other than carbon monoxide and hydrogen. For example, in various embodiments otherwise described herein, the synthesis gas is in the range of 0.1% to 50% by weight (e.g., 1% to 50% by weight, 5% to 50% by weight, 10% to 50% by weight, 15% to 50% by weight, 20% to 50% by weight, 25% to 50% by weight, 0.1% to 40% by weight, 0.1% to 30% by weight, 0.1% to 25% by weight, 0.1% to 20% by weight, 1% to 30% by weight, 2% to 30% by weight, 5% to 30%). For example, in various embodiments otherwise described herein, the synthesis gas contains carbon dioxide in the range of 0.1% to 50% by weight (e.g., 1% to 50% by weight, 5% to 50% by weight, 10% to 50% by weight, 15% to 50% by weight, 20% to 50% by weight, 25% to 50% by weight, 0.1% to 40% by weight, 0.1% to 30% by weight, 0.1% to 25% by weight, 0.1% to 20% by weight, 1% to 30% by weight, 2% to 30% by weight, 5% to 30%).

[0081] Certain processes (e.g., methanol synthesis processes such as CO2 hydrogenation) may become less efficient when given fluctuating inputs or when periodically stopped. Therefore, in various embodiments, the H2 / CO stream can be recirculated to a hydrogenation reactor to continue methanol synthesis. For example, processes otherwise described herein may further include contacting at least a portion of the H2 / CO stream with a hydrogenation catalyst (e.g., within the hydrogenation reactor).

[0082] The H2 / CO stream of this disclosure is available for use in various downstream processes. In other words, this disclosure provides a hydrocarbon production process, which includes preparing an H2 / CO stream by the method described herein and carrying out a Fischer-Tropsch reaction by contacting at least a portion of the H2 / CO stream with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reactor) by the method described elsewhere herein, to obtain a Fischer-Tropsch product stream containing hydrocarbons, water, and optionally oxygenated hydrocarbons.

[0083] In embodiments utilizing the Fischer-Tropsch reaction, the operation of the process described herein may be adjusted in relation to the requirements of the Fischer-Tropsch reaction. For example, in various embodiments described herein, the Fischer-Tropsch reaction may have a desired throughput, and in the first step, power supply from a renewable energy source may be sufficient to provide the desired throughput, while in the second step, power supply from a renewable energy source may be insufficient to provide the desired throughput.

[0084] The Fischer-Tropsch synthesis catalyst can be any suitable catalyst well known to those skilled in the art. For example, the Fischer-Tropsch synthesis catalyst can be an iron-based catalyst or a cobalt-based catalyst. Other examples of suitable catalysts include nickel or platinum-based catalysts. Those skilled in the art can select a suitable catalyst in accordance with this disclosure.

[0085] The Fischer-Tropsch synthesis catalysts used in the Fischer-Tropsch synthesis processes in various embodiments herein (e.g., supported Fischer-Tropsch synthesis catalysts) contain iron or cobalt in an elemental amount ranging from 1% to 35% by weight. Those skilled in the art will select an appropriate amount of iron or cobalt based on the disclosure herein. For example, in various embodiments, the Fischer-Tropsch synthesis catalyst contains elements in amounts ranging from 1 to 30% by weight, or 1 to 25% by weight, or 1 to 20% by weight, or 2 to 35% by weight, or 2 to 30% by weight, or 2 to 25% by weight, or 5 to 35% by weight, or 5 to 30% by weight, or 5 to 25% by weight. In certain embodiments, the Fischer-Tropsch synthesis catalyst contains elements in amounts ranging from 2 to 20% by weight, for example, 2 to 15% by weight, or 2 to 10% by weight, or 5 to 20% by weight, or 5 to 15% by weight, or 5 to 10% by weight, or 7 to 20% by weight, or 7 to 15% by weight.

[0086] In certain embodiments, a suitable Fischer-Tropsch synthesis catalyst may also contain various other transition metals. For example, it may include one or more different promoters such as manganese, ruthenium, palladium, platinum, rhodium, rhenium, chromium, nickel, iron, molybdenum, tungsten, zirconium, gallium, thorium, lanthanum, cerium, copper, and mixtures thereof. Promoters are typically used with an atomic ratio of metal to promoter of up to 250:1, e.g., up to 125:1, up to 25:1, or up to 10:1, where the metal is a catalytically active Fischer-Tropsch metal such as iron or cobalt. In certain embodiments, one or more promoters are present in the resulting Fischer-Tropsch synthesis catalyst in an amount ranging from 0.1% to 3% by weight on an elemental basis based on the total weight of the supported synthesis catalyst. In other embodiments, the Fischer-Tropsch synthesis catalyst does not contain any such promoters.

[0087] Fischer-Tropsch synthesis catalysts may further include a support material (for example, a Fischer-Tropsch synthesis catalyst may be a supported Fischer-Tropsch synthesis catalyst). The support material plays a role in binding and structurally supporting the catalyst particles and may also affect catalytic activity and product selectivity. In various embodiments otherwise described herein, the support material includes at least one of alumina, zirconia, titania, silica, zinc oxide, cerium oxide, or a combination thereof. In certain embodiments, the support material includes any of alumina, zirconia, zinc oxide, cerium oxide, silica, and titanium oxide, for example, the support material is any of alumina, zirconia, zinc oxide, cerium oxide, silica, and titanium oxide. In yet other specific embodiments, the support material includes titanium oxide (for example, at least 90% by weight of titanium oxide, or at least 95% by weight of titanium oxide, or at least 99% by weight of titanium oxide), for example, the support material is titanium oxide.

