Methods for production of hydrocarbons

Abstract

The present disclosure relates generally to integrated processes for the production, storage, and use of methanol. In one aspect, the present disclosure provides a process for producing a hydrocarbon composition, the process comprising for a first period of time, synthesizing methanol by hydrogenation of COx, and contacting at least a portion of the synthesized methanol with a methanol-to-hydrocarbon synthesis catalyst to form a hydrocarbon product stream; and for a second period of time, contacting a third feed stream comprising stored methanol to form a hydrocarbon product stream. A synthesized methanol fraction of the second feed stream is substantially greater than a synthesized methanol fraction of the third feed stream.

Description

METHODS FOR PRODUCTION OF HYDROCARBONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of European Patent Application no. 24219615.2, filed December 12, 2024, which is hereby incorporated herein by reference in its entirety.BACKGROUND OF THE DISCLOSUREFIELD

[0002] The present disclosure relates to integrated processes for the utilization of synthesized and stored methanol, such as in the production of hydrocarbons.TECHNICAL BACKGROUND

[0003] The conversion of methanol into hydrocarbons by the various methanol conversion processes (e.g., methanol-to-olefin; methanol-to-jet) has been known for many years. The use of these gases often requires steady-state production of the methanolcontaining feed stream to provide a steady-state production of hydrocarbons, as once a methanol-to-olefin process is operating, it is highly desirable to maintain operation in a relatively steady state, as opposed to starting-and-stopping it. Methanol can be produced by hydrogenation of carbon dioxide as an initial step in such processes. However, in some cases steady-state production of syngas is not reliable. And any storage and transportation of hydrogen and carbon monoxide required to maintain a steady-state increases the risk and adds additional safety concerns to the overall hydrocarbon production process.

[0004] Additionally, the growing importance of alternative energy sources has resulted in renewed interest in alternative routes to high-quality fuels and feedstock chemicals through use of bio-derived carbon sources. While hydrogen is conventionally produced from natural gas or other fossil fuel sources, it can also be produced through water electrolysis using electricity produced from a renewable source of energy, leading to a hydrogen product with potentially lower associated carbon dioxide emissions. However, renewable sources of energy, such as wind or solar, suffer from significant variability which makes their direct incorporation into steady-state processes challenging.

[0005] Accordingly, there remains a need to develop processes to more efficiently utilize renewable sources of energy in the production of hydrocarbons with safer conditions.SUMMARY

[0006] The present inventors have developed integrated processes for the production and storage of methanol, which can then be used to generated hydrocarbons.Advantageously, these processes can incorporate hydrogen generated using a renewablesource of energy and can serve to smooth the intermittent energy availability sometimes associated with the use of renewable sources, allowing for increased consistency of methanol supply and thus increased consistency of hydrocarbon production.

[0007] Thus, in one aspect, the disclosure provides for processes for the production of a hydrocarbon composition, the process comprising: for a first period of time, providing a first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; providing a second feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form a hydrocarbon product stream comprising one or more hydrocarbons; and for a second period of time, providing a source of stored methanol; providing a third feed stream comprising stored methanol; contacting the third feed stream with the methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form the hydrocarbon product stream comprising one or more hydrocarbons; wherein the synthesized methanol fraction of the second feed stream is greater than the synthesized methanol fraction of the third feed stream. Thus, stored methanol can be used to maintain the methanol-to-hydrocarbon synthesis in steady operation even when a desired source of hydrogen and / or COXis intermittent.

[0008] In some embodiments as described herein, the process further comprises: for a third period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the fourth 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 fourth product stream comprising CO and H2; andproviding at least a portion of the CO and the H2 of the fourth product stream to the first feed stream. Thus, the methanol product of the hydrogenation can be decomposed to CO and H2, and used in a feed stream to maintain operation of the hydrogenation even when a desired source of hydrogen and / or COXis intermittent.

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

[0010] FIG. 1 provides a process schematic according to one embodiment of the disclosure.

[0011] FIG. 2 provides a process schematic according to one embodiment of the disclosure.

[0012] FIG. 3 provides a process schematic according to one embodiment of the disclosure.

[0013] FIG. 4 provides a process schematic according to one embodiment of the disclosure.DETAILED DESCRIPTION

[0014] Energy derived from renewable sources often suffers from intermittency in availability, with large increases and decreases associated with the availability of the source. For example, solar energy can only produce usable energy during daytime, and wind energy is only effective during windy periods. Further, prevailing weather conditions can reduce the effectiveness of power generation from renewable sources, e.g., from solar power during cloudy periods and from wind power during calm periods. Effective large-scale energy storage methods are often prohibitively expensive or inefficient.

[0015] This is especially problematic when the renewable energy is used in industrial chemical processes. Many industrial processes require steady-state operation over long periods of time in order to run efficiently, and frequent process interruptions can lead to increased energy usage, diminished product output and / or quality, and / or increased wear on the process machinery, potentially leading to lower lifetimes of capital equipment. Examples of such processes include those that use hydrogen and oxides of carbon (i.e. COX, meaning CO2 and / or CO) like carbon monoxide as a feed, such as the Fischer-Tropsch process.

[0016] The present disclosure provides methods for managing energy-associated intermittency, for example the intermittency of hydrogen produced through the use of electrolysis powered by renewable sources of energy. Advantageously, the present inventors have recognized that methanol can serve as a storage vehicle for hydrogen andoxides of carbon (i.e. COX, meaning CO2 and / or CO), as it can be easily transported and stored as a liquid. Thus, stored methanol can serve as a buffer against intermittent hydrogen and COXproduction. Furthermore, by storing methanol, the process no longer requires storing hydrogen or COXas a mechanism for maintaining minimum rates of methanol operation, reducing the overall process risk profile.

[0017] Here, renewable energy is used to make hydrogen, which is converted to methanol, which can in turn be decomposed to hydrogen and carbon oxide(s) for use in hydrocarbon synthesis. In times of high availability of renewable energy (e.g., times of high wind or high sunshine), methanol over and above that necessary to maintain the hydrocarbon synthesis process can be produced and stored. In times of lower availability of renewable energy, the stored methanol can be decomposed to maintain the hydrocarbon synthesis process. This provides a significant technical effect, in that it allows the overall hydrocarbon synthesis to continue to operate at a desired throughput during times of lower availability of renewable energy.

[0018] This is significantly advantaged over using methanol as a mere energy storage medium. Simply converting stored methanol to electrical energy, e.g., through combustion or via a direct methanol fuel cell, can provide energy, but would not provide hydrogen. Thus, a separate electrolysis reaction would be necessary to provide hydrogen from water. In contrast, the present invention uses methanol not merely as an energy storage medium, but rather as a storage medium for hydrogen and carbon oxide(s). The renewable energy is not being merely stored, but rather used to provide a hydrogen and carbon oxide(s) precursor that is conveniently stored for use during times of lower renewable energy production.

[0019] Thus, in one aspect, the disclosure provides for processes for the production of a hydrocarbon composition, the process comprising: for a first period of time, providing a first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; providing a second feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form a hydrocarbon product stream comprising one or more hydrocarbons; and for a second period of time, providing a source of stored methanol;providing a third feed stream comprising stored methanol; contacting the third feed stream with the methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form the hydrocarbon product stream comprising one or more hydrocarbons; and wherein the synthesized methanol fraction of the second feed stream is greater than the synthesized methanol fraction of the third feed stream.

[0020] An embodiment according to the present disclosure is shown in FIG. 1 , where in the process 100, the first feed stream 101 is introduced into the hydrogenation reactor 110 with the hydrogenation catalyst 113 and the methanol-containing first product stream 102 is withdrawn. Depending on the time period as described herein, the synthesized methanol can be directly introduced into the second feed stream 103 which enters the methanol-to- hydrocarbon synthesis reactor 130 containing the methanol-to-hydrocarbon synthesis catalyst 133, and the hydrocarbon product stream 106 is withdrawn. Additionally or alternatively, methanol can be withdrawn from the first product stream 102 in stored methanol stream 105 to the methanol storage tank 120. Subsequently, stored methanol can be withdrawn from the methanol storage tank 120 to form the third feed stream 104 which is introduced into the methanol-to-hydrocarbon synthesis reactor 130 containing the methanol- to-hydrocarbon catalyst 122, and the hydrocarbon product stream 106 is withdrawn.

[0021] As used herein, the term “feed stream” is used to mean the total material input to a process step, e.g., hydrogenation of COXor methanol-to-hydrocarbon synthesis, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single inlet or multiple inlets. For example, H2 and COXof the first feed stream can be provided to a hydrogenation reactor in a single physical stream (e.g., in a single pipe to the reactor), or in multiple physical streams (e.g., separate inlets for CO, CO2, and H2, or one inlet for fresh CO, CO2, and H2 and another for recycled CO, CO2, and / or H2). Similarly, a “product stream” is used to refer to the total material output from a process step, e.g., hydrogenation of COXor methanol-to-hydrocarbon synthesis, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single reactor outlet or multiple reactor outlets.

[0022] The process as described herein includes providing a first feed stream comprising hydrogen and COX. Hydrogen may be categorized based on the process used to produce it. Accordingly, in various embodiments as otherwise described herein, at least a portion of the hydrogen (e.g., at least 50%, at least 75%, at least 90% or at least 95%) of the first feed stream is one or more of white hydrogen (“natural” or “geologic” hydrogen found underground); grey hydrogen (produced conventionally from natural gas, or methane using steam reformation without capturing associated greenhouse gases), brown or blackhydrogen (hydrogen produced using black coal or lignite), green hydrogen (made using water electrolysis powered by electricity from renewable sources of energy), pink hydrogen (made from electrolysis powered by nuclear energy), turquoise hydrogen (made from methane pyrolysis to produce hydrogen and solid carbon), blue hydrogen (made from steam reforming of natural gas, where the resulting carbon dioxide is captured), yellow hydrogen (made from electrolysis using solar power) and orange hydrogen (made from electrolysis using wind power). In particular embodiments, at least a portion of the hydrogen of the first feed stream is one or more of green hydrogen, pink hydrogen, white hydrogen, or blue hydrogen (e.g., green hydrogen or blue hydrogen). In particular embodiments, the hydrogen of the first feed stream comprises green hydrogen or blue hydrogen. In particular embodiments, the hydrogen of the first feed stream comprises green hydrogen. The person of ordinary skill in the art is familiar with the color designations of various types of hydrogen. Biomass gasification may also be used to generate hydrogen.

[0023] Advantageously, the process as otherwise described herein may incorporate hydrogen gas prepared through electrolysis. Thus, in various embodiments, the process further comprises electrolyzing water to form an electrolysis product stream comprising hydrogen, and providing hydrogen from the electrolysis product stream to the first feed stream.

[0024] In various embodiments as otherwise described herein, the hydrogen of the first feed stream comprises green hydrogen. For example, in particular embodiments, the process further comprises electrolyzing water using electricity from a renewable source to form an electrolysis product stream comprising hydrogen. Electrolysis is an attractive source of hydrogen gas as it may be principally powered by renewable sources of energy. Accordingly, in various embodiments, the electrolyzing as otherwise described herein is performed using renewable sources of electricity. Examples of renewable sources of electricity include solar power (including photovoltaic solar and solar thermal power), hydroelectric power (e.g., tidal energy), wind power, and geothermal power. Other examples include power derived from biomass. Numerous methods of electrolysis are known in the art. For example, electrolysis may be performed with water to produce a hydrogen gas containing stream. In particular embodiments, the hydrogen is formed through the electrolysis of a water solution (e.g., pure water). Water electrolysis is described further in U.S. Patent No. 4,312,720, U.S. Patent No. 4,021 ,323, and U.S. Patent No. 4,094,751 , each of which is incorporated by reference in their entirety.

[0025] Advantageously, the present inventors have found that the production of methanol can be used as an effective storage vehicle for hydrogen. Converting the hydrogen that is intermittently produced to methanol can reduce or even eliminate the needfor storing hydrogen. One advantage of methanol storage is that, as a liquid at atmospheric temperatures and pressures, it can be more easily and densely stored and transported, such as by pumping through a low-pressure pipeline, which advantageously decreases the overall risk profile of the process. Accordingly, liquid methanol may often be more efficiently stored compared to many gaseous feed components, such as hydrogen (and / or carbon monoxide or carbon dioxide). Thus, storage of methanol, with the capability to produce a hydrocarbon stream from subsequent methanol-to-hydrocarbon synthesis, can obviate the need to store hydrogen gas (and / or carbon monoxide or carbon dioxide) for times of low production. Accordingly, in various embodiments as otherwise described herein, the hydrogen produced by electrolysis is not stored for a substantial amount of time. For example, in particular embodiments, the hydrogen produced by electrolysis is not stored for more than six hours, e.g., not stored for more than 3 hours, or more than 1 hour, or more than 30 minutes. For example, hydrogen is often stored in high pressure tanks and other vessels, which may be advantageously avoided.

