Systems and methods for producing paraffinic kerosene and sustainable aviation fuel using reforming catalysts

Abstract

This document provides systems and methods for converting CO2 and reducing gases, such as H2 or hydrocarbons, into alkane mixtures for use as alkane aviation fuels, and also into mixtures of alkanes and aromatic compounds suitable for use as aviation fuels. The systems and methods disclosed offer advantages over previous methods, involving increased carbon selectivity and improved catalyst stability and lifetime.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 546,900, filed November 1, 2023; U.S. Provisional Application No. 63 / 567,700, filed March 20, 2024; and U.S. Provisional Application No. 63 / 676074, filed July 26, 2024, the contents of each of which are incorporated herein by reference in their entirety. Background Technology

[0003] With increasing atmospheric carbon dioxide concentrations, developing technologies to remove or mitigate CO2 emissions is advantageous. Therefore, developing transportation technologies that reduce CO2 emissions, such as electric vehicles, has become a priority. However, the development of electric aircraft, especially commercial electric aircraft, is problematic due to the low energy density of the required batteries. Therefore, the development of sustainable aviation fuel (SAF) remains necessary, and currently available technologies will not be able to meet market demand.

[0004] Currently, jet fuel (Jet-A) consists of n-alkanes, isoalkanes, cycloalkanes, and aromatic compounds derived from crude oil. To produce a saline fuel oil (SAF) that can directly replace Jet-A, the SAF must match the current composition of Jet-A extracted from crude oil. Current SAF production technologies involve extracting SAF from vegetable oils, animal fats, and waste oils. However, SAF produced through these processes primarily contains alkanes and lacks sufficient cycloalkanes and aromatic compounds to directly replace Jet-A extracted from crude oil. Therefore, a technology is needed to produce an SAF that can directly replace Jet-A extracted from crude oil.

[0005] Furthermore, some processes for producing alkanes and aromatic compounds from CO2 involve the simultaneous use of metal oxide catalysts and zeolite catalysts. However, zeolite catalysts can suffer from deactivation pathways caused by (a) coke (carbon) formation in the zeolite pores and (b) metal migration from metal oxide catalysts to zeolite catalysts, leading to poisoning of zeolite active sites. Therefore, processes for producing aromatic compounds and alkanes from CO2 (e.g., preparing SAF compositions for direct use) are needed to mitigate these zeolite deactivation pathways. In addition, there is a need to improve process selectivity and yield. Summary of the Invention

[0006] This document discloses a method for producing aviation fuel. The method may include: a method of manufacturing aviation fuel comprising: contacting a first reducing gas and a first carbon source gas with a reduction catalyst to provide: a light hydrocarbon product mixture; and a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture; contacting the light hydrocarbon product mixture and optionally at least a portion of the medium hydrocarbon product mixture with an oligomerization catalyst to provide an oligomerization product mixture; hydrogenating the target hydrocarbon product mixture and the oligomerization product mixture to provide a hydrogenated alkane product mixture comprising a light alkane product mixture, a medium alkane product, and a target alkane product mixture; contacting the medium alkane product mixture and optionally at least a portion of the light alkane product mixture with a reforming catalyst to provide a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture; and combining the target aromatic product mixture with the target alkane product mixture to manufacture aviation fuel.

[0007] This document also discloses a system for producing aviation fuel. The system may include: (i) a first reducing gas feed; (ii) a first carbon source gas feed; (iii) a reduction reactor containing a reduction catalyst; (iv) a first separator connected to the reduction reactor; (v) an oligomerization reactor containing an oligomerization catalyst; (vi) a hydrogenator; (vii) a second separator connected to the hydrogenator; and (vii) an aromatic reactor containing a reforming catalyst.

[0008] The reduction reactor may include a first reducing gas feed inlet, a first carbon source feed inlet, and a mixed hydrocarbon outlet. The first reducing gas feed inlet may be connected to the first reducing gas feed, and the first carbon source gas feed inlet may be connected to the first carbon source gas feed. The system may also include a second reducing gas feed and / or a second carbon source gas feed. The first separator may include a mixed hydrocarbon inlet, a light hydrocarbon product outlet, and a target hydrocarbon outlet. The mixed hydrocarbon inlet on the first separator may be connected to the mixed hydrocarbon outlet on the reduction reactor.