[0088] In various embodiments otherwise described herein, the Fischer-Tropsch synthesis catalyst used in accordance with this disclosure may be prepared by any suitable method. For example, the Fischer-Tropsch synthesis catalyst may be prepared by impregnating a support material with cobalt.

[0089] One example of a suitable impregnation method is to impregnate the support material with a metal-containing compound that can be thermally decomposed into an oxide form. Impregnation of the support material with a metal-containing compound can be achieved by any suitable method known to those skilled in the art, such as vacuum impregnation, initial wetting, or immersion in an excess liquid.

[0090] The initial wetting method, as its name suggests, requires pre-determining the volume of impregnation solution to provide the minimum amount of solution (no excess liquid) necessary to wet the entire surface of the support. The excess solution method, as its name suggests, requires an excess amount of impregnation solution, after which the solvent is usually removed by evaporation.

[0091] In various embodiments, if a support material is present, it may take the form of a powder, granules, molded particles (such as pre-formed spheres or microspheres), or an extruded article. References herein to powder or granules of the support material are understood to refer to fluid particles of the support material, or particles of the support material that have been granulated and / or sieved to have a specific shape (e.g., spherical) and particle size range. “Extruded article” herein means a carrier material formed by an extrusion process.

[0092] It will be understood that the support material may be in any form suitable for use as a support for the Fischer-Tropsch synthesis catalyst. A preferred support material is one that is substantially free of impurities that may adversely affect the catalytic activity of the system. Therefore, in certain embodiments, the support material is at least 95% by weight pure, more preferably at least 98% by weight pure, and most preferably at least 99% by weight pure. The amount of impurities is preferably less than 1% by weight, more preferably less than 0.50% by weight, and most preferably less than 0.25% by weight. The pore volume of the support is preferably greater than 0.150 ml / g, more preferably greater than 0.30 ml / g. The average pore radius (before impregnation) of the support material is 10-500 Å, preferably 15-100 Å, more preferably 20-80 Å, and most preferably 25-60 Å. The BET specific surface area is 2-1000 m². 2 / g is appropriate, preferably 10-600m 2 / g, more comfortably 15-300m 2 / g, most preferably 30-150m 2 It is / g.

[0093] The solvent of the impregnation solution is either an aqueous solvent or a non-aqueous organic solvent. Suitable non-aqueous organic solvents include, for example, alcohols (methanol, ethanol, and / or propanol), ketones (acetone, etc.), liquid paraffinic hydrocarbons, and ethers. Alternatively, an aqueous organic solvent, such as an aqueous alcohol solvent, can also be used. Preferably, the solvent of the impregnation solution is an aqueous solvent.

[0094] If the carrier material is in powder or granular form, it will be understood that after impregnation with a suitable metallic compound such as a cobalt-containing compound or an iron-containing compound, the impregnated carrier material can be processed into extruded or molded particles at an appropriate stage either before or after drying and calcination.

[0095] After impregnation of the support, it is desirable to dry the impregnation solution, thereby allowing the metal-containing compound to precipitate on the support and to remove the binding solvent (e.g., water) from the impregnation solution. In embodiments where extrusion molding is performed, it will be understood that after the formation of molded particles (e.g., by extrusion molding), the impregnation solution is completely dried and the solvent (e.g., the binding solvent) is removed. Drying is appropriately carried out in a temperature range of 50°C to 150°C, preferably 75°C to 125°C. A suitable drying time is, for example, 5 minutes to 72 hours. Drying can be appropriately carried out in a drying oven or box oven, for example, under a flow of inert gas at a high temperature.

[0096] The preparation of Fischer-Tropsch synthesis catalysts may include a calcination step. In certain embodiments otherwise described herein, it will be understood that calcination is necessary to convert a metal-containing compound impregnated in a carrier material into an oxide of that metal. For example, if the metal is cobalt, calcination results in the thermal decomposition of the cobalt-containing compound rather than the removal of the binding solvent in the impregnation solution (e.g., by drying).

[0097] The firing is carried out by any method well known to those skilled in the art, for example, in a fluidized bed or rotary kiln, at a temperature of at least 250°C, preferably 275°C to 500°C.

[0098] Fischer-Tropsch synthesis catalysts are conveniently reductively activated by any known method recognized by those skilled in the art. For example, in embodiments in which the catalyst contains cobalt, activation conditions are used that allow the conversion of cobalt oxide to activated cobalt metal (e.g., to form a reduced Fischer-Tropsch synthesis catalyst), such as by using a reducing gas. In certain embodiments, the reducing gas includes hydrogen gas. The step of forming a reduced synthesis catalyst can be carried out in batch or continuous manner in a fixed-bed, fluidized-bed, or slurry-phase reactor, or in situ in the same reactor used for the subsequent Fischer-Tropsch synthesis reaction. Reduction is carried out in the range of 150°C to 350°C, for example, 150°C to 325°C, or 200°C to 325°C, or 200°C to 300°C, or 200°C to 250°C.

[0099] In various embodiments described separately herein, the process includes electrolyzing water to produce hydrogen gas. In certain embodiments, the process may further include activating a Fischer-Tropsch catalyst by contacting it with at least a portion of the hydrogen gas produced by electrolyzing water, for example, in the electrolysis step described separately herein.