[0026] In various embodiments as described herein, methanol synthesis through hydrogenation may be performed by the reaction of hydrogen with COX. In general, CO2 hydrogenation to produce methanol proceeds according to the reaction: CO2 + 3H2 — > CH3OH + H2O. CO hydrogenation to produce methanol proceeds according to the reaction: CO + 2H2 — > CH3OH. Accordingly, in various embodiments, the first feed stream may comprise CO2, CO, or combinations thereof.

[0027] In particular, carbon dioxide is a common waste material often desirable to be removed from waste streams rather than be vented to the atmosphere. Such capture of carbon dioxide is critical to the implementation of many initiatives as it may be one pathway to lower the carbon emissions of the associated process. Advantageously, the carbon dioxide utilized in the processes described herein may be carbon dioxide collected from the atmosphere or that would otherwise have been released into the atmosphere, e.g., from a combustion or other industrial process. The carbon dioxide may be captured, where it is collected or absorbed after release from an industrial process, or harvested directly from the atmosphere. Methods of carbon dioxide capture are known to those of skill in the art. In various embodiments, at least a portion of the CO2 of the first feed stream is from direct air capture. Additionally or alternatively, carbon dioxide is often scrubbed from industrial effluent, especially processes that generate large amounts of carbon dioxide as a byproduct.

[0028] In various embodiments as otherwise described herein, the carbon dioxide of the first feed stream comprises captured carbon dioxide (e.g., direct air captured CO2, or captured waste CO2, such as biomass-derived CO2)., e.g., comprises at least 50%, at least 75%, at least 90% or at least 95% captured CO2.

[0029] One source of biomass is agricultural products in the form of dedicated energy crops such as switchgrass, miscanthus, bamboo, sorghum, tall fescue, kochia, wheatgrass, poplar, willow, silver maple, eastern cottonwood, green ash, black walnut, sweetgum, and sycamore. Another biomass source is agricultural waste or agricultural crop residue. Conventional agricultural activities, including the production of food, feed, fiber, and forest products, generate large amounts of waste plant material. Examples of such materials include corn stover, wheat straw, oat straw, barley straw, sorghum stubble, and rice straw. A third biomass source is through forestry residues left after timber operations. Biomass may also be in the form of commercial waste, industrial waste, sewage sludge, and municipal waste, which includes commercial and residential garbage, including yard trimmings, paper and paperboard, plastics, rubber, leather, textiles, and food waste. Accordingly, in various embodiments as otherwise described herein, at least a portion (e.g., at least 20%, at least 50%, at least 75%, at least 90% or at least 95%) of the CO2 of the first feed stream is derived from biomass gasification, for example, agricultural biomass or municipal waste biomass. Additional sources of agricultural biomass will be apparent to one of skill in the art as dictated by local availability, economics, and process compatibility.

[0030] To generate carbon dioxide from a carbon-containing material, such as biomass, the material is typically subjected to gasification. Gasification involves heating the material under controlled conditions to generate gaseous streams of carbon monoxide, hydrogen, and carbon dioxide. Controlled amounts of other reactants, such as oxygen and / or steam, may be used to tune the process. Gasification conditions are tuned in accordance with the carbon-containing material being gasified in order to efficiently produce gaseous products. The biomass may be any source as described above, or from multiple sources may be combined.

[0031] Biomass gasification can, in some embodiments, produce gas mixtures comprising carbon dioxide in admixture with other gases, such as methane and / or hydrogen sulfide. Accordingly, in various embodiments, the first feed stream comprises carbon dioxide derived from biogas. For example, entrained methane may also be included. Thus, in various embodiments, the first feed stream further comprises methane. However, in some embodiments relatively low levels of methane are desirable, for example, no more than 50 mol% of carbon-bearing species, e.g., no more than 30 mol%, or no more than 20 mol%, or no more than 10 mol%, or no more than 5 mol%. Hydrogen sulfide is a common component of biogas. However, in various embodiments, hydrogen sulfide may have a deleterious effect on certain catalysts of the process as disclosed herein. Accordingly, in various embodiments as otherwise described herein, the biogas further comprises a scrubbing step to remove at least a portion of the hydrogen sulfide.

[0032] Carbon from renewable sources, such as biomass gasification, may be differentiated from fossil-derived carbon through techniques known in the art, for example through carbon radioisotope analysis.

[0033] Methanol is a valuable feedstock for a variety of chemical processes. And when made using oxides of carbon from renewable sources using the processes described herein (e.g., CO2 capture from atmosphere or other chemical processes, or biomass conversion), it can advantageously be considered as a carrier for renewable carbon. Similarly, when made using green hydrogen and / or blue hydrogen as described herein (e.g., hydrogen formed from water electrolysis or steam reforming), the methanol can be considered as a carrier of hydrogen from such sources.

[0034] In various embodiments, the first feed stream comprises H2 and COX, as these can be reacted in contact with a hydrogenation catalyst to produce methanol. As described above the COXof the first feed stream may be selected from CO2, CO, or combinations thereof. Accordingly, in various embodiments as otherwise described herein, the first feed stream includes at least 10 mol% H2. For example, in various embodiments, the first feed stream includes at least 20 mol% H2, e.g., at least 30 mol% H2. In various embodiments as otherwise described herein, the first feed stream includes at least 5 mol% CO2. For example, in various embodiments, the first feed stream includes at least 10 mol% CO2, e.g., at least 15 mol% CO2. In various embodiments as otherwise described herein, the first feed stream includes at least 5 mol% CO. For example, in various embodiments, the first feed stream includes at least 10 mol% CO, e.g., at least 15 mol% CO.

[0035] In general, CO2 hydrogenation to produce methanol proceeds according to the reaction: CO2 + 3H2 — > CH3OH + H2O. CO hydrogenation to produce methanol proceeds according to the reaction CO + 2H2 — > CH3OH . Accordingly, in various embodiments as otherwise described herein, the ratio of H2:COXof the first feed stream is at least 1 :1 , e.g., at least 1.5:1 , on a molar basis. For example, in various embodiments as otherwise described herein, the ratio of H2:COXof the first feed stream is at least 2:1 , e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1 , or at least 6:1 , or at least 8:1. In particular embodiments, the ratio of H2:COXof the first feed stream is no more than 25:1 , e.g., no more than 20:1 , or no more than 15:1 , or no more than 12:1. In various embodiments as otherwise described herein, the ratio of H2:CO2 of the first feed stream is at least 1 :1 , e.g., at least 1.5:1 , on a molar basis. For example, in various embodiments as otherwise described herein, the ratio of H2:CO2 of the first feed stream is at least 2:1 , e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1 , or at least 6:1 , or at least 8:1. In particular embodiments, the ratio of H2:CC>2 of the first feed stream is no more than 25:1 , e.g., no more than 20:1 , or no more than 15:1 , or no more than 12:1. In various embodiments asotherwise described herein, the ratio of H2:CO of the first feed stream is at least 1 :1 , e.g., at least 1.5:1 , on a molar basis. For example, in various embodiments as otherwise described herein, the ratio of H2:CO of the first feed stream is at least 2:1 , e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1 , or at least 6:1 , or at least 8:1. In particular embodiments, the ratio of H2:CO of the first feed stream is no more than 25:1 , e.g., no more than 20: 1 , or no more than 15:1 , or no more than 12:1.

[0036] As described herein, the first feed stream may comprise CO2, CO, or combinations thereof. In various particular embodiments, the first feed stream comprises no more than 10 vol% CO (e.g., no more than 5 vol%, or 3 vol%, or 2 vol%, or 1 vol%, or 0.1 vol% CO), e.g., during the first time period. In some embodiments, the first feed stream comprises substantially no CO. In various embodiments as described herein, the first feed stream comprises a greater amount of CO2 than CO. For example, in various embodiments as described herein, the ratio of CO2:CO of the first feed stream is at least 1.5: 1 , on a molar basis. In various embodiments as otherwise described herein, the ratio of CO2:CO of the first feed stream is at least 2:1 , e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1 , or at least 6:1 , or at least 8:1. In particular embodiments, the ratio of CO2:CO of the first feed stream is no more than 25:1 , e.g., no more than 20:1 , or no more than 15:1 , or no more than 12:1.

[0037] Optionally, the first feed stream may also comprise one or more additional gases. In particular embodiments, the first feed stream further comprises an inert carrier gas, wherein the inert carrier gas includes one or more of CH4 or N2, e.g., N2. In various embodiments as otherwise described herein, at least 50 vol% of the of the first feed stream is made up of the combination of hydrogen, COXand nitrogen, e.g., at least 60 vol%, at least 70 vol%, at least 80 vol%, or at least 90 vol%. For example, in particular embodiments, the first feed stream comprises other gases in addition to COXand H2 (e.g., one or more of CH4, and N2) in an amount up to 70 mol%. In various embodiments, the first feed stream comprises no more than 1 vol% O2, for example, no more than 0.1 vol% O2, or no more than 0.01 vol% O2, or substantially no O2.

[0038] As otherwise described herein, the first feed stream is contacted with a hydrogenation catalyst. The hydrogenation catalyst may be selected by the person of ordinary skill in the art. Examples of suitable catalysts include Cu / ZnO catalysts, for example supported on aluminum oxide or zirconium oxide.

[0039] Advantageously, the COXhydrogenation reaction may be performed at a relatively low temperature, leading to increased energy efficiency and integration of the overall process. For example, in various embodiments as otherwise described herein, thecontacting of the first feed stream with the hydrogenation catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C. In various embodiments, the contacting of the first feed stream with the hydrogenation catalyst is performed at a pressure of no more than 100 bar, for example, no more than 80 bar, or no more than 60 bar.

[0040] The COXhydrogenation caused by contacting the first feed stream with the hydrogenation catalyst produces a first product stream. As described herein, the formation of the first product stream advantageously produces methanol with high selectivity.Accordingly, in various embodiments as otherwise described herein, the formation of the first product stream is performed with a selectivity of at least 50% for methanol, e.g., at least 55%, or at least 60%. For example, in particular embodiments, the formation of the first product stream is performed with a selectivity of at least 65% for methanol (e.g., at least 70%, or at least 75%, or at least 80% for methanol). Advantageously, the formation of the first product stream can be performed with a low selectivity for methane. In various embodiments as otherwise described herein, the formation of the first product stream is performed with a selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane.

[0041] As used herein, “selectivity” for a given component is measured as the molar fraction of a particular reactant that is reacted in the process (i.e. , not including any unreacted portion of that particular reactant) and is converted to that product. For example, in the reaction of carbon dioxide and hydrogen to provide product components including methanol, “selectivity” for a given component is defined as the molar fraction of carbon dioxide that is reacted in the process and is converted to the product of interest, not including any unreacted carbon dioxide.

[0042] Importantly, the COXhydrogenation reaction used to form the first product stream as described herein is not a reverse water-gas shift reaction. As known in the art, the reverse water-gas shift reaction transforms CO2 and H2 into CO and H2O by the reaction: CO2 + H2CO + H2O. However, the reverse water gas shift reaction is typically performed at extreme conditions, with reaction temperatures in excess of 900 °C to drive high rates of conversion. Additionally, the operating conditions required to provide adequate rates of conversion for the reverse water-gas shift reaction often lead to deposits of coke on the reverse water-gas shift catalyst which impacts the longevity of the catalyst life. Thus, the reaction is costly from an energy and catalyst lifetime standpoint, and specialized equipment must be used. An advantage of the processes of the present disclosure is the ability, in various embodiments, to convert carbon dioxide to hydrocarbons through a methanolintermediate without using the reverse water gas shift reaction. Accordingly, in various embodiments as otherwise described herein, the process does not include a reverse water gas shift reaction. It is possible that a small proportion of carbon dioxide are converted to carbon monoxide by the reverse water-gas shift reaction as a reaction side product during normal operation of the processes described herein. Accordingly, the absence of a reverse water-gas shift reaction is understood to mean that there is not a distinct reaction zone dedicated to the reverse water-gas shift reaction. Accordingly, in various embodiments as otherwise described herein, the formation of the first product stream is performed with a selectivity of no more than 20% for CO, e.g., no more than 10%, or no more than 5% for CO. In particular embodiments, the formation of the first product stream is performed with a selectivity of no more than 2% for CO, or 1% for CO.