[0009] The oligomerization reactor may have a light hydrocarbon product inlet and an oligomer product outlet. The light hydrocarbon product inlet on the oligomerization reactor may be connected to the light hydrocarbon product outlet on the first separator.

[0010] The hydrogenator may include an oligomer inlet and a hydrogenated alkane product outlet. The oligomer inlet on the hydrogenator may be connected to the oligomer product outlet on the oligomer reactor. The second separator may include a hydrogenated alkane product inlet, a medium-quality alkane outlet, and a target alkane outlet. The hydrogenated alkane product inlet on the second separator may be connected to the hydrogenated alkane product outlet on the hydrogenator.

[0011] The aromatic reactor may include a medium-chain alkane inlet, a second reducing agent optionally serving as a feed inlet, a second carbon source gas feed inlet optionally, and a mixed aromatic product outlet. The medium-chain alkane inlet on the aromatic reactor may be connected to the medium-chain alkane outlet on the second separator; the second reducing gas feed inlet (if present) may be connected to the second reducing gas feed; and the second carbon source gas feed inlet (if present) may be connected to the second carbon source gas feed.

[0012] A system for producing alkane kerosene for aviation fuel is also disclosed. The system includes: (i) a first reducing gas feed; (ii) a first carbon source gas feed; (iii) a reduction reactor containing a reduction catalyst; (iv) a first separator connected to the reduction reactor; a second separator connected to the first separator; (v) an oligomerization reactor containing an oligomerization catalyst and connected to the first and second separators; and (vi) a third separator having an oligomerization product inlet connected to an oligomerization product outlet. The system may also include a hydrogenator connected to the third separator, the hydrogenator being configured to receive a target olefin product mixture and hydrogenate it to produce alkane kerosene. Attached Figure Description

[0013] Figure 1 This is a process flow diagram for a system used to manufacture aviation fuel, in which an aromatic reactor containing a reforming catalyst is used.

[0014] Figure 2 This is a process flow diagram for a system used to manufacture aviation fuel, in which an aromatic reactor containing a reforming catalyst is used and an intermediate quench agent is provided between two sections of the oligoalkylation reactor.

[0015] Figure 3 This is a process flow diagram of a system for producing alkane kerosene, in which an intermediate quench agent is provided between two sections of an oligomer reactor.

[0016] Figure 4 This is a process flow diagram of a system for producing alkane kerosene, which includes two oligomerization reactors. Detailed Implementation

[0017] Aviation fuels typically contain four classes of hydrocarbons: n-(linear) alkanes, branched alkanes, cycloalkanes, and aromatics. The most commonly used Jet A and Jet A-1 fuel blends are formulated to meet the specifications defined by ASTM International (formerly the American Society for Testing and Materials) standard D1655. The ASTM D1655 aviation turbine fuel standard specification includes tests for the physical and chemical properties that Jet A or Jet A-1 must meet for use in aircraft. This standard also includes concentration limits for acidic and sulfur-containing compounds, as well as minimum and maximum concentrations of aromatics, referencing ASTM standard tests for these limits. While O-ring material compatibility in existing turbine engines requires aromatics, most synthetically produced aviation fuel blends lack aromatics.

[0018] In aromatics, there is no significant difference in O-ring compatibility between monocyclic and bicyclic aromatic compounds (compounds containing two fused aromatic rings), and petroleum-derived jet fuels typically contain both. ASTM D1655 also does not distinguish between them. However, polycyclic aromatic compounds (compounds containing two or more fused aromatic rings), such as naphthalene, produce significantly higher levels of harmful particulate matter emissions upon combustion than their monocyclic counterparts. For example, the soot produced when n-butylbenzene burns is approximately 62% that of naphthalene. Therefore, it is advantageous to synthesize Jet A containing monocyclic aromatic compounds rather than polycyclic aromatic compounds.