[0100] As you know, in some embodiments, it is possible to form a situ-reduced Fischer-Tropsch synthetic catalyst using an H2 / CO stream supplied to the Fischer-Tropsch synthetic catalyst, without requiring a prior reduction activation step or a separate reduction activation step.

[0101] Those skilled in the art will carry out the processes described herein using any preferred reaction system. For example, a wide variety of reactors can be used, such as fixed-bed reactors, slurry-bed reactors, and fluidized-bed reactors.

[0102] In this specification, "selectivity" for a given component is measured as the mole fraction of a specific reactant that reacts in the process (i.e., excluding the unreacted portion of the reactant) and is converted into the product. For example, when reacting carbon dioxide with hydrogen to obtain a product component containing methane, "selectivity" for a given component means the mole fraction of carbon dioxide that reacts in the reaction process and is converted into the desired product, excluding unreacted carbon dioxide.

[0103] One way to utilize carbon dioxide is through the reverse water-gas shift reaction, in which carbon dioxide and hydrogen are converted into carbon monoxide and water. CO2 + H2 ⇔ CO + H2O

[0104] However, the reverse water-gas shift reaction is typically carried out under harsh conditions, with reaction temperatures exceeding 900°C. Therefore, the reaction cost is high from an energy standpoint and requires the use of specialized equipment. Furthermore, this process consumes hydrogen, which is often expensive from a process economic perspective. The advantage of the process described herein is that, in various embodiments, carbon dioxide can be converted to synthesis gas via a methanol intermediate without using the reverse water-gas shift reaction. Therefore, in various embodiments otherwise described herein, the process does not involve the reverse water-gas shift reaction. During normal operation of the process described herein, small amounts of carbon dioxide may be converted to carbon monoxide as a byproduct via the reverse water-gas shift reaction. Therefore, the absence of the reverse water-gas shift reaction is understood to mean the absence of a distinct reaction zone dedicated to the reverse water-gas shift reaction.

[0105] In other embodiments described herein, the process includes a water-gas shift reaction, but in certain embodiments, the water-gas shift reaction is operated to consume carbon monoxide and water and produce carbon dioxide and hydrogen.

[0106] Thus, in various embodiments, the Fischer-Tropsch product stream may further contain carbon dioxide. In such embodiments, the process may further include recycling at least a portion of the carbon dioxide to the first feed stream.

[0107] Also, as described herein, a mixture of carbon monoxide and hydrogen is useful for the synthesis of higher hydrocarbons by the Fischer-Tropsch process. Thus, another aspect of the present disclosure is to contact a hydrocarbon synthesis mixture containing carbon monoxide and hydrogen with a Fischer-Tropsch hydrocarbon synthesis catalyst to produce a 5+ Fischer-Tropsch process for producing a hydrocarbon composition comprising hydrocarbons and / or oxygen compounds, and 5+ the selectivity for hydrocarbons is at least 50% and / or the selectivity for oxygen compounds is at least 20%. Suitable techniques for hydrocarbon synthesis, particularly the synthesis of 5+ hydrocarbons and / or oxygen compounds, are described in International Patent Application Publication No. 2019 / 154885, which is hereby incorporated by reference in its entirety.

[0108] The Fischer-Tropsch processes described herein may advantageously have a high C5+ selectivity. For example, in various embodiments, the process has a C 5+ selectivity of at least 75%, such as at least 80%, at least 85%, or at least 90%. The Fischer-Tropsch processes described herein may advantageously have a low methane selectivity. For example, in various embodiments, this process has a methane selectivity of 6% or less, such as 5% or less, 4%, or 3% or less.

[0109] The CO conversion rate is defined as the number of moles of CO used / the number of moles of CO fed × 100. 5+ The hydrocarbon selectivity is 5+ defined as the number of moles of CO attributable to hydrocarbons / the number of moles of CO converted × 100. The alcohol selectivity is defined as the number of moles of CO attributable to alcohol / the number of moles of CO converted × 100.

[0110] Liquid hydrocarbons can be produced using the catalyst described herein at conventional Fischer-Tropsch temperatures. For example, the temperature at which a mixture of hydrogen and gaseous carbon monoxide (e.g., in the form of a synthesis gas mixture) is brought into contact with the Fischer-Tropsch catalyst is in the range of 100-400°C, e.g., 100-350°C, or 100-300°C, 100-250°C, 150-400°C, 150-350°C, or 150-300°C. In various embodiments, the contact is carried out at temperatures below 350°C, e.g., below 325°C, or below 300°C, or below 280°C. The contact pressure (i.e., the temperature of the Fischer-Tropsch reaction) is in various embodiments in the range of 10-100 bar (1-10 MPa), e.g., 15-75 bar (1.5-7.5 MPa), or 20-50 bar (2.0-5.0 MPa). For example, in various embodiments, contact is performed at a pressure of 7.5 MPa absolute or less.

[0111] In certain embodiments, the temperature of the Fischer-Tropsch reaction is in the range of 150 to 350°C, more preferably in the range of 180 to 300°C. In preferred embodiments, the pressure of the Fischer-Tropsch reaction is in the range of 10 to 100 bar (1 to 10 MPa), more preferably in the range of 10 to 60 bar (1 to 6 MPa), and most preferably in the range of 20 to 45 bar (2 to 4.5 MPa).