[0043] In other embodiments as otherwise described herein, the process includes a water gas shift reaction, however, in particular embodiments, the water gas shift reaction is operated so as to consume carbon monoxide and water and generate carbon dioxide and hydrogen.

[0044] During the COXhydrogenation reaction used to form the first product stream, at least a portion of the COXis hydrogenated into MeOH and H2O. Advantageously, this process may be performed with a relatively high conversion of CO2 and / or CO. Accordingly, in various embodiments as otherwise described herein, the formation of the first product stream is performed with a conversion of CO2 of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%. In various embodiments as otherwise described herein, the formation of the first product stream is performed with a conversion of CO of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%.

[0045] The person of ordinary skill in the art will be familiar with catalytic methods for the hydrogenation of carbon monoxide and carbon dioxide to methanol. Various examples of catalysts and catalytic processes are described in R.Guil-Lopez et al., Materials, 12, 3902 (2019); Xiao et al., In: Aresta et al. (eds) An Economy Based on Carbon Dioxide and Water (2019); Marlin et al., Front. Chem. (2018); Rodriguez et al., ACS Cat. 5(11), 6696 (2015); Choundhury, Chem. Cat. Chem. 4(5), 609 (2012), each of which is hereby incorporated herein by reference in its entirety.

[0046] In various embodiments as otherwise described herein, the first product stream includes at least 15 mol% methanol, e.g., at least 25 mol%, or at least 35 mol% methanol. As described herein, the COXhydrogenation also has advantageously low selectivity for other products such as methane and / or carbon monoxide. Accordingly, in various embodiments as otherwise described herein, the first product stream includes no more than 10 mol% methane, e.g., no more than 5 mol% methane, or no more than 2 mol% methane.In various embodiments as otherwise described herein, the first product stream includes no more than 10 mol% CO, e.g., no more than 5 mol% CO, or no more than 2 mol% CO. Of course, in some embodiments, there may be more methane and / or CO present.

[0047] As described above, through COXhydrogenation the contacting of the first feed stream with the hydrogenation catalyst produces both methanol and water. The formed water can in some cases be deleterious to subsequent processes. For example, excess water present in a subsequent methanol-to-hydrocarbon process step can kinetically inhibit conversion. Accordingly, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of water of the first product stream therefrom. For example, in particular embodiments, the process further comprises 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 of the first product stream therefrom. In various embodiments as otherwise described herein, the portion of the first product stream that is included in the second feed stream has a water content of no more than 10 mol%, e.g., no more than 2 mol%, or no more than 1 mol%, or no more than 0.5 mol%.

[0048] In embodiments in which water is separated from the first product stream, the water may be disposed of as waste, or recycled into other processes. For example, in various embodiments, the separated water is directed to an electrolysis reactor for the formation of H2 gas, e.g., for use in this integrated process or in other processes. In various embodiments, the separated water is subjected to a purification step before introduction into the electrolysis reactor.

[0049] In various embodiments as otherwise described herein, not all H2 gas input to the COx hydrogenation is reacted. Accordingly, in such embodiments, the process may further comprise separating at least a portion of H2 from the first product stream. For example, in particular embodiments as otherwise described herein, the process further comprises separating at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 in the first product stream. The separated H2 may be optionally purified, and then optionally recycled. In various embodiments, the at least a portion of the separated H2 may be recycled to the first feed stream, and / or may be directed to another reactor.

[0050] Compared to gaseous compositions, compositions that are liquid at ambient temperature and pressure generally possess lower capital expenditure for handling due to their increased density and decreased need for high pressures and / or low temperatures. The present inventors have noted that the methanol product of the COXhydrogenation can be simply stored and / or transported. Accordingly, in various embodiments as otherwise described herein, the contacting of the second feed stream and / or third feed stream with themethanol-to-hydrocarbon synthesis catalyst and the contacting of the first feed stream with the hydrogenation catalyst may be performed in different plants. For example, in some embodiments, the contacting of the second feed stream and / or third feed stream with the methanol-to-hydrocarbon synthesis catalyst and the contacting of the first feed stream with the hydrogenation catalyst are performed in different plants. As used herein, a different “plant” is not merely a different catalyst bed or different vessel, but rather a different facility than the facility in which the COXhydrogenation is performed. In such embodiments, the plant in which the second feed stream and / or third feed stream is contacted with the methanol-to-hydrocarbon synthesis catalyst can be, e.g., at least 1 km away from the plant in which the first feed stream is contacted with the hydrogenation catalyst.

[0051] The duration of the first period of time can vary. In various embodiments, the first period of time is at least 2 hours, e.g., at least 4 hours, at least 8 hours, or at least 24 hours.

[0052] In various embodiments as otherwise described herein, a synthesized methanol fraction of the second feed stream is substantially greater than a synthesized methanol fraction of the third feed stream. As used herein, the term “synthesized methanol” signifies methanol that is provided substantially directly to methanol-to-hydrocarbon synthesis, without storage to significantly delay its use. “Synthesized methanol” is methanol that is contacted with a methanol-to-hydrocarbon synthesis catalyst under methanol-to- hydrocarbon synthesis conditions within a first period of time of its synthesis from hydrogenation of COXas described herein. The synthesized methanol may be transported from a COXhydrogenation reactor to a methanol-to-hydrocarbon synthesis reactor, such as via pipeline, railcar, or truck. The “synthesized methanol fraction” of a feed stream is the fraction of methanol of the feed stream that is “synthesized methanol” as described above. As used herein, “stored methanol” is methanol that is made by hydrogenation of COXas described herein, and is contacted with a methanol-to-hydrocarbon synthesis catalyst under methanol-to-hydrocarbon synthesis conditions only after the lapse of a first period of time from its synthesis from hydrogenation of COX. The “stored methanol fraction” of a feed stream is the fraction of methanol of the feed stream that is “stored methanol” as described above. The stored methanol may be transported from a COXhydrogenation reactor to a methanol-to-hydrocarbon synthesis reactor, such as via pipeline, railcar, or truck.

[0053] The first period of time is a value that distinguishes between substantially immediate use of methanol from a COXhydrogenation on one hand, and the longer-term storage of such methanol on the other hand. This value can be selected by the person of ordinary skill in the art based on the present description, taking into account a variety of factors, for example, the size of the plant, the distance between a COXhydrogenation reactorand a methanol decomposition reactor, and the potential for intermittency of provision of hydrogen for the synthesis of methanol.

[0054] The synthesized methanol fraction of a feed stream is determined at time of contact with the methanol-to-hydrocarbon synthesis catalyst, as the fraction of total methanol that is synthesized methanol. Thus, a feed stream having 10 kg of methanol provided directly from COXhydrogenation (i.e., within a first period of time as described herein) and 40 kg of methanol stored from much earlier COXhydrogenation would have a synthesized methanol fraction of 0.20.

[0055] As described above, the present inventors have recognized that methanol can serve as a storage vehicle for COXand H2, as it can be easily transported and stored as a liquid. Thus, stored methanol can serve as a buffer against intermittent hydrocarbon production. Thus, methanol can be synthesized (e.g., by COXhydrogenation), or otherwise provided, and stored for later use, acting essentially as a stockpile of stored COXand H2. During times when hydrogen production is high, such as in some embodiments during the first period of time, a portion of the methanol made by COXhydrogenation may be stored for later use. Accordingly, in various embodiments as otherwise described herein, the method further comprises, during the first period of time, storing at least a portion of the methanol of the first product stream. In various embodiments as otherwise described herein, at least a portion of the methanol stored during the first period of time is provided to the third feed stream during the second period of time.

[0056] For example, in various embodiments as otherwise described herein, the process further comprises storing at least a portion of the methanol of the first product stream to provide stored methanol. Methanol can be stored, e.g., in various embodiments as otherwise described herein, in a storage tank, railcar, pipeline under stopped flow conditions, or other suitable holding vessel. For example, as shown in FIG. 1 , at least a portion of the methanol of the first product stream 102 is provided to the methanol storage tank 120 via stored methanol stream 105.

[0057] In various embodiments as otherwise described herein, the first period of time can be characterized by abundant hydrogen production such that methanol can be directly synthesized and then subjected to methanol-to-hydrocarbon synthesis to produce a hydrocarbon stream, and / or diverted to storage for later use. In various embodiments, H2 production through electrolysis, and therefore methanol production, may vary in proportion to the availability of renewable sources of energy, such a wind or solar. For example, in various embodiments, synthesized methanol of the first product stream may be divided between the second feed stream and a storage stream, wherein the storage streamtransmits the synthesized methanol to storage. In time periods when methanol production is high, synthesized methanol may be provided to both the second feed stream and to the storage stream. In embodiments where methanol production is moderate, for example commensurate with the demands of a downstream process, such as methanol-to- hydrocarbon production, synthesized methanol may be provided to the second feed stream, and essentially no methanol provided to the storage stream. In embodiments where methanol production is low, for example below the demands of a downstream process, such as methanol-to-hydrocarbon production, synthesized methanol may be provided to the second feed stream, for example, all synthesized methanol may be provided to the second feed stream. In such embodiments, stored methanol may be also provided to the second feed stream, for example sufficient stored methanol to meet the needs of a downstream process when provided in combination with the synthesized methanol. In embodiment where methanol production is essentially zero, no synthesized methanol may be provided to the second feed stream, and stored methanol may be supplied to the second feed stream.

[0058] Accordingly, in various embodiments as otherwise described herein, substantially all of the methanol of the second feed stream is synthesized methanol. For example, in various embodiments, the second feed stream has a synthesized methanol fraction of at least 95%, e.g., at least 98%, or at least 99%. However, substantial amounts of methanol other than synthesized methanol may be present in the second feed stream in some embodiments. For example, in various embodiments, the second feed stream has a synthesized methanol fraction of at least 50%, e.g., at least 65%, or at least 75%. In various embodiments, the second feed stream has a synthesized methanol fraction of at least 80%, e.g., at least 85%, or at least 90%.

[0059] In various embodiments as described here, the second feed stream further comprises stored methanol. For example, in various embodiments, a portion of methanol stored during the first period of time is provided to the second feed stream. An example of such an embodiment is shown in FIG. 2, in the process 200, where stored methanol can be withdrawn from methanol storage tank 220 to the second feed stream 203 via the stored methanol stream 208 during the first time period. As otherwise described herein, the process 200 of FIG. 2 includes the first feed stream 201 is introduced into the hydrogenation reactor 210 with the hydrogenation catalyst 213 and the methanol-containing first product stream 202 is withdrawn. Depending on the time period as described herein, the synthesized methanol can be directly introduced into the second feed stream 203 which enters the methanol-to-hydrocarbon synthesis reactor 230 containing the methanol-to- hydrocarbon synthesis catalyst 133, and a hydrocarbon product stream 206 is withdrawn. Additionally or alternatively, methanol can be withdrawn from the first product stream 202 inthe stored methanol stream 205 to the methanol storage tank 220. Subsequently, stored methanol can be withdrawn from methanol storage tank 220 to form third feed stream 204 which is introduced into the methanol-to-hydrocarbon synthesis reactor 230 containing a methanol-to-hydrocarbon catalyst 233, and the hydrocarbon product stream 206 is withdrawn.

[0060] In various embodiments as otherwise described herein, during a second period of time a third feed stream comprising stored methanol is provided to the methanol-to- hydrocarbon synthesis catalyst. Advantageously, stored methanol can be used during times when the supply of hydrogen is relatively lower than in the first period of time, such as times when energy production from renewable sources is low. In such times, the output of synthesized methanol may be decreased and stored methanol used to continue a relatively constant methanol supply to the methanol-to-hydrocarbon synthesis catalyst, thereby enabling the maintenance of a desirable production of a hydrocarbon stream. Accordingly, in various embodiments as otherwise described herein, the third feed stream has a synthesized methanol fraction of no more than 90%, e.g., no more than 85%, or no more than 80%. In various embodiments, the third feed stream has a synthesized methanol fraction of no more than 75%, e.g., no more than 70%, or no more than 65 wt%. In various embodiments, the third feed stream has a synthesized methanol fraction of no more than 60 wt%, e.g., no more than 55 wt%, or no more than 50 wt%. In various embodiments, the third feed stream has a synthesized methanol fraction of no more than 45%, e.g., no more than 40%, or no more than 35%. In various embodiments, the third feed stream has a synthesized methanol fraction of no more than 30%, e.g., no more than 25%, or no more than 20%. In various embodiments, the third feed stream has a synthesized methanol fraction of no more than 15%, e.g., no more than 10%, or no more than 5%.