[0019] Among the processes for synthesizing synthetic blends of sustainable aviation fuels, the Fischer-Tropsch (FT) process is the most commonly used because it is a proven process that has been operating since the early 1900s for converting syngas (a mixture of carbon monoxide and hydrogen) into alkanes. The FT product liquid, Fischer-Tropsch hydrosynthetic alkane kerosene (FT-SPK), is the subject of Annex A1 to ASTM D7566, the first approved SAF synthetic blend component annex. This alkane kerosene consists primarily of n-alkanes and isoalkanes, containing little or no cycloalkanes or aromatic compounds. Therefore, FT-SPK must be blended with the corresponding conventional Jet A to achieve the desired concentration of cyclic compounds, thus meeting the ASTM D1655 specification. Additional annexes to ASTM D7566 have been approved for synthetic blends using the ASTM D4054 process, which facilitates the formation of fully formulated Jet A.

[0020] In some aspects, this disclosure describes a fully formulated Jet A synthesized from carbon dioxide. The fully formulated synthetic Jet A can be added directly dropwise, meaning that the chemical and physical properties of the synthetic Jet A are nearly identical to those of conventional jet fuels, and it can be safely mixed with the latter to varying degrees, using the same supply infrastructure, and without requiring adaptation to the aircraft or engine. As described herein, in some embodiments, the production process assembles aromatic compounds from carbon dioxide. This bottom-up process design significantly reduces the accessibility to synthesizing larger molecules. Therefore, the synthetic Jet A disclosed herein contains fewer polycyclic aromatic compounds than Jet A made from petroleum-derived components. In some embodiments, the synthetic Jet A of this disclosure contains less than about 1 wt% polycyclic aromatic compounds.

[0021] The compositions described herein also contain significantly less sulfur-containing substances than comparable fossil fuels, less than 1 ppm in some embodiments. This is achieved through the thermochemical synthesis of jet fuel using CO2 and H2.

[0022] The two characteristics of the fuels described in this article (low polycyclic aromatic compounds and sulfur content) are difficult or impossible to achieve with petroleum-derived fuels because these fuels are prepared by conventional methods that ultimately retain a variety of characteristic compounds from petroleum sources, such as sulfur substances and polycyclic aromatic compounds, which are extremely expensive or impossible to completely remove from the final fuel products.

[0023] This article also provides systems and processes for producing SAF, which in some embodiments can directly replace Jet-A made from petroleum-derived components, CO2, and renewable energy.

[0024] The above process can produce jet fuel that can directly replace crude oil-derived Jet-A, because the ratio of isoalkanes to n-alkanes, and aromatics to cycloalkanes, can be controlled via oligomerization, alkylation, isomerization, and / or hydrogenation reactors. Furthermore, the ratio of alkanes to aromatics can be adjusted by controlling the feed rate into an aromatics reactor equipped with a reforming catalyst to prepare aromatic compounds. Those skilled in the art will understand that the flexibility of this system design allows these ratios to be adjusted as needed for other applications.

[0025] This article also provides a system and process for producing alkane kerosene from CO2. This CO2-derived alkane kerosene consists primarily of n-alkanes and isoalkanes, contains little or no cycloalkanes or aromatic compounds, and can be blended with conventional Jet A to achieve desired concentrations of cyclic compounds, thus meeting ASTM D1655 specifications.

[0026] The advantage of the scheme disclosed herein is the improved carbon selectivity compared to previously known processes. By using the methods and systems disclosed herein to produce alkane kerosene, the overall carbon selectivity (i.e., the carbon converted from the first carbon source gas (plus any additional carbon sources added to the system) to the alkane kerosene) can exceed about 50% mol%, exceed about 60% mol%, exceed about 65% mol%, exceed about 67% mol%, or exceed about 68% mol%. Carbon selectivity can be about 50% mol% to about 80% mol%, about 60% mol% to about 75% mol%, about 62% mol% to about 70% mol%, or about 65% mol%. Unless otherwise explicitly stated, the selectivity values ​​disclosed herein are in mol% mol% carbon.

[0027] Similarly, by using the methods and systems disclosed herein, aviation fuels are produced using aromatic reactors and reforming catalysts, achieving overall carbon selectivity (i.e., conversion from a primary carbon source gas (plus any additional carbon sources added to the system) to a target SAF compound (i.e., containing one or more C244 carbon atoms). 9-14 The target aromatic product mixture of aromatic compounds plus one or more C 10-16 The carbon content of the target hydrocarbon product mixture (of alkanes and / or olefins) may exceed about 50%, about 60%, about 65%, or about 70%. The overall carbon selectivity may be about 50% to about 75%, about 55% to about 70%, about 60% to about 68%, or about 65%.