[0112] The Fischer-Tropsch product stream may contain, in addition to hydrocarbons, other components derived from and / or generated in-situ from the feed stream. Examples include light hydrocarbons (such as methane and C2-C4 hydrocarbons), nitrogen, water, and / or carbon dioxide. Advantageously, it is possible to separate specific substance species and reuse them in other processes. For example, in various embodiments described separately herein, the Fischer-Tropsch product stream may contain carbon dioxide, and the process may further include supplying at least a portion of the carbon dioxide in the Fischer-Tropsch product stream to a first feed stream.

[0113] In various embodiments otherwise described herein, the process includes electrolyzing water to form a fluid containing hydrogen gas. In such embodiments, and where the Fischer-Tropsch product stream contains water, the process further includes supplying at least a portion of the hydrogen gas-containing fluid to a first feed stream, where at least a portion of the water in the Fischer-Tropsch product stream is supplied to the electrolysis step.

[0114] Unless otherwise specified, the temperatures described in the embodiments are applicable temperatures, not catalyst / floor temperatures. Unless otherwise specified, the pressures described in the embodiments are absolute pressures.

[0115] The disclosure process will be further described with reference to the embodiments shown below. However, these embodiments are for illustrative purposes only.

[0116] Figure 1 shows one embodiment according to the present disclosure. The hydrolysis reactor 110 generates a hydrogen stream 101, which is mixed with a carbon monoxide (e.g., containing at least one of carbon dioxide and carbon monoxide) stream 102 to form a first feed stream 103. The first feed stream 103 is introduced into a hydrogenation reactor 120 equipped with a hydrogenation catalyst 140, and a first product stream 104 containing methanol is withdrawn. Depending on the time described herein, the synthesized methanol is introduced directly into a second feed stream 106 that enters a methanol decomposition reactor 130 equipped with a methanol decomposition catalyst 160, and a second product stream 108 is withdrawn. Furthermore, or alternatively, methanol is withdrawn from the first product stream 104 through a methanol storage stream 105 to a methanol storage tank 140. The stored methanol is then withdrawn from the storage methanol tank 140 to form a third feed stream 107. This third feed stream 107 is introduced into the methanol decomposition reactor 130, which contains the methanol decomposition catalyst 160, and the second product stream 108 is drawn out. Embodiment 1. A process for producing an H2 / CO stream containing hydrogen and carbon monoxide, wherein the process is: In the first step, A first supply stream containing hydrogen and CO2 is supplied, The first feed stream is brought into contact with a hydrogenation catalyst (for example, in a hydrogenation reactor) to form a first product stream containing synthesized methanol. A second feed stream is supplied, containing at least a portion of the synthetic methanol from the first product stream. The second feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol and form a second product stream containing CO and H2. At least a portion of the CO and H2 from the second product stream is supplied to the H2 / CO stream. In the second step, Supply a storage methanol source, A third feed stream containing stored methanol is supplied, The third feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol and form a third product stream consisting of CO and H2. At least a portion of the CO and H2 from the third product stream is supplied to the H2 / CO stream. Herein, the process includes the fact that the synthetic methanol fraction of the second feed stream is greater than the synthetic methanol fraction of the third feed stream. Embodiment 2. A process in which the hydrogen in the first feed stream includes green hydrogen or blue hydrogen, in the process of Embodiment 1. Embodiment 3. A process in which the hydrogen in the first feed stream contains green hydrogen, in the process of Embodiment 1 or Embodiment 2. Embodiment 4. A process according to any of Embodiments 1 to 3, further comprising the steps of: electrolyzing water to form an electrolysis product stream containing hydrogen; and supplying the hydrogen obtained from the electrolysis product stream to a first feed stream. Embodiment 5. In the process of Embodiment 4, electrolysis is a process carried out using electricity from a renewable energy source. Embodiment 6. The process of Embodiment 5, wherein the renewable power source is provided by one or more of the following: solar energy, wind energy, and hydroelectric energy (e.g., tidal energy). Embodiment 7. A process in which the hydrogen produced by electrolysis is not stored for a considerable amount of time (e.g., 1 hour or less) in any of the processes of Embodiments 4 to 6. Embodiment 8. A process in which, in any of the processes of Embodiments 4 to 7, at least a portion of the hydrogen produced by electrolysis is supplied to the H2 / CO stream while bypassing the hydrogenation of CO2. Embodiment 9. A process according to any of Embodiments 1 to 8, wherein the first feed stream contains at least 10 volume% of H2, for example, at least 20 volume% of H2, or at least 30 volume% of H2. Embodiment 10. A process according to any of Embodiments 1 to 9, wherein the first feed stream contains at least 5 volume% CO2, for example, at least 10 volume% CO2, or at least 15 volume% CO2. Embodiment 11. A process in any of Embodiments 1 to 10 in which the CO2 of the first feed stream includes recovered CO2 (e.g., directly recovered air CO2, or recovered waste CO2 such as biomass-derived CO2), and includes, for example, at least 50%, at least 75%, at least 90%, or at least 95% recovered CO2. Embodiment 12. A process in any of Embodiments 1 to 10 in which the CO2 of the first feed stream includes biomass gasification-derived carbon dioxide, for example, a process containing at least 20%, at least 50%, at least 75%, at least 90%, or at least 95% biomass gasification-derived carbon dioxide. Embodiment 13. A process in which the first feed stream further contains methane, in any of the methods of Embodiments 1 to 11. Embodiment 14. A process according to any of Embodiments 1 to 11, wherein the amount of methane in the first feed stream is 50 mol% or less of the carbon-containing compound, for example, 30 mol% or less, or 20 mol% or less, or 10 mol% or less, or 5 mol% or less. Embodiment 15. A process according to any of Embodiments 1 to 14, wherein the molar ratio of H2:CO2 in the first feed stream is at least 1:1, for example, at least 1.5:1. Embodiment 16. A process according to any of Embodiments 1 to 14, wherein the H2:CO2 ratio of the first feed stream is at least 2:1, for example, at least 2.5:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 8:1. Embodiment 17. A process according to any of Embodiments 1 to 16, wherein the H2:CO2 ratio of the first feed stream is 25:1 or less, for example, 20:1 or less, or 15:1 or less, or 12:1 or less. Embodiment 18. A process according to any of Embodiments 1 to 17, wherein