[0061] Substantial amounts of methanol of the third feed stream can be provided by stored methanol. For example, in various embodiments, substantially all of the methanol of the third feed stream is stored methanol. But amounts can vary. In various embodiments, the third feed stream has a stored methanol fraction of at least 5%, e.g., at least 10%, or at least 15%. In various embodiments, the third feed stream has a stored methanol fraction of at least 20%, e.g., at least 25%, or at least 30%. In various embodiments, the third feed stream has a stored methanol fraction of at least 35%, e.g., at least 40%, or at least 45%. In various embodiments, the third feed stream has a stored methanol fraction of at least 50%, e.g., at least 55%, or at least 60%. In various embodiments, the third feed stream has a stored methanol fraction of at least 65%, e.g., at least 70%, or at least 75%. In various embodiments, the third feed stream has a stored methanol fraction of at least 80%, e.g., atleast 85%, or at least 90%. In various embodiments, the third feed stream has a stored methanol fraction of at least 95%, e.g., at least 98%, or at least 99%.

[0062] Stored methanol can conveniently be stored for substantial periods of time. The storage time of a body of methanol is the weight-average storage time over the body, e.g., a sample that includes 1 kg of methanol stored for 5 hours and 1 kg of methanol stored for 25 hours would have a storage time of 15 hours. A storage tank is assumed for this purpose to be homogenously mixed.

[0063] In various embodiments as otherwise described herein, stored methanol of the third feed stream has a storage time of at least three hours, e.g., at least 5 hours, or at least 8 hours. In various embodiments, stored methanol of the third feed stream has a storage time of at least 12 hours, e.g., at least 18 hours or at least 24 hours. In various embodiments, stored methanol has a storage time of at least 36 hours, e.g., at least three days or at least seven days.

[0064] Stored methanol can be stored for significant amounts of time. Of course, while it can be desirable to store methanol for use when methanol production by hydrogenation of COx is reduced, it can also be desirable not to stockpile too much methanol. Accordingly, especially when the reduced methanol production is a cyclical phenomenon (e.g., as when depending on solar or tidal power), it can be desirable to use stored methanol reasonably regularly, so as to avoid stockpiling too much methanol, to limit working capital, and / or limit the total inventory of flammable material at a particular site. Accordingly, in various embodiments, stored methanol of the third feed stream has a storage time of no more than 30 days, e.g., no more than 21 days, or no more than 14 days, or no more than seven days. In various embodiments, stored methanol of the third feed stream has a storage time of no more than three days, e.g., no more than two days, or no more than one day.

[0065] In various embodiments as described herein, the process further comprises, during the first period of time, storing at least a portion of the methanol of the first product stream. For example, in some embodiments, the methanol stored during the first period of time is provided to the third feed stream during the second period of time. Of course, stored methanol can come from a variety of sources (including external sources), and need not be provided by methanol synthesis during a first time period.

[0066] In some embodiments as described herein, the process further comprises providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; and including at least a portion of synthesized methanol of the first product stream in the third feed stream. An example of such an embodiment isshown in FIG. 3, in the process 300, where methanol can be withdrawn from the first product stream 302 and provided to the third feed stream 304 via synthesized methanol stream 307. As otherwise described herein, the process 300 of FIG. 3 includes the first feed stream 301 is introduced into the hydrogenation reactor 310 with the hydrogenation catalyst 313 and the methanol-containing first product stream 302 is withdrawn. Depending on the time period as described herein, the synthesized methanol can be directly introduced into the second feed stream 303 which enters the methanol-to-hydrocarbon synthesis reactor 330 containing the methanol-to-hydrocarbon synthesis catalyst 333, and a hydrocarbon product stream 306 is withdrawn. Additionally or alternatively, methanol can be withdrawn from the first product stream 302 in stored methanol stream 305 to methanol storage tank 320. Additionally or alternatively, stored methanol can be withdrawn from methanol storage tank 320 to form third feed stream 304 which is introduced into the methanol-to-hydrocarbon synthesis reactor 330 containing the methanol-to-hydrocarbon catalyst 322, and the hydrocarbon product stream 306 is withdrawn.

[0067] In some desirable embodiments the second feed stream and / or the third feed stream are substantially made up of synthesized methanol and stored methanol. For example, in various embodiments, the second feed stream and / or the third feed stream has a sum of a synthesized methanol fraction and a stored methanol fraction of at least 95%, e.g., at least 98%, or at least 99%. However, methanol of the second feed stream and / or the third feed stream can be provided by other sources, and so in some cases the sum of the synthesized methanol fraction of the second feed stream and / or the third feed stream is substantially less than 100%.

[0068] As described herein, in various embodiments, the synthesized methanol fraction of the second feed stream is substantially greater than the synthesized methanol fraction of the third feed stream. For example, in various embodiments, a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 5%, e.g., at least 10%, or at least 15%. In various embodiments, a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 20%, e.g., at least 25%, or at least 30%. In various embodiments, a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 35%, e.g., at least 40%, or at least 45%. In various embodiments, a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 50%, e.g., at least 55%, or at least 60%. In various embodiments, a difference between thesynthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 65%, e.g., at least 70%, or at least 75%.

[0069] The processes described herein can be especially useful in addressing intermittent loss of hydrogen used to make methanol via COXhydrogenation, for example, due to an intermittent decrease or loss of renewable sources of energy used to make the hydrogen. This can occur, e.g., due to a loss of solar power, for example, at night or during cloudy weather, or a loss of wind power, or a loss of tidal power. In such cases, stored methanol can be used to maintain the hydrocarbon synthesis process, e.g., during the second period of time. In various embodiments, the second period of time is in the range of 30 minutes to 24 hours in length (e.g., 30 minutes to 18 hours, or 30 minutes to 12 hours, or 1-24 hours, or 1-18 hours, or 1-12 hours, or 3-24 hours, or 3-18 hours, or 3-12 hours, or 6-24 hours, or 6-18 hours, or 6-12 hours), and occurs after the first period of time.

[0070] After the second period of time, when a renewable source of energy is restored, the use of stored methanol can be reduced or ceased. Accordingly, in various embodiments, the second period of time is followed by another first period of time (i.e., in which the synthesized methanol fraction of the second feed stream is substantially greater than the synthesized methanol fraction of the third feed stream as used during the second period of time, e.g., within 20% (e.g., within 10% of) of the synthesized / stored ratio of the first period of time.

[0071] In various embodiments, e.g., especially when the loss of renewable sources of energy is due to a regular phenomenon such as nightfall or tidal patterns, the process includes a plurality of first and second periods of time.

[0072] Of course, the use of a stream of stored methanol as described herein may require heating or otherwise modifying the stream to integrate it with the downstream methanol decomposition process, especially in cases where syngas is produced by methanol synthesis followed immediately by methanol decomposition during the first period of time. The person of ordinary skill based on the disclosure herein can provide suitable reaction systems to perform such processes.

[0073] As described above, in some conventional implementations the intermittency of renewable energy sources used for producing hydrogen can interrupt a steady-state production of hydrocarbons downstream. Here, the present inventors have found that methanol can be a useful way to store both hydrogen and carbon to maintain the steadystate production of hydrocarbons. Accordingly, in various embodiments as described herein, the rate of production of the hydrocarbon product stream during the first period of time is at least 70% of the rate of production of the hydrocarbon product stream during the secondperiod of time. For example, in various embodiments as described herein, the rate of production of the hydrocarbon product stream during the first period of time is at least 80%, or at least 85%, or at least 90%, or at least 95%, of the rate of production of the hydrocarbon product stream during the second period of time. In some embodiments as described herein, the rate of production of the hydrocarbon product stream during the first period of time is at least 99% of the rate of production of the hydrocarbon product stream during the second period of time. In some embodiments as described herein, the rate of production of the hydrocarbon product stream during the first period of time is the same as of the rate of production of the hydrocarbon product stream during the second period of time.

[0074] In some embodiments as described herein, not all of the synthesized methanol produced by COXhydrogenation is stored or sent to the methanol-to-hydrocarbon synthesis reactor. In various embodiments, at least a portion of the synthesized methanol can be used for other processes, such as methanol decomposition, for production of other useful compounds for the processes as otherwise described herein.

[0075] Notably, it can be desirable to operate the methanol-forming hydrogenation process in a relatively steady-state, which can also be impacted by intermittent supply of hydrogen and / or COX. The present inventor has noted that decomposition of methanol can provide another means to provide a feed stream for the hydrogenation during intermittent production from renewable sources. Methanol used in decomposition to CO and H2 can come from stored methanol. But it can also come from the methanol synthesis itself, i.e. , decomposing the synthesized methanol just to use the resulting CO and H2 in the methanol synthesis. This looped operation of methanol synthesis / methanol decomposition can allow the methanol synthesis to continue operating without substantial H2 / COXinput, but it may often be desirable to decompose a small amount of stored methanol to ensure steady state operation. By introducing a methanol decomposition to the overall process, interruption of the methanol synthesis itself from intermittent hydrogen production from renewable sources can be limited, allowing for the steady-state production of methanol. This in turn can provide overall benefits in maintaining a steady-state production of hydrocarbons downstream.

[0076] For example, in various embodiments, the process as otherwise described herein further comprises for a third period of time: providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol);contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.

[0077] Production of the fourth product stream need not be limited to the third period of time, but can also be carried out during the first and / or second periods of time as described herein. Accordingly, in various embodiments, the process further comprises, during the first period of time, providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.

[0078] Additionally or alternatively, in various embodiments, the process as otherwise described herein further comprises, during the second period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.

[0079] In various methanol decomposition-based embodiments as described above with respect to the first, second, and third periods of time, the fourth feed stream includes at least a portion of the synthesized methanol of the first product stream. In various such embodiments, the fourth feed stream further comprises stored methanol.

[0080] In various methanol decomposition-based embodiments as described above with respect to the first, second, and third periods of time, the fourth feed stream includes stored methanol.

[0081] An example of such an embodiment is shown in FIG. 4. In the process 400, methanol can be withdrawn from the first product stream 402 and provided to the methanol decomposition reactor 440 with the methanol decomposition catalyst 443 via methanol stream 409. CO and H2 can be withdrawn from the fourth product stream 411 and provided to the first feed stream 401. Subsequently, stored methanol can be withdrawn from methanol storage tank 420 and provided to the methanol decomposition reactor 440 via stored methanol stream 412. As otherwise described herein, the process 400 of FIG. 4 includes the first feed stream 401 is introduced into hydrogenation reactor 410 with a hydrogenation catalyst 413 and the methanol-containing first product stream 402 is withdrawn. Depending on the time period as described herein, the synthesized methanol can be directly introduced into second feed stream 403 which enters methanol-to-hydrocarbon synthesis reactor 430 containing a methanol-to-hydrocarbon synthesis catalyst 433, and a hydrocarbon product stream 406 is withdrawn. Additionally or alternatively, methanol can be withdrawn from the first product stream 402 in stored methanol stream 405 to methanol storage tank 420. Subsequently, stored methanol can be withdrawn from methanol storage tank 420 to form third feed stream 404 which is introduced into the methanol-to-hydrocarbon synthesis reactor 430 containing a methanol-to-hydrocarbon catalyst 422, and the hydrocarbon product stream 406 is withdrawn.

[0082] As described herein, the fourth feed stream is contacted with a methanol decomposition catalyst. Any suitable decomposition catalyst may be used; a variety are known in the art. For example, the decomposition catalyst may include a transition metal, for example, Ni, Co, Rh, Ir, Cu, Pt, Ru, or mixtures thereof. The decomposition catalyst may be a supported catalyst, wherein the support is a refractory oxide, such as oxidized diamond, silica, zirconia, ceria, titania, alumina, or magnesia. In some embodiments, the methanol decomposition catalyst is a copper / zinc oxide catalyst, e.g., on alumina.

[0083] The contacting of the fourth feed stream with the methanol decomposition catalyst occurs at a temperature suitable to effect efficient methanol decomposition. In various embodiments as otherwise described herein, the contacting of the fourth feed stream with the methanol decomposition catalyst is performed at a temperature in the range of 200- 500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400 °C. The contacting may be performed at a variety of suitable pressures, for example, in the range of 0 to 50 barg, wherein barg is a unit of gauge pressure, being the pressure in barsabove ambient or atmospheric pressure. Accordingly, in such embodiments, the contacting with the methanol decomposition catalyst may be performed at relatively high pressures, for example, in the range of up to 50 barg, e.g., 20 to 40 barg.

[0084] As described herein, the contacting of the fourth feed stream with the methanol decomposition catalyst may be performed in the same plant as the contacting of the first feed stream with the hydrogenation catalyst. In such examples, it may be advantageous to coordinate the temperatures of the methanol decomposition reaction and the hydrogenation reaction in order to avoid excessive heating and cooling capital costs and energy costs. Accordingly, in particular embodiments as otherwise described herein, the contacting of the fourth feed stream with the methanol decomposition catalyst is performed at a temperature within 75 °C of a temperature of the contacting of the first feed stream with the hydrogenation catalyst, e.g., within 50 °C.