[0028] fuel composition

[0029] This disclosure provides systems and methods for producing alkane kerosene and fuel compositions from a carbon source gas (e.g., CO2) and a reducing gas (e.g., H2). Fuel compositions produced by these systems and / or methods, such as those described below, exhibit certain unique properties and compositional characteristics. For example, these compositions have a low total sulfur content because they (or their main components) are produced by CO2 synthesis. As another example, the systems and processes disclosed herein for preparing aromatic components are highly favorable for the production of monocyclic aromatic compounds and unfavorable for the production of polycyclic aromatic compounds. These compositional characteristics (e.g., low sulfur content and low polycyclic aromatic content) resulting from the systems and processes described herein are advantageous compared to conventional (petroleum-derived) fuels.

[0030] This document provides fuel compositions comprising: monocyclic aromatic compounds; cycloalkanes; n-alkanes; and iso-alkanes. The composition may contain less than about 1 wt% of polycyclic aromatic compounds.

[0031] The fuel composition may contain less than about 5 wt% of tetrahydronaphthalene and dihydroindene, or less than about 1 wt% of tetrahydronaphthalene and dihydroindene. In some embodiments, the fuel composition contains 0 wt% to about 5 wt% of tetrahydronaphthalene and dihydroindene, or 0 wt% to about 1 wt% of tetrahydronaphthalene and dihydroindene. In some embodiments, the composition substantially does not contain tetrahydronaphthalene and dihydroindene.

[0032] The fuel composition may contain less than about 0.5 wt% of a polycyclic aromatic hydrocarbon (PAH). The fuel composition may contain about 0 wt% to about 0.5 wt% of a PAH, or about 0.1 wt% to about 1 wt% of a PAH. In some embodiments, the fuel composition contains about 0.1 wt% or less, about 0.2 wt% or less, about 0.3 wt% or less, about 0.4 wt% or less, or about 0.5 wt% or less of a PAH. In some embodiments, the fuel composition substantially does not contain a PAH, for example, as determined by GC-MS.

[0033] In some embodiments, substantially all aromatic compounds present in the fuel compositions of this disclosure are monocyclic aromatic compounds.

[0034] The fuel composition may contain about 5 wt% to about 25 wt% of a monocyclic aromatic compound. The fuel composition may contain about 8 wt% to about 15 wt% of a monocyclic aromatic compound. The fuel composition may contain about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, or about 14 wt% of a monocyclic aromatic compound. The fuel composition may contain about 13.5 wt% of a monocyclic aromatic compound.

[0035] The fuel composition may contain about 15 wt% to about 65 wt% cycloalkanes. The fuel composition may contain about 15 wt% to about 35 wt% cycloalkanes. The fuel composition may contain about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, or about 35 wt% cycloalkanes. The fuel composition may contain about 29 wt% cycloalkanes.

[0036] The fuel composition may contain about 5 wt% to about 40 wt% of isoparaffins. The fuel composition may contain about 15 wt% to about 35 wt% of isoparaffins, or about 25 wt% to about 35 wt% of isoparaffins. The fuel composition may contain about 15 wt%, about 20 wt%, about 25 wt%, about 28 wt%, about 30 wt%, or about 35 wt% of isoparaffins.

[0037] The fuel composition can meet ASTM D4054-1 standards.

[0038] The fuel composition may have a total acidity of less than about 0.10 mg KOH / g. In some embodiments, the composition has a total acidity of about 0.05 mg KOH / g to about 0.10 mg KOH / g. In further embodiments, the composition has a total acidity of about 0.05 mg KOH / g, about 0.06 mg KOH / g, about 0.07 mg KOH / g, about 0.08 mg KOH / g, about 0.09 mg KOH / g, or about 0.10 mg KOH / g. In some embodiments, the composition has a total acidity of about 0.07 mg KOH / g.