the first feed stream contains 1% or less O2, for example, 0.1% or less O2, or 0.01% or less O2, or substantially no O2, and / or 10 volume% or less CO (for example, 5 volume% or less, 3 volume% or less, 2 volume% or less, 1 volume% or less, or 0.1 volume% or less CO). Embodiment 19. A process in which, in any of Embodiments 1 to 18, the contact between the first feed stream and the hydrogenation catalyst is carried out at a temperature in the range of 200 to 500°C, for example, 200 to 450°C, or 200 to 400°C, or 200 to 350°C, or 200 to 300°C, or 250 to 500°C, or 250 to 450°C, or 250 to 400°C, or 250 to 300°C, or 300 to 500°C, or 300 to 450°C, or 300 to 400°C. Embodiment 20. A process in which, in any of the processes of Embodiments 1 to 19, the contact between the first feed stream and the hydrogenation catalyst is carried out at a pressure of, for example, 100 bar or less, 80 bar or less, or 60 bar or less. Embodiment 21. A process in which the first product stream is generated with at least 50% selectivity for methanol, for example, at least 55%, or at least 60%, in any of the processes of Embodiments 1 to 20. Embodiment 22. A process in which the generation of the first product stream is carried out with at least 65% selectivity relative to methanol (e.g., at least 70%, or at least 75%, or at least 80% relative to methanol) in any of the processes of Embodiments 1 to 20. Embodiment 23. In any of the processes of Embodiments 1 to 20, the formation of the first product stream is carried out with a selectivity of 20% or less for methane, for example, 10% or less, or 5% or less. Embodiment 24. A process in which the formation of the first product stream is carried out with a selectivity of 20% or less, for example, 10% or less, or 5% or less, relative to CO, in any of the processes of Embodiments 1 to 23. Embodiment 25. A process in which the formation of the first product stream is carried out with a selectivity of 2% or less relative to CO, or 1% or less relative to CO, in any of the processes of Embodiments 1 to 23. Embodiment 26. In any of the processes of Embodiments 1 to 25, the formation of the first product stream is carried out in a process in which the conversion rate of CO2 is at least 25%, for example at least 35%, for example at least 45%, or at least 50%. Embodiment 27. A process in any of Embodiments 1 to 26, wherein the first product stream comprises at least 15% by volume of methanol, for example, at least 25% by volume, or at least 35% by volume of methanol. Embodiment 28. A process according to any of Embodiments 1 to 27, wherein the first product stream contains methane with a methane content of 10% by volume or less, for example, 5% by volume or less, or 2% by volume or less. Embodiment 29. A process in any of Embodiments 1 to 28 in which the first product stream contains 10% by volume or less of CO, for example, 5% by volume or less of CO, or 2% by volume or less of CO. Embodiment 30. A process of any of Embodiments 1 to 29, further comprising separating at least a portion of the water content from the first product stream, for example, separating at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or at least 99.5% of the water content from the first product stream. Embodiment 31. A process according to any of Embodiments 1 to 30, wherein the water content of the portion of the first product stream contained in the second feed stream is 10 mol% or less, for example, 2 mol% or less, or 1 mol% or less, or 0.5 mol% or less. Embodiment 32. A process of any of Embodiments 1 to 31, further comprising separating at least a portion of hydrogen (H2) from the first product stream, for example, comprising separating at least 50% of the hydrogen (H2) in the first product stream, or at least 60%, or at least 75%, or at least 90%, or at least 95%. Embodiment 33. A process in which, in the process of Embodiment 32, at least a portion of the separated H2 is recycled to a first feed stream and / or at least a portion of the separated H2 is supplied as part of a Fischer-Tropsch feed stream and / or at least a portion of the separated H2 is used to activate a methanol decomposition catalyst and / or a Fischer-Tropsch catalyst. Embodiment 34. A process in which, in any of Embodiments 1 to 33, the contact between the second feed stream and / or third feed stream and the methanol decomposition catalyst, and the contact between the first feed stream and the hydrogenation catalyst are carried out in different plants. Embodiment 35. A process in any of Embodiments 1 to 34 in which the first step is in the range of 30 minutes to 4 hours, for example, in the range of 30 minutes to 3.5 hours, for example, 30 minutes to 3 hours, or 30 minutes to 2.5 hours, or 30 minutes to 2 hours, or 30 minutes to 1.5 hours, or 30 minutes to 1 hour. Embodiment 36. A process in any of Embodiments 1 to 34 in which the first step is in the range of 1 to 4 hours, for example, 1 to 3.5 hours, or 1 to 3 hours, or 1 to 2.5 hours, or 1 to 2 hours, or 1 to 1.5 hours. Embodiment 37. A process in which the first step is in the range of 1.5 to 4 hours, for example, 1.5 to 3.5 hours, or 1.5 to 3 hours, or 1.5 to 2.5 hours, or 1.5 to 2 hours, in any of the processes of Embodiments 1 to 34. Embodiment 38. A process in which the first step is in the range of 2 to 4 hours, for example, 2 to 3.5 hours, or 2 to 3 hours, or 2 to 2.5 hours, in any of the processes of Embodiments 1 to 34. Embodiment 39. A process in which the first step is in the range of 2.5 to 4 hours, for example, 2.5 to 3.5 hours, or 2.5 to 3 hours, in any of the processes of Embodiments 1 to 34. Embodiment 40. A process in which the first step is in the range of 3 to 4 hours, for example, 3 to 3.5 hours, or 3.5 to 4 hours, according to any of the processes of Embodiments 1 to 34. Embodiment 41. A process in which the first step is 30 minutes, in any of the processes of Embodiments 1 to 34. Embodiment 42. A process in which the first step is 1 hour, in any of the processes of Embodiments 1 to 34. Embodiment 43. A process in which the first step is 1.5 hours, in any of the processes of Embodiments 1 to 34. Embodiment 44. A process in which the first step is 2 hours, in any of the processes of Embodiments 1 to 34. Embodiment 45. A process in which the first step is 2.5 hours, in any of the processes of Embodiments 1 to 34. Embodiment 46. A process in which the first step is 3 hours, in any of the processes of Embodiments 1 to 34. Embodiment 47. A process in which the first step is 3.5 hours, in any of the processes of Embodiments 1 to 34. Embodiment 48. A process in which the first step is 4 hours, in any of the processes of Embodiments 1 to 34. Embodiment 49. A process of any of Embodiments 1 to 45, further comprising storing at least a portion of the methanol in the first product stream during the first step. Embodiment 50. A process in which methanol stored during the first step is supplied to a third feed stream during the second step, in the process 49 of Embodiment 49. Embodiment 51. A process in any of Embodiments 1 to 50 in which substantially all of the methanol in the second feed stream is synthetic methanol. Embodiment 52. A process according to any of Embodiments 1 to 50, wherein the second feed stream has a synthetic methanol fraction of at