[0085] Methanol decomposition reaction generates CO and H2, ideally with minimal other products. Accordingly, in various embodiments as otherwise described herein, the decomposition of methanol is performed with a carbon product selectivity of at least 50% for CO, e.g., at least 60%, or at least 70%, or at least 80%, or at least 90% for CO. Advantageously, in various embodiments, the decomposition of methanol is performed with a selectivity of no more than 20% for CO2, e.g., no more than 15%, or no more than 10%, or no more than 5%. In various embodiments as otherwise described herein, the decomposition of methanol is performed with a conversion of methanol of at least 30%, e.g., at least 40%, or at least 50%, or at least 60%, or at least 65%, or at least 70%, or at least 75%.

[0086] As described herein, the decomposition of methanol, such as through the contacting of the fourth feed stream with a methanol decomposition catalyst, generates CO and H2. Accordingly, in various embodiments as otherwise described herein, the fourth product stream comprises at least 20 mol% total of CO and H2, e.g., at least 35 mol%, or at least 50 mol%, or at least 65 mol%. Without wishing to be bound by theory, methanol decomposition under these conditions is expected to generate two moles of H2 per mole of CO. Accordingly, in various embodiments as otherwise described herein, the fourth product stream has a molar ratio of hydrogen to carbon monoxide 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 be different, e.g., as a consequence of inclusion of H2 and / or CO in the fourth feed stream.

[0087] Advantageously, a proportion of methanol is consumed during the methanol decomposition reaction. Accordingly, in various embodiments as otherwise describedherein, the fourth product stream includes no more than 75 mol% methanol, e.g., no more than 60 mol% methanol, no more than 50 mol% methanol, or no more than 25 mol% methanol.

[0088] In some embodiments, further removal of methanol from the fourth product stream is desired. For example, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of methanol from the fourth product stream, e.g., separating at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the fourth product stream. Advantageously, methanol of the fourth product stream, e.g., at least a portion of the methanol separated from the fourth product stream, may be transferred or recycled to other processes. For example, in various embodiments as otherwise described herein, the process further comprises recycling to the fourth feed stream at least a portion of the methanol separated from the fourth product stream. In other embodiments, the process further comprises storing at least a portion of the methanol from the fourth product stream to form recycled and stored methanol, and then providing at least a portion of the recycled and stored methanol to the fourth feed stream.

[0089] The person of ordinary skill in the art will be familiar with catalytic methods for the decomposition of methanol to CO and H2. Various examples of catalysts and catalytic processes are described in U.S. Patent no. 6,541,142, U.S. Patent no, 9,883,773, and U.S. Patent no. 4,716,859 each of which is hereby incorporated herein by reference in its entirety.

[0090] In various embodiments as otherwise described herein, the second feed stream and / or third feed stream introduces methanol to a methanol-to-hydrocarbon synthesis catalyst to form a hydrocarbon product stream comprising one or more hydrocarbons.

[0091] As described herein, methanol-to-hydrocarbon synthesis is utilized to form a hydrocarbon product stream that includes one or more hydrocarbons. Accordingly, in various embodiments as otherwise described herein, the second feed stream comprises at least 5 mol% methanol. For example, in particular embodiments, the second feed stream comprises at least 7.5% methanol, e.g., at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol. Similarly, in various embodiments as otherwise described herein, the third feed stream comprises at least 5 mol% methanol. For example, in particular embodiments, the third feed stream comprises at least 7.5% methanol, e.g., at least 10% methanol, or at least 15% methanol, or at least 20% methanol, or at least 25 mol% methanol.

[0092] Optionally, the second feed stream and / or third feed stream may also comprise one or more additional gases. In such embodiments, the second feed stream and / or third feed stream may further comprise one or more of H2, CO, CH4, CO2, and N2. In particularembodiments, the second feed stream and / or third feed stream comprises an inert carrier gas, wherein the inert carrier gas includes one or more of CH4, CO2 and N2. In various embodiments as otherwise described herein, one or more of H2, CO, CH4, CO2, and N2 are present in second feed stream and / or third feed stream in an amount in the range of up to 50 mol%, e.g., up to 40 mol%, or up to 30 mol%.

[0093] In various embodiments, the second feed stream and / or third feed stream has a low water content. Any water present can react with methanol via reforming to provide H2 and CO2, and water can also react with CO to be at least partially converted to CO2 and H2 through the water-gas shift reaction. Accordingly, in various embodiments as otherwise described herein, the second feed stream and / or third feed stream has a concentration of water of no more than 5 mol%, e.g., no more than 2 mol%, or no more than 1 mol %, or no more than 0.5 mol%, or no more than 0.3 mol%, or no more than 0.2 mol%, or no more than 0.1 mol%.

[0094] In certain embodiments, the second feed stream and / or third feed stream may be provided at elevated temperature. For example, in various embodiments as otherwise described herein, the second feed stream and / or third feed stream has a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250- 500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300- 400 °C.

[0095] As described herein, an aspect of the present disclosure is the production of hydrocarbons. As described above, the process includes contacting the second and third feed streams with a methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to- hydrocarbon synthesis reactor) to from a hydrocarbon product stream comprising one or more hydrocarbons. Any suitable methanol-to-hydrocarbon catalyst may be used; a variety are known in the art. Various methanol-to-hydrocarbon synthesis process are known in the art, including methanol-to-gasoline synthesis, methanol-to-olefin synthesis, methanol-to- propene synthesis, and methanol-to-aromatics catalyst. Such methods and catalyst can be chosen by the skilled person to provide the desired hydrocarbon product.

[0096] For example, in various embodiments as described herein, the methanol-to- hydrocarbon synthesis catalyst is a methanol-to-gasoline catalyst, a methanol-to-olefins catalyst, a methanol-to-propene catalyst, or a methanol-to-aromatics catalyst. In particular embodiments as described herein, the methanol-to-hydrocarbon synthesis catalyst is a methanol-to-olefins catalyst.

[0097] In some embodiments as described herein, the methanol-to-hydrocarbon synthesis catalyst is a solid acid catalyst (e.g., a solid Bronsted acid catalyst). In someembodiments as described herein, the methanol-to-hydrocarbon synthesis catalyst is a zeolite-based catalyst. For example, in various embodiments as described herein, the zeolite-bed based catalyst is based on a zeolite of type ZSM-5, SAPO-34, ZSM-11, ZSM-12, ZSM-21 and TEA-Mordenite. The zeolite-based catalyst may be further doped with a variety of metals. For example, in various embodiments, the zeolite-based catalyst is doped with phosphorous, boron, magnesium, antimony, or silicon.

[0098] In various embodiments as described herein, contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature of at least 250 °C (e.g., at least 300 °C, or at least 350 °C). For example, in some embodiments as described herein, contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature in the range of 250-750 °C (e.g., in the range of 250-700 °C, or 250-650 °C, or 250-600 °C, or 300-750 °C, or 300-700 °C, or 300- 650 °C, or 300-600 °C).

[0099] In various embodiments as described herein, contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure of no more than 100 bar (e.g., in more than 50 bar, or no more than 20 bar). For example, in various embodiments, contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure in the range of 1-20 bar (e.g., in the range of 1-15, or 1- 10 bar).

[0100] In various embodiments as described herein, contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature of at least 250 °C (e.g., at least 300 °C, or at least 350 °C). For example, in some embodiments as described herein, contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature in the range of 250-750 °C (e.g., in the range of 250- 700 °C, or 250-650 °C, or 250-600 °C, or 300-750 °C, or 300-700 °C, or 300-650 °C, or 300- 600 °C).

[0101] In various embodiments as described herein, contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure of no more than 100 bar (e.g., in more than 50 bar, or no more than 20 bar). For example, in various embodiments, contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure in the range of 1-20 bar (e.g., in the range of 1-15, or 1- 10 bar).

[0102] In various embodiments as described herein, contacting the second feed stream and / or contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted for a time sufficient to form a hydrocarbon product stream.

[0103] The person of ordinary skill in the art will be familiar with catalytic methods for the methanol-to-hydrocarbon synthesis. Various examples of catalysts and catalytic processes are described in U.S. Patent No. 3,894,107; U.S. Patent No. 3,911 ,041 ; U.S. Patent No. 4,025,571 ; U.S. Patent No. 4,025,575; U.S. Patent No. 4,046,825; U.S. Patent No.4,049,573; U.S. Patent No. 4,052,479; U.S. Patent No. 4,059,646; U.S. Patent No.4,059,647; U.S. Patent No. 4,062,905; U.S. Patent No. 4,079,095; U.S. Patent No.4,079,096; U.S. Patent No. 4,088,706; U.S. Patent No. 4,387,263; U.S. Patent No.4,499,314; U.S. Patent No. 4,677,242; U.S. Patent No. 5,095,163; U.S. Patent No.5,126,308; U.S. Patent No. 5,191 ,141 ; U.S. Patent No. 6,613,951 ; U.S. Patent No.7,148,172; U.S. Patent No. 7,825,287; U.S. Patent No. 11 ,492,307B2; Liu et al., Chem. Synth. 2(21), (2022); Stocker, Micropor. Mesopor. Mat. 29(1-2), 3-48, (1999); Liu et al. Chinese J. Catal. 47, 67-92, (2023); each of which is hereby incorporated herein by reference in its entirety.

[0104] Advantageously the methanol-to-hydrocarbon synthesis can be conducted at a high selectivity for hydrocarbons. In some embodiments as described herein, the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C2-C4 olefins (e.g., at least 40%, or at least 50% for C2-C4 olefins). In some embodiments as described herein, the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C5+ olefins (e.g., at least 40%, or at least 50% for C5+ olefins). In some embodiments as described herein, the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C2-C4 alkanes (e.g., at least 40%, or at least 50% for C2-C4 alkanes). In some embodiments as described herein, the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C5+ alkanes (e.g., at least 40%, or at least 50% for C5+ alkanes). In some embodiments as described herein, the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for aromatics (e.g., at least 40%, or at least 50% for aromatics). For example, in various embodiments as described herein, the aromatics comprise xylenes, trimethyl benzene, tetramethyl benzene, or combinations thereof.

[0105] Advantageously, the formation of the hydrocarbon product stream can be performed with a low selectivity for methane. In various embodiments as otherwise described herein, the formation of the hydrocarbon product stream is performed with a selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane.

[0106] As would be understood by the person of ordinary skill in the art, methanol-to- hydrocarbon synthesis proceed by an initial C-C bond formation mechanism and a later stage C-C bond formation mechanism. It is hypothesized that the initial C-C bond formation mechanism involves the direct coupling of methanol with its derivatives such as methoxymethyl cations, CO, carbene, and formaldehyde, although the details of the direct coupling mechanism are still disputed. It is generally accepted that the later stage C-C bond formation is accomplished via an indirect hydrocarbon pool mechanism. In the indirect hydrocarbon pool mechanism, a pool of hydrocarbon species (e.g., (CH2)n) are first generated and then further reacted with methanol to olefins, alkanes, and aromatics. Accordingly, in various embodiments as described herein, the one or more hydrocarbons of the hydrocarbon product stream comprise one or more olefins, alkanes, or aromatics. For example, in some embodiments, the one of more hydrocarbons of the hydrocarbon product stream are olefins. In some embodiments as described herein, the hydrocarbon product stream comprises at least 5 mol% C2-C4 olefins (e.g., at least 10 mol% C2-C4 olefins, or at least 15 mol% C2-C4 olefins). In some embodiments as described herein, the hydrocarbon product stream comprises at least 5 mol% C5+ olefins (e.g., at least 10 mol% C5+ olefins, or at least 15 mol% C5+ olefins). In some embodiments as described herein, the one or more hydrocarbons of the hydrocarbon product stream are alkanes. In some embodiments as described herein, the hydrocarbon product stream comprises at least 5 mol% C2-C4 alkanes (e.g., at least 10 mol% C2-C4 alkanes, or at least 15 mol% C2-C4 alkanes). In some embodiments as described herein, the hydrocarbon product stream comprises at least 5 mol% C5+ alkanes (e.g., at least 10 mol% C5+ alkanes, or at least 15 mol% C5+ alkanes). In some embodiments as described herein, the one or more hydrocarbons of the hydrocarbon product stream are aromatics. In some embodiments as described herein, the hydrocarbon product stream comprises at least 5 mol% C5-C10 aromatics (e.g., at least 10 mol% C5-C10 aromatics, or at least 15 mol% C5-C10 aromatics). For example, in various embodiments as described herein, the aromatics comprise xylenes, trimethyl benzene, tetramethyl benzene, or combinations thereof.