[0039] In some embodiments, the composition contains less than about 0.3 wt% total sulfur, for example, as measured by ASTM D2622. In some embodiments, the composition contains less than about 1 ppm of sulfur-containing impurities. In some embodiments, the composition contains substantially no sulfur-containing impurities. In some embodiments, the composition contains less than about 0.003 wt% thiol sulfur. In other embodiments, the composition contains about 0 wt% thiol sulfur, for example, as measured by ASTM D3227.

[0040] The fuel composition may have a flash point of at least about 38°C. In some embodiments, the composition has a flash point of about 38°C to about 370°C, or about 38°C to about 100°C. In further embodiments, the composition has a flash point of about 38°C to about 50°C. In still further embodiments, the composition has a flash point of about 38°C, about 39°C, about 40°C, about 41°C, about 42°C, about 43°C, about 44°C, about 45°C, about 46°C, about 47°C, about 48°C, about 49°C, or about 50°C. In some embodiments, the composition has a flash point of about 42°C.

[0041] The fuel composition may have a strength of approximately 775 kg / m³ at 15°C. 3 Approximately 840 kg / m 3 The density. In some embodiments, the composition has a density of approximately 775 kg / m³ at 15°C. 3 Approximately 810 kg / m 3 Approximately 785 kg / m³ at 15℃ 3 Approximately 810 kg / m 3 Or approximately 800 kg / m³ at 15°C 3 Approximately 810 kg / m 3 The density. In some embodiments, the composition has a density of approximately 775 kg / m³ at 15°C. 3 Approximately 780 kg / m 3 Approximately 800 kg / m 3 Or approximately 810 kg / m 3The density of this composition is approximately 800 kg / m³ at 15°C. 3 The density.

[0042] The fuel composition may have a freezing point below about -40°C. In some embodiments, the composition has a freezing point of about -70°C to about -40°C. In further embodiments, the composition has a freezing point of about -70°C, about -65°C, about -60°C, about -55°C, about -50°C, about -45°C, or about -40°C. In some embodiments, the composition has a freezing point of about -51°C.

[0043] The fuel composition may have a viscosity of less than about 8.0 cSt at -20°C. In some embodiments, the composition has a viscosity of less than about 12 mm at -40°C. 2 The viscosity is approximately 3.2 mm / s. In some embodiments, the composition has a viscosity of approximately 3.2 mm / s at –20°C. 2 Viscosity per second.

[0044] The fuel composition may have a net heat of combustion of at least about 42.8 MJ / kg. In some embodiments, the composition has a net heat of combustion of about 42.8 MJ / kg to about 51 MJ / kg. In further embodiments, the composition has a net heat of combustion of about 42.8 MJ / kg, about 43.4 MJ / kg, about 45 MJ / kg, about 47 MJ / kg, about 49 MJ / kg, or about 51 MJ / kg. In some embodiments, the composition has a net heat of combustion of about 43.4 MJ / kg.

[0045] The fuel composition may have a smoke point of at least about 18 mm. In some embodiments, the composition has a smoke point of at least about 25 mm. In further embodiments, the composition has a smoke point of about 25 mm to about 45 mm. In still further embodiments, the composition has a smoke point of about 25 mm, about 30 mm, about 35 mm, about 40 mm, or about 45 mm. In some embodiments, the composition has a smoke point of about 36 mm.

[0046] The fuel composition may have a filter pressure drop of less than about 25 mm Hg. In some embodiments, the composition provides a filter pressure drop of 0 mm Hg to about 25 mm Hg. In certain embodiments, the composition provides a filter pressure drop of about 0 mm Hg.

[0047] The fuel composition may have a pipe deposit grade of less than about 3, with virtually no peacock or unusual color deposits. In some embodiments, the composition gives a pipe deposit grade of 1 VTR color code.

[0048] The fuel composition may have a lubricity of less than about 0.85 mm wear track diameter (WSD). In some embodiments, the composition has a lubricity of 0 mm WSD to about 0.85 mm WSD. In some embodiments, the composition has a lubricity of about 0.52 mm WSD.

[0049] The fuel composition may conform to ASTM D1655.