least 95%, for example, at least 98%, or at least 99%. Embodiment 53. A process according to any of Embodiments 1 to 50, wherein the second feed stream has a synthetic methanol fraction of at least 50%, for example, at least 65%, or at least 75%. Embodiment 54. A process according to any of Embodiments 1 to 50, wherein the second feed stream has a synthetic methanol fraction of at least 80%, for example, at least 85%, or at least 90%. Embodiment 55. A process according to any of Embodiments 1 to 54, wherein the third feed stream has a synthetic methanol fraction of 90% or less, for example, 85% or less, or 80% or less. Embodiment 56. A process according to any of Embodiments 1 to 54, wherein the third supply stream has a synthetic methanol fraction of 75% or less, for example, 70% or less, or 65% by weight or less. Embodiment 57. A process according to any of Embodiments 1 to 54, wherein the third feed stream has a synthetic methanol fraction of 60% by weight or less, for example, 55% by weight or less, or 50% by weight or less. Embodiment 58. A process according to any of Embodiments 1 to 54, wherein the third feed stream has a synthetic methanol fraction of 45% or less, for example, 40% or less, or 35% or less. Embodiment 59. A process according to any of Embodiments 1 to 54, wherein the third feed stream has a synthetic methanol fraction of 30% or less, for example, 25% or less, or 20% or less. Embodiment 60. A process according to any of Embodiments 1 to 54, wherein the third feed stream has a synthetic methanol fraction of 15% or less, for example, 10% or less, or 5% or less. Embodiment 61. A process in any of Embodiments 1 to 60 in which substantially all of the methanol in the third feed stream is storage methanol. Embodiment 62. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 5%, for example, at least 10%, or at least 15%. Embodiment 63. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 20%, for example, at least 25%, or at least 30%. Embodiment 64. A process in any of the processes of Embodiments 1 to 60 in which the third feed stream has a storage methanol fraction of at least 35%, for example, at least 40%, or at least 45%. Embodiment 65. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 50%, for example, at least 55%, or at least 60%. Embodiment 66. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 65%, for example, at least 70%, or at least 75%. Embodiment 67. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 80%, for example, at least 85%, or at least 90%. Embodiment 68. A process according to any of Embodiments 1 to 60, wherein the third feed stream has a storage methanol fraction of at least 95%, for example, at least 98%, or at least 99%. Embodiment 69. A process according to any of Embodiments 61 to 68, wherein the storage time for the storage methanol in the third feed stream is at least 3 hours, for example, at least 5 hours, or at least 8 hours. Embodiment 70. A process according to any of Embodiments 61 to 68, wherein the storage time of the storage methanol in the third feed stream is at least 12 hours, for example, at least 18 hours, or at least 24 hours. Embodiment 71. A process according to any of Embodiments 61 to 68, wherein the storage time for the storage methanol in the third feed stream is at least 36 hours, for example, at least 3 days or at least 7 days. Embodiment 72. A process according to any of Embodiments 61 to 68, wherein the storage time of the stored methanol in the third feed stream is 30 days or less, for example, 21 days or less, or 14 days or less, or 7 days or less. Embodiment 73. A process according to any of Embodiments 61 to 68, wherein the storage time of the stored methanol in the third feed stream is 3 days or less, for example, 2 days or less, or 1 day or less. Embodiment 74. A process according to any of Embodiments 1 to 73, wherein the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 5%, for example, at least 10%, or at least 15%. Embodiment 75. A process according to any of Embodiments 1 to 73, wherein the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 20%, for example, at least 25%, or at least 30%. Embodiment 76. A process according to any of Embodiments 1 to 73, wherein the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 35%, for example, at least 40%, or at least 45%. Embodiment 77. A process according to any of Embodiments 1 to 73, wherein the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 50%, for example, at least 55%, or at least 60%. Embodiment 78. A process according to any of Embodiments 1 to 73, wherein the difference between the synthetic methanol fraction of the second feed stream and the synthetic methanol fraction of the third feed stream is at least 65%, for example, at least 70%, or at least 75%. Embodiment 79. A process in any of Embodiments 1 to 78 in which the second step is in the range of 30 minutes to 24 hours (for example, 30 minutes to 18 hours, or 30 minutes to 12 hours, or 1 to 24 hours, or 1 to 18 hours, or 1 to 12 hours, or 3 to 24 hours, or 3 to 18 hours, or 3 to 12 hours, or 6 to 24 hours, or 6 to 18 hours, or 6 to 12 hours), and which occurs after the first step. Embodiment 80. A process in which, in any of Embodiments 1 to 79, another first step follows the second step. Embodiment 81. A process according to any of Embodiments 1 to 79, the process comprising a plurality of first and second steps that are repeated alternately. Embodiment 82. A process of any of Embodiments 1 to 81, further comprising including at least a portion of the second product stream in the first feed stream. Embodiment 83. A process in any of Embodiments 1 to 82, wherein the H2 / CO stream further comprises at least a portion of hydrogen not derived from methanol decomposition. Embodiment 84. A process according to any of Embodiments 1 to 83, wherein the first feed stream contains 10% by volume or less of CO. Embodiment 85. A process in any of Embodiments 1 to 84, wherein the H2 / CO stream further comprises at least a portion of carbon monoxide not derived from methanol decomposition. Embodiment 86. A process in which, in any of Embodiments 1 to 85, at least a portion of the H2 / CO stream is further brought into contact with a hydrogenation catalyst (for example, in a hydrogenation reactor). Embodiment 87. A hydrocarbon production process, the process comprising preparing an H2 / CO stream by any of the processes of Embodiments 1 to 86, contacting at least a portion of the H2 / CO stream with a Fischer-Tropsch catalyst (for example, in a Fischer-Tropsch reactor) to carry out a Fischer-Tropsch reaction, and supplying a Fischer-Tropsch product stream comprising hydrocarbons, water, and optionally oxygenated hydrocarbons. Embodiment 88. A process in which the Fischer-Tropsch reaction has a desired throughput, in the first step the power supply from a renewable energy source is sufficient to provide the desired throughput, and in the second step the power supply from a renewable energy source is insufficient to provide the desired throughput. Embodiment 89. The process of Embodiment 87 or Embodiment 88, wherein the Fischer-Tropsch product stream contains carbon dioxide, and the process further includes recirculating at least a portion of the carbon dioxide to a first feed stream.