[0107] As described herein, the methanol-to-hydrocarbon synthesis provides a variety of hydrocarbon product, but advantageously, has a low selectivity for methane. Accordingly, in various embodiments as otherwise described herein, the first product stream includes no more than 10 mol% methane, e.g., no more than 5 mol% methane, or no more than 2 mol% methane.

[0108] Advantageously, a proportion of methanol is consumed during the methanol-to- hydrocarbon reaction. Accordingly, in various embodiments as otherwise described herein, the hydrocarbon product stream includes no more than 75 mol% methanol, e.g., no morethan 60 mol% methanol, no more than 50 mol% methanol, or no more than 25 mol% methanol.

[0109] In some embodiments, further removal of methanol from the hydrocarbon product stream is desired. For example, in various embodiments as otherwise described herein, the process further comprises separating at least a portion of methanol from the hydrocarbon product stream, e.g., separating at least 50%, or at least 75%, or at least 90%, or at least 95% of the methanol from the hydrocarbon product stream. Advantageously, methanol of the hydrocarbon product stream, e.g., at least a portion of the methanol separated from the hydrocarbon product stream, may be transferred or recycled to other processes. For example, in various embodiments as otherwise described herein, the process further comprises recycling to the hydrocarbon feed stream at least a portion of the methanol separated from the hydrocarbon product stream. In other embodiments, the process further comprises storing at least a portion of the methanol from the hydrocarbon product stream to form recycled and stored methanol, and then providing at least a portion of the recycled and stored methanol to the hydrocarbon feed stream.

[0110] The hydrocarbon product stream can further comprise other compounds. For example, in various embodiments as described herein, the hydrocarbon product stream comprises dimethyl ether, methanol, water, CO, CO2, formaldehyde, or combinations thereof. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% dimethyl ether, e.g., no more than 5 mol%, or no more than 1 mol% dimethyl ether. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% methanol, e.g., no more than 5 mol%, or no more than 1 mol% methanol. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% water, e.g., no more than 5 mol%, or no more than 1 mol% water. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% CO, e.g., no more than 5 mol%, or no more than 1 mol% CO. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% CO2, e.g., no more than 5 mol%, or no more than 1 mol% CO2. In various embodiments as described herein, the hydrocarbon product stream comprises no more than 10 mol% formaldehyde, e.g., no more than 5 mol%, or no more than 1 mol% formaldehyde.

[0111] As described herein, in addition to hydrocarbons, the hydrocarbon product stream may further include other components from the feed stream and / or formed in situ, such as methane, nitrogen, water, and / or carbon dioxide. Advantageously, certain species may be separated and recycled to other processes. For example, in various embodiments as otherwise described herein, wherein the hydrocarbon product stream comprises carbondioxide, and wherein the process further comprises providing at least a portion of the carbon dioxide of the hydrocarbon product stream to the first feed stream. In various embodiments as otherwise described herein, wherein the hydrocarbon product stream comprises carbon monoxide, and wherein the process further comprises providing at least a portion of the carbon monoxide of the hydrocarbon product stream to the first feed stream.

[0112] In various embodiments as otherwise described herein, the process comprises electrolyzing water to form a hydrogen gas containing stream to provide to the first feed stream. In such embodiments, and wherein the hydrocarbon product stream comprises water, the process further comprises providing at least a portion of the water of the hydrocarbon product stream is provided to the electrolyzing step.

[0113] The process as described herein provides a hydrocarbon product stream that includes one or more hydrocarbons. Accordingly, in various embodiments, one or more products are provided from at least a portion of the hydrocarbon produce stream. The hydrocarbons can be used as the basis of a variety of fuels, e.g., gasoline, diesel, and aviation fuel. Other products, like waxes and lubricants, can also be made from the hydrocarbons. Additionally, olefins can be used as feedstocks in a variety of other processes.

[0114] Further processing of the one or more hydrocarbons may be desired to provide the hydrocarbon product. For example, in some embodiments, the process further comprising contacting the hydrocarbon product stream with an oligomerization catalyst to form an oligomerized hydrocarbon product stream. An example of such an embodiment is shown in FIG. 4, in a process 400, wherein the hydrocarbon product stream 406 is contacted with an oligomerization catalyst 453 in an oligomerization reactor 450 to provide an oligomerization product 414.

[0115] The olefin oligomerization catalysts as used herein are not particularly limited, and the person of ordinary skill in the art would be able to choose a catalyst as appropriate for the olefin oligomerization processes. In various embodiments as otherwise described herein, the olefin oligomerization catalyst is a zeolite-based catalyst. For example, in various embodiments, the olefin oligomerization catalyst is a zeolite of type USY, ZSM-5, ZSM-12, ZSM-22, MCM-22, and MCM-36. In various embodiments, the zeolite-based catalyst is metal-promoted. For example, the zeolite-based catalyst can be promoted with molybdenum or nickel. In various embodiments, the zeolite-based catalyst is ion-exchanged. For example, the zeolite-based catalyst can be ion-exchanged one or more of sodium, potassium, iron, zinc and gallium. But the person of ordinary skill in the art will appreciate that a variety of other materials can act as oligomerization catalysts, including a variety ofcrystalline and amorphous aluminosilicates (e.g., amorphous silica alumina) and silicoaluminophosphates. As the person of ordinary skill in a variety of modifications of ths pore structure of the oligomerization catalyst may be made, e.g., to improve accessibility and slow deactivation by adding mesoporosity to otherwise microporous materials.

[0116] The person of ordinary skill in the art will select appropriate reaction conditions in conjunction with the particular feed and catalyst used to provide desired olefin oligomerization processes. In various embodiments as described herein, the temperature for the olefin oligomerization process is in the range of 150-300 °C, e.g., in the range of ISO- 275 °C, or 150-250 °C.

[0117] Additionally, the olefin oligomerization processes as described herein can be performed at a variety of pressures, as would be appreciated by the person of ordinary skill in the art. In various embodiments, the process for performing the olefin oligomerization is conducted at a pressure in the range of 30-100 barg, or 30-90 barg, or 30-80 barg, or 30-70 barg, or 30-60 barg, or 30-50 barg, or 30-40 barg, or 40-100 barg, or 40-90 barg, or 40-80 barg, or 40-70 barg, or 40-60 barg, or 40-50 barg.

[0118] The process as described herein provides an oligomerization product stream that includes oligomerized hydrocarbons. Accordingly, in various embodiments, one or more products are provided from at least a portion of the oligomerized hydrocarbons. The oligomerized hydrocarbons can be used as the basis of a variety of fuels, e.g., gasoline, diesel, and aviation fuel. Other products, like waxes and lubricants, can also be made from the oligomerized hydrocarbons. Additionally, olefins can be used as feedstocks in a variety of other processes.

[0119] Certain processes, such as a methanol synthesis process such as COXhydrogenation, may suffer from reduced efficiency if given variable input quantities or periodically idled. Accordingly, in various embodiments, the H2 and COXfrom the product streams as described herein may be recycled to the hydrogenation reactor in order to continue methanol synthesis. For example, in some embodiments as described herein, the H2 and / or COXfrom the first product stream may be recycled to the hydrogenation reactor in order to continue methanol synthesis. For example, as shown in FIG. 1, a recycle stream 160 comprising H2 and / or COXfrom the first product stream 102 is recycled to the hydrogenation reactor 110. In some embodiments as described herein, the H2 and / or COXfrom the hydrocarbon product stream may be recycled to the hydrogenation reactor in order to continue methanol synthesis. For example, as shown in FIG. 1, a recycle stream 261 comprising H2 and / or COXfrom the hydrocarbon product stream 206 is recycled to the hydrogenation reactor 210. Similarly, the methanol-to-hydrocarbon reaction may run withless than 100% conversion of methanol, and in various processes as described herein can further include separating methanol from the hydrocarbon product stream and providing it to one or more of the second feed stream, the third feed stream and the fourth feed stream.

[0120] In embodiments utilizing a methanol-to-hydrocarbon reaction, the operation of the process as otherwise described herein may be modulated in relation to the requirements of the methanol-to-hydrocarbon reaction. For example, in various embodiments as otherwise described herein, wherein the methanol-to-hydrocarbon reaction has a desired throughput, and wherein during the first period of time, a supply of electricity from a renewable source is sufficient to provide the desired throughput, and wherein during the second period of time, the supply of electricity from a renewable source is insufficient to provide the desired throughput.

[0121] The person of ordinary skill in the art will perform the processes described herein using any desirable reaction systems. For example, a wide variety of reactors can be used, e.g., a fixed bed reactor, a slurry bed reactor, or a fluid bed reactor.