[0050] In some embodiments, the monocyclic aromatic compound is not petroleum-derived. In some embodiments, the monocyclic aromatic compound is derived from CO2. In some embodiments, the monocyclic aromatic compound, cycloalkanes, n-alkanes, and isoalkanes are not petroleum-derived. In other embodiments, the monocyclic aromatic compound, cycloalkanes, n-alkanes, and isoalkanes are derived from CO2.

[0051] The fuel composition may further comprise at least one fuel additive. The fuel additive may be any such additive known in the art. For example, a fuel additive may be incorporated to impart certain desired properties or characteristics to the fuel.

[0052] Systems for producing alkane kerosene and aviation fuel

[0053] This document provides systems for converting carbon source gases and reducing gases into aviation fuel. Certain components of these systems are described as being “interconnected” to each other. It should be understood that, as used herein, the term “interconnected” describes components that are operationally linked to each other but does not exclude the presence of intermediate components between the components referred to as interconnected. Additionally, as understood, individual system components are described as “having” certain characteristics. For example, in some embodiments, a reduction reactor

[25] is described as having a first reducing gas feed inlet

[23] , a first carbon source inlet

[23] , and a product outlet

[27] . Such descriptions do not exclude and specifically take into account the presence of additional features such as inlets, outlets, valves, control mechanisms, measuring devices, heating and / or cooling systems, etc. Additionally, in the systems disclosed herein, certain components are described as having one or more outlets or inlets. Such outlets and inlets may represent individual structural elements or may be combined as a single inlet or outlet as needed. Those skilled in the art will recognize that once the key characteristics and operating conditions of a system (such as those described herein) are understood, the detailed design and operation of such systems involve many choices, such as specific reagent flows, separation steps, etc. Although this disclosure provides several specific embodiments, these design options can be combined in any suitable way.

[0054] Furthermore, the various systems and methods disclosed herein sometimes reference systems with a specific carbon number (e.g., C30, C40, C50, C60, C7 ... X–YThe fractions are distillates. As will be understood, these carbon numbers refer to the carbon composition of the majority of the fraction, but the fraction may include additional components with carbon numbers higher or lower than the indicated carbon numbers. Separators capable of producing these fractions are well known in the art and can be adapted as needed to obtain a suitable product mixture as disclosed herein or as the operator otherwise desires. Certain components of the system are referred to by numbers in parentheses (i.e.,

[10] ).

[0055] This document also discloses a system for producing aviation fuel. The system may include: a first reducing gas feed; a first carbon source gas feed; a reduction reactor containing a reduction catalyst; an oligomerization reactor; a hydrogenator; and an aromatic reactor containing a reforming catalyst. One or more separators may be present between the reduction reactor and the aromatic reactor for separating light hydrocarbons, medium hydrocarbons, target hydrocarbons, and / or heavy hydrocarbons in gaseous, liquid, and / or stream form, and optionally aromatic compounds. The system may include a reduction reactor coupled to a first separator, which may be further coupled to one or more separators (e.g., distillation columns or absorbers). The first separator may be a three-phase separator. The three-phase separator may be any such separator known in the art for separating gases, liquids, and wastewater. The first separator may have a water outlet (which may also be referred to herein as a wastewater outlet), C6 or higher (“C…”). 6+ Hydrocarbon exports and CO2, H, C 1-5 Hydrocarbon export.

[0056] In one embodiment, the first separator is connected to a device connected to CO2, H2, and C2C. 1-5 The absorber at the inlet of the hydrocarbon outlet, and the three-phase separator are also connected to a connection to C 6+ The distillation tower at the hydrocarbon outlet.

[0057] The reduction reactor may have a first reducing gas inlet, a first carbon source inlet, and a mixed hydrocarbon outlet. The first reducing gas inlet may be connected to a first reducing gas feed. The first carbon source gas inlet may be connected to a first carbon source gas feed. The reduction reactor may further include a light hydrocarbon outlet.