[0117] The details provided herein are illustrative and intended to illustrate various embodiments of the disclosure, and are presented to provide the most useful and easily understandable explanation of the principles and conceptual aspects of the various embodiments of the disclosure. In this regard, no attempt has been made to provide details relating to the disclosed methods beyond what is necessary for a basic understanding of the methods described herein. By considering the descriptions and examples herein together, those skilled in the art will be able to see how various forms of the disclosed methods can actually be embodied. Therefore, before describing the disclosed processes and apparatus, it should be understood that the aspects described herein are not limited to any particular embodiment, apparatus, or configuration, but can naturally take various forms. It should also be understood that the terms used herein are for the purpose of describing particular aspects only and are not intended to be limiting unless specifically defined herein.

[0118] As used in the context describing the methods disclosed herein (particularly in the embodiments and claims below), “a,” “an,” “the,” and similar demonstrative pronouns are to be interpreted as encompassing both singular and plural forms, unless otherwise stated herein or if the context clearly contradicts them.

[0119] All methods described herein may be carried out in any suitable order, unless otherwise stated herein or unless it is clearly inconsistent with the context. Any examples or illustrative expressions described herein (e.g., “for example”) are intended merely to provide a clearer explanation of the disclosed methods and do not constitute a limitation on the scope of the disclosure. No expression in the specification should be construed as indicating an element that is essential for carrying out the disclosed methods but is not described in the claims.

[0120] Unless otherwise clearly required by the context, the words “including,” “including,” and similar phrases in the specification and claims as a whole shall be interpreted in a comprehensive sense, not exclusive or exhaustive; that is, “including, but not limited to.” Words used in the singular or plural form shall also include the plural and singular forms, respectively. Furthermore, as used in this application, “in this specification,” “above,” “below,” and similar phrases shall refer to the entire application, not to any particular part thereof.

[0121] As those skilled in the art will understand, each embodiment disclosed herein encompasses, essentially constitutes, or may constitute its particular described element, process, component, or constituent. As used herein, the transition terms “contains” or “plurally contains” mean to contain, but are not limited to, the inclusion of unspecified elements, processes, components, or constituents, even if they are in a major quantity. The transition phrase “consists of” excludes elements, processes, components, or constituents that are not explicitly stated. The transition phrase “essentially consists of” limits the scope of the embodiment to the explicitly stated elements, processes, components, or constituents, and those that do not substantially affect the embodiment.