[0122] Additional aspects of the disclosure are provided by the following enumerated embodiments, which may be combined in any number and in any combination that is not logically or technically inconsistent.Embodiment 1. A process for the production of a hydrocarbon composition, the process comprising: for a first period of time, providing a first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; providing a second feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form a hydrocarbon product stream comprising one or more hydrocarbons; and for a second period of time, providing a source of stored methanol; providing a third feed stream comprising stored methanol; contacting the third feed stream with the methanol-to-hydrocarbon synthesis catalyst (e.g., in the methanol-to-hydrocarbon synthesis reactor) to form the hydrocarbon product stream comprising one or more hydrocarbons,wherein the synthesized methanol fraction of the second feed stream is greater than the synthesized methanol fraction of the third feed stream.Embodiment 2. The process of embodiment 1 , wherein the hydrogen of the first feed stream comprises green hydrogen or blue hydrogen.Embodiment 3. The process of embodiment 1 or embodiment 2, wherein the hydrogen of the first feed stream comprises green hydrogen.Embodiment 4. The process of any of embodiments 1-3, wherein the process further comprises electrolyzing water to form an electrolysis product stream comprising hydrogen, and providing hydrogen from the electrolysis product stream to the first feed stream.Embodiment 5. The process of embodiment 4, wherein the electrolysis is performed using electricity from a renewable source.Embodiment 6. The process of embodiment 5, wherein the renewable source of electricity is provided by one or more of solar energy, wind energy, and hydroelectric energy (such as tidal energy).Embodiment 7. The process of any of embodiments 4-6, wherein the hydrogen produced by electrolysis is not stored for a substantial amount of time (e.g., no more than one hour).Embodiment 8. The process of any of embodiments 1-7, wherein the first feed stream comprises at least 10 vol% H2, e.g., at least 20 vol% H2, or at least 30 vol% H2.Embodiment 9. The process of any of embodiments 1-8, wherein the first feed stream comprises at least 5 vol% CO2, e.g., at least 10 vol% CO2, or at least 15 vol% CO2.Embodiment 10. The process of any of embodiments 1-9, wherein the first feed stream comprises at least 5 vol% CO, e.g., at least 10 vol% CO, or at least 15 vol% CO.Embodiment 11. The process of any of embodiments 1-10, wherein the CO2 of the first feed stream comprises captured CO2 (e.g., direct air captured CO2, or captured waste CO2, such as biomass-derived CO2), e.g., comprises at least 50%, at least 75%, at least 90% or at least 95% captured CO2.Embodiment 12. The process of any of embodiments 1-10, wherein the CO2 of the first feed stream comprises carbon dioxide from biomass gasification, e.g., comprises at least 20%, at least 50%, at least 75%, at least 90% or at least 95% carbon dioxide from biomass gasification.Embodiment 13. The process of any of embodiments 1-12, wherein the first feed stream further comprises methane.Embodiment 14. The process of any of embodiments 1-13, wherein an amount of methane in the first feed stream is no more than 50 mol% of carbon-bearing species, e.g., no more than 30 mol%, or no more than 20 mol%, or no more than 10 mol%, or no more than 5 mol%.Embodiment 15. The process of any of embodiments 1-14 wherein a ratio of H2:COXof the first feed stream is at least 1:1, e.g., at least 1.5:1 , on a molar basis.Embodiment 16. The process of any of embodiments 1-14, wherein a ratio of H2:COXof the first feed stream is at least 2:1, e.g., at least 2.5:1 , or at least 3:1 , or at least 4:1 , or at least 5:1, or at least 6: 1 , or at least 8: 1.Embodiment 17. The process of any of embodiments 1-14, wherein a ratio of H2:COXof the first feed stream is no more than 25:1 , e.g., no more than 20:1 , or no more than 15:1 , or no more than 12:1.Embodiment 18. The process of any of embodiments 1-17, wherein the first feed stream comprises no more than 1 vol% O2, for example, no more than 0.1 vol% O2, or no more than 0.01 vol% O2, or substantially no O2; and / or no more than 10 vol% CO (e.g., no more than 5 vol%, or 3 vol%, or 2 vol%, or 1 vol%, or 0.1 vol% CO).Embodiment 19. The process of any embodiments 1-18, wherein the contacting of the first feed stream with the hydrogenation catalyst is performed at a temperature in the range of 200-500 °C, e.g., 200-450 °C, or 200-400 °C, or 200-350 °C, or 200-300 °C, or 250-500 °C, or 250-450 °C, or 250-400 °C, or 250-300 °C, or 300-500 °C, or 300-450 °C, or 300-400Embodiment 20. The process of any of embodiments 1-19, wherein the contacting of the first feed stream with the hydrogenation catalyst is performed at a pressure of no more than 100 bar, for example, no more than 80 bar, or no more than 60 bar.Embodiment 21. The process according to any of embodiments 1-20, wherein the formation of the first product stream is performed with a selectivity of at least 50% for methanol, e.g., at least 55%, or at least 60%.Embodiment 22. The process according to any of embodiments 1-20, wherein the formation of the first product stream is performed with a selectivity of at least 65% for methanol (e.g., at least 70%, or at least 75%, or at least 80% for methanol).Embodiment 23. The process according to any of embodiments 1-22, wherein the formation of the first product stream is performed with a selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane.Embodiment 24. The process according to any of embodiments 1-23, wherein the formation of the first product stream is performed with a selectivity of no more than 20% for CO, e.g., no more than 10%, or no more than 5% for CO.Embodiment 25. The process according to any of embodiments 1-23, wherein the formation of the first product stream is performed with a selectivity of no more than 2% for CO, or 1% for CO.Embodiment 26. The process according to any of embodiments 1-25, wherein the formation of the first product stream is performed with a conversion of CO2 of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%.Embodiment 27. The process according to any of embodiments 1-26, wherein the formation of the first product stream is performed with a conversion of CO of at least 25%, e.g. at least 35%, e.g., at least 45% or at least 50%.Embodiment 28. The process according to any of embodiments 1-27, wherein the first product stream comprises at least 15 vol% methanol, e.g., at least 25 vol%, or at least 35 vol% methanol.Embodiment 29. The process according to any of embodiments 1-28, wherein the first product stream comprises no more than 10 vol% methane, e.g., no more than 5 vol% methane, or no more than 2 vol% methane.Embodiment 30. The process according to any of embodiments 1-29, wherein the first product stream includes no more than 10 vol% CO, e.g., no more than 5 vol% CO, or no more than 2 vol% CO.Embodiment 31. The process according to any of embodiments 1-30, further comprising separating at least a portion of water of the first product stream therefrom, e.g., 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 of the first product stream.Embodiment 32. The process according to any of embodiments 1-31 , wherein the portion of the first product stream that is included in the second feed stream has a water content of no more than 10 mol%, e.g., no more than 2 mol%, or no more than 1 mol%, or no more than 0.5 mol%.Embodiment 33. The process according to any of embodiments 1-32, further comprising separating at least a portion of H2 from the first product stream, e.g., at least 50%, or at least 60%, or at least 75%, or at least 90%, or at least 95% of the H2 of the first product stream.Embodiment 34. The process according to embodiment 33, wherein at least a portion of the separated H2 is recycled to the first feed stream, and / or wherein at least a portion of the separated H2 is used to activate the methanol-to-hydrocarbon synthesis catalyst.Embodiment 35. The process according to any of embodiments 1-34, wherein the contacting of the second feed stream and / or third feed stream with the methanol-to- hydrocarbon synthesis catalyst and the contacting of the first feed stream with the hydrogenation catalyst are performed in different plants.Embodiment 36. The process according to any of embodiments 1-35, wherein the first period of time is at least two hours, e.g., at least four hours, at least eight hours, or at least 24 hours.Embodiment 37. The process of any of embodiments 1-36, wherein substantially all of the methanol of the second feed stream is synthesized methanol.Embodiment 38. The process of any of embodiments 1-36, wherein the second feed stream has a synthesized methanol fraction of at least 95%, e.g., at least 98%, or at least 99%.Embodiment 39. The process of any of embodiments 1-36, wherein the second feed stream has a synthesized methanol fraction of at least 50%, e.g., at least 65%, or at least 75%.Embodiment 40. The process of any of embodiments 1-36, wherein the second feed stream has a synthesized methanol fraction of at least 80%, e.g., at least 85%, or at least 90%.Embodiment 41. The process of any of embodiments 1-36 and 38-54, wherein the second feed stream further comprises stored methanol.Embodiment 42. The process of embodiment 41 , wherein a portion of methanol stored during the first period of time is provided to the second feed stream.Embodiment 43. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 90%, e.g., no more than 85%, or no more than 80%.Embodiment 44. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 75%, e.g., no more than 70%, or no more than 65 wt%.Embodiment 45. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 60 wt%, e.g., no more than 55 wt%, or no more than 50 wt%.Embodiment 46. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 45%, e.g., no more than 40%, or no more than 35%.Embodiment 47. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 30%, e.g., no more than 25%, or no more than 20%.Embodiment 48. The process of any of embodiments 1-42, wherein the third feed stream has a synthesized methanol fraction of no more than 15%, e.g., no more than 10%, or no more than 5%.Embodiment 49. The process of any of embodiments 1-48, wherein substantially all of the methanol of the third feed stream is stored methanol.Embodiment 50. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 5%, e.g., at least 10%, or at least 15%.Embodiment 51. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 20%, e.g., at least 25%, or at least 30%.Embodiment 52. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 35%, e.g., at least 40%, or at least 45%.Embodiment 53. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 50%, e.g., at least 55%, or at least 60%.Embodiment 54. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 65%, e.g., at least 70%, or at least 75%.Embodiment 55. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 80%, e.g., at least 85%, or at least 90%.Embodiment 56. The process of any of embodiments 1-48, wherein the third feed stream has a stored methanol fraction of at least 95%, e.g., at least 98%, or at least 99%.Embodiment 57. The process of any of embodiments 49-56, wherein stored methanol of the third feed stream has a storage time of at least three hours, e.g., at least five hours, or at least eight hours.Embodiment 58. The process of any of embodiments 49-56, wherein stored methanol of the third feed stream has a storage time of at least twelve hours, e.g., at least 18 hours, or at least 24 hours.Embodiment 59. The process of any of embodiments 49-56, wherein stored methanol of the third feed stream has a storage time of at least thirty-six hours, e.g., at least three days or at least seven days.Embodiment 60. The process of any of embodiments 49-56, wherein stored methanol of the third feed stream has a storage time of no more than 30 days, e.g., no more than 21 days, or no more than 14 days, or no more than seven days.Embodiment 61. The process of any of embodiments 49-56, wherein stored methanol of the third feed stream has a storage time of no more than three days, e.g., no more than two days, or no more than one day.Embodiment 62. The process of any of embodiments 1-61, further comprising, during the first period of time, storing at least a portion of the methanol of the first product stream.Embodiment 63. The process of embodiment 62, wherein methanol stored during the first period of time is provided to the third feed stream during the second period of time.Embodiment 64. The process of any of embodiments 1-47 and 50-63, further comprising: providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; and including at least a portion of synthesized methanol of the first product stream in the third feed stream.Embodiment 65. The process of any of embodiments 1-64, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 5%, e.g., at least 10%, or at least 15%.Embodiment 66. The process of any of embodiments 1-64, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 20%, e.g., at least 25%, or at least 30%.Embodiment 67. The process of any of embodiments 1-64, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 35%, e.g., at least 40%, or at least 45%.Embodiment 68. The process of any of embodiments 1-64, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 50%, e.g., at least 55%, or at least 60%.Embodiment 69. The process of any of embodiments 1-62, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 65%, e.g., at least 70%, or at least 75%.Embodiment 70. The process of any of embodiments 1-69, wherein the second period of time is in the range of 30 minutes to 24 hours in length (e.g., 30 minutes to 18 hours, or 30 minutes to 12 hours, or 1-24 hours, or 1-18 hours, or 1-12 hours, or 3-24 hours, or 3-18 hours, or 3-12 hours, or 6-24 hours, or 6-18 hours, or 6-12 hours), and occurs after the first period of time.Embodiment 71. The process of any of embodiments 1-70, wherein the second period of time is followed by another first period of time.Embodiment 72. The process of any of embodiments 1-70, wherein the process includes a plurality of first and second periods of time.Embodiment 73. The process of any of embodiments 1-72, wherein the rate of production of the hydrocarbon product stream during the first period of time is at least 70% (e.g., at least 80%, at least 85%, at least 90%, or at least 95%) of the rate of production of the hydrocarbon product stream during the second period of time.Embodiment 74. The process of any of embodiments 1-72, wherein the rate of production of the hydrocarbon product stream during the first period of time is at least 99% of the rate of production of the hydrocarbon product stream during the second period of time.Embodiment 75. The process of any of embodiments 1-72, wherein the rate of production of the hydrocarbon product stream during the first period of time is the same as of the rate of production of the hydrocarbon product stream during the second period of time.Embodiment 76. The process of any of embodiments 1-72, further comprising for a third period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.Embodiment 77. The process of embodiment 76, wherein the fourth feed stream comprises at least a portion of the synthesized methanol of the first product stream.Embodiment 78. The process of embodiment 76 or embodiment 77, wherein the fourth feed stream comprises stored methanol.Embodiment 79. The process of any of embodiments 1-78, further comprising, during the first period of time, providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.Embodiment 80. The process of embodiment 79, wherein the fourth feed stream comprises at least a portion of the synthesized methanol of the first product stream.Embodiment 81. The process of embodiment 79 or embodiment 80, wherein the fourth feed stream comprises stored methanol.Embodiment 82. The process of any of embodiments 1-81, further comprising, during the second period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.Embodiment 83. The process of embodiment 82, wherein the fourth feed stream comprises at least a portion of the synthesized methanol of the first product stream.Embodiment 84. The process of embodiment 82 or embodiment 83, wherein the fourth feed stream comprises stored methanol.Embodiment 85. The process of any of embodiments 1-84, wherein during the first time period the first feed stream comprises no more than 10 vol% CO.Embodiment 86. The process of any of embodiments 1-85, wherein the second feed stream comprises at least 5 mol% methanol (e.g., 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).Embodiment 87. The process of any of embodiments 1-86, wherein methanol-to- hydrocarbon synthesis catalyst comprises one or more of a methanol-to-gasoline catalyst, a methanol-to-olefins catalyst, a methanol-to-propene catalyst, or a methanol-to-aromatics catalyst.Embodiment 88. The process of any of embodiments 1-86, wherein the methanol-to- hydrocarbon synthesis catalyst is a methanol-to-gasoline catalyst, a methanol-to-olefins catalyst, a methanol-to-propene catalyst, or a methanol-to-aromatics catalyst.Embodiment 89. The process of any of embodiments 1-86, wherein the methanol-to- hydrocarbon synthesis catalyst is a methanol-to-olefins catalyst.Embodiment 90. The process of any of embodiments 1-89, wherein the methanol-to- hydrocarbon synthesis catalyst is a solid acid catalyst.Embodiment 91. The process of any of embodiments 1-89, wherein the methanol-to- hydrocarbon synthesis catalyst is a zeolite-based catalyst, e.g., based on a zeolite of type ZSM-5, SAPO-34, ZSM-11 , ZSM-12, ZSM-21 and TEA-Mordenite.Embodiment 92. The process of embodiment 91 , wherein the zeolite-based catalyst is further doped (e.g., with phosphorous, boron, magnesium, antimony, or silicon).Embodiment 93. The process of any of embodiments 1-92, wherein contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature of at least 250 °C (e.g., at least 300 °C, or at least 350 °C).Embodiment 94. The process of any of embodiments 1-92, wherein contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature in the range of 250-750 °C (e.g., in the range of 250-700 °C, or 250-650 °C, or 250-600 °C, or 300-750 °C, or 300-700 °C, or 300-650 °C, or 300-600 °C).Embodiment 95. The process of any of embodiments 1-94, wherein contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure of no more than 100 bar (e.g., in more than 50 bar, or no more than 20 bar).Embodiment 96. The process of any of embodiments 1-94, wherein contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure in the range of 1-20 bar (e.g., in the range of 1-15, or 1-10 bar).Embodiment 97. The process of any of embodiments 1-96, wherein contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature of at least 250 °C (e.g., at least 300 °C, or at least 350 °C).Embodiment 98. The process of any of embodiments 1-96, wherein contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a temperature in the range of 250-750 °C (e.g., in the range of 250-700 °C, or 250-650 °C, or 250-600 °C, or 300-750 °C, or 300-700 °C, or 300-650 °C, or 300-600 °C)Embodiment 99. The process of any of embodiments 1-98, wherein contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure of no more than 100 bar (e.g., in more than 50 bar, or no more than 20 bar).Embodiment 100. The process of any of embodiments 1-98, wherein contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted at a pressure in the range of 1-20 bar (e.g., in the range of 1-15, or 1-10 bar).Embodiment 101. The process of any of embodiments 1-100, wherein contacting the second feed stream and / or contacting the third feed stream with a methanol-to-hydrocarbon synthesis catalyst is conducted for a time sufficient to form a hydrocarbon product stream.Embodiment 102. The process of any of embodiments 1-101 , wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C2-C4 olefins (e.g., at least 40%, or at least 50% for C2-C4 olefins).Embodiment 103. The process of any of embodiments 1-101 , wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C5+ olefins (e.g., at least 40%, or at least 50% for C5+ olefins).Embodiment 104. The process of any of embodiments 1-103, wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C2-C4 alkanes (e.g., at least 40%, or at least 50% for C2-C4 alkanes).Embodiment 105. The process of any of embodiments 1-103, wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C5+ alkanes (e.g., at least 40%, or at least 50% for C5+ alkanes).Embodiment 106. The process of any of embodiments 1-105, wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for aromatics (e.g., at least 40%, or at least 50% for aromatics).Embodiment 107. The process of embodiment 106, wherein the aromatics comprise xylenes, trimethyl benzene, tetramethyl benzene, or combinations thereof.Embodiment 108. The process of any of embodiments 1-107, wherein the formation of the hydrocarbon product stream is performed with a selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane.Embodiment 109. The process of any of embodiments 1-108, wherein the one or more hydrocarbons of the hydrocarbon product stream comprise one or more olefins, alkanes, or aromatics.Embodiment 110. The process of embodiment 109, wherein the one of more hydrocarbons of the hydrocarbon product stream are olefins.Embodiment 111. The process of embodiment 110, wherein the hydrocarbon product stream comprises at least 5 mol% C2-C4 olefins (e.g., at least 10 mol% C2-C4 olefins, or at least 15 mol% C2-C4 olefins).Embodiment 112. The process of embodiment 110 or embodiment 111 , wherein the hydrocarbon product stream comprises at least 5 mol% C5+ olefins (e.g., at least 10 mol% C5+ olefins, or at least 15 mol% C5+ olefins).Embodiment 113. The process of embodiment 109, wherein the one or more hydrocarbons of the hydrocarbon product stream are alkanes.Embodiment 114. The process of embodiment 113, wherein the hydrocarbon product stream comprises at least 5 mol% C2-C4 alkanes (e.g., at least 10 mol% C2-C4 alkanes, or at least 15 mol% C2-C4 alkanes).Embodiment 115. The process of embodiment 113 or embodiment 114, wherein the hydrocarbon product stream comprises at least 5 mol% C5+ alkanes (e.g., at least 10 mol% C5+ alkanes, or at least 15 mol% C5+ alkanes).Embodiment 116. The process of embodiment 109, wherein the one or more hydrocarbons of the hydrocarbon product stream are aromatics.Embodiment 117. The process of embodiment 116, wherein the hydrocarbon product stream comprises at least 5 mol% C5-C10 aromatics (e.g., at least 10 mol% C5-C10 aromatics, or at least 15 mol% C5-C10 aromatics).Embodiment 118. The process of embodiment 116 or embodiment 117, wherein the aromatics comprise xylenes, trimethyl benzene, tetramethyl benzene, or combinations thereof.Embodiment 119. The process of any of embodiments 1-118, wherein the hydrocarbon product stream further comprises dimethyl ether, methanol, water, CO, CO2, formaldehyde, or combinations thereof.Embodiment 120. The process of any of embodiments 1-119, wherein the hydrocarbon product stream comprises no more than 10 mol% dimethyl ether, e.g., no more than 5 mol%, or no more than 1 mol% dimethyl ether.Embodiment 121. The process of any of embodiments 1-120, wherein the hydrocarbon product stream comprises no more than 10 mol% methanol, e.g., no more than 5 mol%, or no more than 1 mol% methanol.Embodiment 122. The process of any of embodiments 1-121 , wherein the hydrocarbon product stream comprises no more than 10 mol% water, e.g., no more than 5 mol%, or no more than 1 mol% water.Embodiment 123. The process of any of embodiments 1-122, wherein the hydrocarbon product stream comprises no more than 10 mol% CO, e.g., no more than 5 mol%, or no more than 1 mol% CO.Embodiment 124. The process of any of embodiments 1-123, wherein the hydrocarbon product stream comprises no more than 10 mol% CO2, e.g., no more than 5 mol%, or no more than 1 mol% CO2.Embodiment 125. The process of any of embodiments 1-124, wherein In the hydrocarbon product stream comprises no more than 10 mol% formaldehyde, e.g., no more than 5 mol%, or no more than 1 mol% formaldehyde.Embodiment 126. The process of any of embodiments 1-125, wherein the hydrocarbon product stream comprises carbon dioxide, and the process further comprises providing at least a portion of the carbon dioxide of the hydrocarbon product stream to the first feed stream.Embodiment 127. The process of any of embodiments 1-126, wherein the hydrocarbon product stream comprises carbon monoxide, and wherein the process further comprises providing at least a portion of the carbon monoxide of the hydrocarbon product stream to the first feed stream.Embodiment 128. The process of any of embodiments 1-127, wherein the hydrocarbon product stream comprises water, and the process further comprises providing at least a portion of the water of the hydrocarbon product stream is provided to the electrolyzing step.Embodiment 129. The process of any of embodiments 1-128, wherein the H2 and / or COXfrom the first product stream is recycled to the hydrogenation reactor in order to continue methanol synthesis.Embodiment 130. The process of any of embodiments 1-129, wherein the H2 and / or COXfrom the hydrocarbon product stream may be recycled to the hydrogenation reactor in order to continue methanol synthesis.Embodiment 131. The process of any of embodiments 1-129, wherein at least a portion of methanol from the hydrocarbon product stream is separated and provided to one or more of the second feed stream, the third feed stream, the fourth feed stream, and stored methanol.Embodiment 132. The process of any of embodiments 1-131 , wherein the process further comprises contacting the hydrocarbon product stream with an oligomerization catalyst to form an oligomerized hydrocarbon product stream.Embodiment 133. The process according to embodiment 132, wherein the olefin oligomerization catalyst is a zeolite-based catalyst, e.g., based on a zeolite of type USY, ZSM-5, ZSM-12, ZSM-22, MCM-22, and MCM-36.Embodiment 134. The process of embodiment 133, wherein the zeolite-based catalyst is metal-promoted, e.g., with molybdenum or nickel.Embodiment 135. The process of embodiment 133 or embodiment 134, wherein the zeolite-based catalyst is ion-exchanged, e.g., with one or more of sodium, potassium, iron, zinc and gallium.Embodiment 136. The process according to any of embodiments 1-135, wherein the olefin oligomerization catalyst is an amorphous silica alumina catalyst.Embodiment 137. The process according to any of embodiments 132-136, wherein the contacting the hydrocarbon product stream with the olefin oligomerization catalyst in the olefin oligomerization reaction zone is conducted at a temperature in the range of 150-300 °C, e.g., in the range of 150-275 °C, or 150-250 °C.Embodiment 138. The process according to any of embodiments 132-137, wherein the contacting of the hydrocarbon product stream with the olefin oligomerization catalyst in the olefin oligomerization reaction zone is conducted at a pressure of 30-100 barg.Embodiment 139. The process according to any of embodiments 1-138, wherein the hydrocarbon product stream and / or oligomerized hydrocarbon product stream is used for fuels (e.g., gasoline, diesel, and aviation fuels).