[0058] The oligomerization reactor contains an oligomerization catalyst. The oligomerization reactor may include an oligomerization product outlet and a light hydrocarbon inlet connected to a first separator or optionally to a distillation column. The oligomerization reactor may be connected to a first separator and a third separator. The oligomerization reactor may be configured to receive a light hydrocarbon product mixture from the first separator. The oligomerization reactor may be configured to receive a light aromatic product mixture from the third separator. The light hydrocarbon product mixture may contain one or more C4 ... 1-5 Alkanes and / or alkenes, or one or more C464 compounds 3-5Alkanes and / or alkenes. The parameters of the separator can be adjusted as readily understood by one of ordinary skill in the art to change the carbon range of the separated stream (e.g., light, medium, heavy). It may be necessary to change the carbon range of alkanes and alkenes in the light hydrocarbon product mixture and increase the yield according to the desired product.

[0059] An oligomerization reactor may contain two or more sections within a single reactor, each containing an oligomerization catalyst. The oligomerization catalysts in the sections of the oligomerization reactor may be the same or different. An intermediate quencher may be supplied between the sections of the oligomerization reactor to lower the temperature in the bottom section of the reactor. The intermediate quencher may be a mixture of light aromatic products from a second separator and / or a portion of a mixture of light hydrocarbon products from a first separator. The oligomerization reactor may be configured to receive a mixture of light aromatic products from the second separator as an intermediate quencher. The oligomerization reactor may be configured to receive a portion of a mixture of light hydrocarbon products from the first separator as an intermediate quencher and / or receive the remainder of the mixture of light hydrocarbon products from the first separator at its top, such that the remainder of the light hydrocarbon product mixture undergoes two dimerizations within the oligomerization reactor. The system may be configured such that the top section of the oligomerization reactor dimers the hydrocarbons provided therein, and then the dimerized hydrocarbon mixture contacts the oligomerization catalyst in the bottom section of the oligomerization reactor to undergo alkylation and dimerization to produce olefins and alkanes in the jet fuel range (i.e., C14). 10-16 ).

[0060] A hydrogenator can be coupled to an oligomerization reactor to saturate the olefins in the oligomerization product, thereby producing more alkanes. The hydrogenator may have an oligomerization product inlet and a hydrogenated alkane product outlet. The oligomerization product inlet may be coupled to the oligomerization product outlet on the oligomerization reactor. The hydrogenator may be coupled to a second separator and a first separator to improve the overall selectivity of the method. The hydrogenator may be configured to receive a mixture of light alkane products from a second separator. The hydrogenator may be configured to receive a target hydrocarbon product mixture from a reduction reactor. The hydrogenator may be coupled to an additional reducing gas feed. The hydrogenator may include two sections, or it may be two separate reactors with different temperatures to fully saturate the olefins and aromatics as needed, thereby providing the target alkane product mixture.

[0061] The second separator can be a distillation column, or a separator plus a flash tank. The second separator can be any such device or combination of devices known in the art for separating hydrocarbons. The second separator may have a hydrogenated alkane product inlet connected to the hydrogenated alkane product outlet of the hydrogenator. The second separator may have a medium-quality alkane outlet and a target alkane outlet. The second separator may have a light-quality alkane outlet.

[0062] The aromatic reactor described herein may also be referred to as a reforming unit. The aromatic reactor contains a reforming catalyst. The aromatic reactor may include a medium-chain alkane inlet, optionally a second reducing gas feed inlet, optionally a second carbon source gas feed inlet, and a mixed aromatic product outlet. The medium-chain alkane inlet may be connected to a medium-chain alkane outlet on a second separator, the second reducing gas feed inlet (if present) may be connected to a second reducing gas feed, and the second carbon source gas feed inlet (if present) may be connected to a second carbon source gas feed.

[0063] The system may include a second reducing gas feed. The system may also include a second carbon source gas feed.

[0064] The system disclosed herein may include a first adsorbent bed having a light hydrocarbon inlet and a light hydrocarbon outlet. The light hydrocarbon inlet may be coupled to a first separator, and the light hydrocarbon outlet may be coupled to a distillation column. The first adsorbent bed may have a medium alkane inlet coupled to a medium alkane outlet on a second separator.

[0065] The oligomer reactor can be configured to process C 2-5 Olefin conversion (also known as dimerization) to C 4-8 Alkenes, and optionally C 6-10 Alkenes, then C 4-8 Olefin conversion (also known as dimerization) to C 10-16 Olefins. The oligomerization reactor may include two sections, each containing an oligomerization catalyst. The oligomerization catalysts in each or more sections may be the same or different. An intermediate quencher may be included between the two sections of the oligomerization reactor. The intermediate quencher may be supplied by a first separator, a third separator, or both a first separator and a third separator. The oligomerization reactor may be a stacked bed reactor.