[0122] Unless otherwise stated, all percentages, ratios, and proportions in this document are based on weight.

[0123] Although the numerical ranges and parameters indicating the general scope of the disclosed information are approximations, the numerical values ​​shown in the specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error that inevitably arises from the standard deviation of each test measurement.

[0124] The grouping of alternative elements or embodiments herein should not be construed as limitation. Each group component may be referred to or claimed individually or in any combination with other components within the group or other elements described herein. For convenience and / or patentability, it is assumed that one or more components within a group may be included in or removed from the group. If such addition or removal occurs, the specification shall be deemed to include the modified group, thereby satisfying the written description of all Markash groups used in the appended claims.

[0125] This specification describes several embodiments relating to various aspects of the disclosure, including the best embodiment known to the inventors for carrying out the methods described herein. Naturally, variations of these described embodiments will be obvious to those skilled in the art who have read the preceding description. Skilled artisans will adopt such variations where they deem appropriate. Thus, the disclosed methods can be carried out in ways other than those specifically described herein. Accordingly, the scope of this disclosure includes all variations and equivalents of the subject matter described in the appended claims, to the extent permitted by applicable law. Furthermore, unless otherwise stated herein or unless it is clearly inconsistent with the context, all combinations in any possible variation of the above elements are included in this disclosure.

[0126] As used herein, the expression "at least a portion" means that at least a partial amount is required, up to the maximum possible amount.

[0127] Finally, it should be understood that the various embodiments described herein are examples of the disclosed method. Other modifications that may be adopted are within the scope of the disclosure. Therefore, alternative configurations of the method can be utilized, exemplary but not restrictively, in accordance with the teachings herein. Thus, the method of this disclosure is not limited to those precisely shown and described.

Claims

1. H containing hydrogen and carbon monoxide ２ A process for manufacturing a CO stream, the process is In the first step, Hydrogen and CO ２ A first supply stream containing the following is supplied: The first feed stream is brought into contact with a hydrogenation catalyst (for example, in a hydrogenation reactor) to form a first product stream containing synthesized methanol. A second feed stream containing at least a portion of the synthetic methanol from the first product stream is supplied. The second feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol into CO and H ２ Forms a second product stream including CO and H in the second product stream ２ At least a portion of H ２ / Supplies to the CO stream, In the second step, Supply a storage methanol source, A third feed stream containing stored methanol is supplied, A third feed stream is brought into contact with a methanol decomposition catalyst (for example, in a methanol decomposition reactor) to decompose at least a portion of the methanol into CO and H ２ A third product stream consisting of the above is formed, CO and H in the third product stream ２ At least a portion of H ２ / Supplies to the CO stream, The process here includes the condition that the synthetic methanol fraction of the second feed stream is greater than the synthetic methanol fraction of the third feed stream.

2. A process according to claim 1, further comprising electrolyzing water to form an electrolytic product stream containing hydrogen, and supplying the hydrogen obtained from the electrolytic product stream to a first feed stream, wherein the electrolysis is performed using electricity from a renewable energy source.

3. A process according to claim 1 or claim 2, wherein the formation of the first product stream is carried out with at least 65% selectivity for methanol.

4. A process according to any one of claims 1 to 3, wherein the water content of a portion of the first product stream contained in the second feed stream is 2 mol% or less.

5. The process according to any one of claims 1 to 4, further comprising separating at least a portion of H ２ from the first product stream, wherein at least a portion of the separated H ２ is recycled to the first feed stream and / or at least a portion of the separated H ２ is supplied as part of the Fischer-Tropsch feed stream and / or at least a portion of the separated H ２ is used to activate the methanol decomposition catalyst and / or the Fischer-Tropsch catalyst.

6. A process according to any one of claims 1 to 5, wherein the first step is in the range of 30 minutes to 4 hours.

7. A process according to any one of claims 1 to 6, wherein the first step is 30 minutes or 2 hours.

8. A process according to any one of claims 1 to 7, wherein the synthetic methanol fraction of the second feed stream is at least 95%.

9. A process according to any one of claims 1 to 8, wherein the synthetic methanol fraction of the third feed stream is 70% or less.

10. A process according to any one of claims 1 to 9, wherein the storage methanol fraction of the third feed stream is at least 20%.

11. The process according to claim 10, wherein the storage time of the stored methanol in the third feed stream is at least 3 hours.

12. A process according to any one of claims 1 to 11, wherein the difference between the synthetic methanol fraction of a second feed stream and the synthetic methanol fraction of a third feed stream is at least 20%.

13. A process according to any one of claims 1 to 12, the process comprising a plurality of first and second steps that are repeated alternately.

14. A process according to any one of claims 1 to 13, wherein H ２ The CO stream is a process that further includes at least some hydrogen that does not originate from methanol decomposition.

15. A hydrocarbon production process, wherein the process is carried out by the process described in any one of claims 1 to 14. ２ Prepare the / CO stream and the H ２ A process comprising contacting at least a portion of a CO stream with a Fischer-Tropsch catalyst (e.g., in a Fischer-Tropsch reactor) to carry out a Fischer-Tropsch reaction, thereby supplying a Fischer-Tropsch product stream containing hydrocarbons, water, and optionally oxygenated hydrocarbons.

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