[0123] The particulars shown herein are by way of example and for purposes of illustrative discussion of various embodiments of the present disclosure only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the disclosure. In this regard, no attempt is made to show details associated with the methods of the disclosure in more detail than is necessary for the fundamentalunderstanding of the methods described herein, the description taken with the examples making apparent to those skilled in the art how the several forms of the methods of the disclosure may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatus, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0124] The terms “a,” “an,” “the” and similar referents used in the context of describing the methods of the disclosure (especially in the context of the following embodiments and claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0125] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the methods of the disclosure and does not pose a limitation on the scope of the disclosure. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the methods of the disclosure.

[0126] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0127] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of’ excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0128] All percentages, ratios and proportions herein are by weight, unless otherwise specified.

[0129] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0130] Groupings of alternative elements or embodiments of the disclosure are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0131] Some embodiments of various aspects of the disclosure are described herein, including the best mode known to the inventors for carrying out the methods described herein. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The skilled artisan will employ such variations as appropriate, and as such the methods of the disclosure can be practiced otherwise than specifically described herein. Accordingly, the scope of the disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.

[0132] The phrase “at least a portion” as used herein is used to signify that, at least, a fractional amount is required, up to the entire possible amount.

[0133] In closing, it is to be understood that the various embodiments herein are illustrative of the methods of the disclosures. Other modifications that may be employed are within the scope of the disclosure. Thus, by way of example, but not of limitation, alternative configurations of the methods may be utilized in accordance with the teachings herein. Accordingly, the methods of the present disclosure are not limited to that precisely as shown and described.

Claims

\Ne Claim:

1. A process for the production of a hydrocarbon composition, the process comprising: for a first period of time, providing a first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form a first product stream comprising synthesized methanol; providing a second feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the second feed stream with a methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form a hydrocarbon product stream comprising one or more hydrocarbons; and for a second period of time, providing a source of stored methanol; providing a third feed stream comprising stored methanol; contacting the third feed stream with the methanol-to-hydrocarbon synthesis catalyst (e.g., in a methanol-to-hydrocarbon synthesis reactor) to form the hydrocarbon product stream comprising one or more hydrocarbons; wherein the synthesized methanol fraction of the second feed stream is greater than the synthesized methanol fraction of the third feed stream.

2. The process of claim 1 , further comprising, during the second period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising methanol (e.g., at least a portion of the synthesized methanol of the first product stream and / or stored methanol); contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2of the fourth product stream to the first feed stream.

3. The process of claim 1 , further comprisingfor a third period of time, providing the first feed stream comprising hydrogen and COX; contacting the first feed stream with a hydrogenation catalyst (e.g., in a hydrogenation reactor) to form the first product stream comprising synthesized methanol; providing a fourth feed stream comprising at least a portion of the synthesized methanol of the first product stream; contacting the fourth 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 fourth product stream comprising CO and H2; and providing at least a portion of the CO and the H2 of the fourth product stream to the first feed stream.

4. The process of any of claims 1-3, wherein the first feed stream comprises at least 10 vol% H2 and at least 5 vol% CO2.

5. The process of any of claims 1-4, wherein the first feed stream comprises no more than 10 vol% CO.

6. The process of any of claims 1-5, wherein the process further comprises electrolyzing water to form an electrolysis product stream comprising hydrogen, and providing hydrogen from the electrolysis product stream to the first feed stream, wherein the electrolysis is performed using electricity from a renewable source.

7. The process of any of claims 1-6, wherein the formation of the first product stream is performed with a selectivity of at least 65% for methanol.

8. The process of any of claims 1-7, wherein the portion of the first product stream that is included in the second feed stream has a water content of no more than 2 mol%.

9. The process of any of claims 1-8, wherein the formation of the first product stream is performed with a selectivity of no more than 20% for methane, e.g., no more than 10%, or no more than 5% for methane.

10. The process of any of claims 1-8, wherein the second feed stream has a synthesized methanol fraction of at least 95%.11 . The process of any of claims 1-10, wherein the third feed stream has a synthesized methanol fraction of no more than 70% and a stored methanol fraction of at least 20%.

12. The process of claim 11 , wherein stored methanol of the third feed stream has a storage time of at least three hours.

13. The process of any of claims 1-12, wherein a difference between the synthesized methanol fraction of the second feed stream and the synthesized methanol fraction of the third feed stream is at least 20%.

14. The process of any of claims 1-13, wherein the process includes a plurality of alternating first and second periods of time.

15. The process of any of claims 1-14, wherein the contacting of the second feed stream and / or the third feed stream with a methanol-to-hydrocarbon catalyst is performed with a selectivity of at least 30% for C2-C4 olefins, of at least 30% for C5+ olefins, of at least 30% for C2-C4 alkanes, of at least 30% for C5+ alkanes, and / or of at least 30% for aromatics.

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