[0066] In addition to or instead of an oligomerization reactor, the system disclosed herein may also include an oligomerization alkylation reactor. The oligomerization alkylation reactor may comprise an oligomerization catalyst and an alkylation catalyst. The oligomerization catalyst and the alkylation catalyst may be stacked separately, layered, or mixed. The oligomerization alkylation reactor may have one or more light hydrocarbon product inlets, light aromatic product inlets, and oligomer product outlets. The light hydrocarbon inlet may be connected to the light hydrocarbon outlet on a first separator, and the light aromatic product inlet may be connected to the light aromatic product outlet on an aromatic reactor. The oligomerization alkylation reactor may be configured to receive a mixture of light aromatic products from a second separator as an intermediate quenching agent.

[0067] Although the oligomerization reactor is depicted in the figures as a single oligomerization alkylation reactor having one or two sections, it can also be replaced by two separate oligomerization reactors connected in series, or by one oligomerization reactor (having one or two sections) and a separate alkylation reactor connected in series, wherein the oligomerization reactor is located upstream of the alkylation reactor. The system of this disclosure may further include a fourth separator configured to contain one or more C... 10-16 Target alkane product mixtures containing one or more C 17+ Separation of a mixture of heavy alkane products. A fourth separator may have a heavy alkane product outlet and a target SAF alkane product outlet. The fourth separator may be coupled to the second separator. The fourth separator may also have a target alkane inlet coupled to the target alkane outlet of the second separator.

[0068] The system may include an alkylation reactor configured to receive at least a portion of a mixture of light aromatic products for contact with an alkylation catalyst to provide a target alkyl aromatic product mixture comprising one or more alkylated aromatic compounds. The alkylated aromatic compounds may be directly contacted with a hydrogenation catalyst to provide cycloalkanes.

[0069] The system disclosed herein may further include: a third reducing gas feed; and a hydrocracking reactor containing a hydrocracking catalyst. The hydrocracking reactor may have a reducing gas inlet, a heavy alkane product inlet, and a hydrocracking product outlet. The reducing gas inlet may be coupled to the third reducing gas feed; the heavy alkane product inlet (if present) may be coupled to the heavy alkane product outlet on a fourth separator.

[0070] In some embodiments, the reduction reactor further includes a reducing gas outlet, wherein the reducing gas outlet is coupled to a first carbon source gas feed and / or a first reducing gas feed.

[0071] The system disclosed herein may further include a mixer having a target aromatic product inlet, a target SAF alkane product inlet, and an aviation fuel outlet. The mixer may be configured to mix the alkane product and aromatic product produced by the system disclosed herein in a predetermined ratio to obtain the desired aviation fuel.

[0072] A system for producing alkane kerosene for aviation fuel is disclosed. The system includes: a first reducing gas feed; a first carbon source gas feed; a reduction reactor containing a reducing catalyst; a first separator connected to the reduction reactor; a second separator connected to the first separator; an oligomerization reactor containing an oligomerization catalyst and connected to the first and second separators; and a third separator having an oligomerization product inlet connected to an oligomerization product outlet. The reduction reactor has a first reducing gas feed inlet, a first carbon source feed inlet, and a mixed hydrocarbon outlet. The first reducing gas feed inlet is connected to the first reducing gas feed, and the first carbon source gas feed inlet is connected to the first carbon source gas feed. The first separator has a mixed hydrocarbon inlet connected to the mixed hydrocarbon outlet on the reduction reactor. The first separator is configured to separate a light hydrocarbon product mixture from a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture. In some embodiments, the light hydrocarbon product mixture may contain one or more C... 1-4 Alkanes and / or olefins, while in other embodiments, the mixture of light hydrocarbon products may contain one or more C44 hydrocarbons. 1-5 Alkanes and / or alkenes. The parameters of the separator can be adjusted as readily understood by one of ordinary skill in the art to change the carbon range of the separated stream (e.g., light, medium, heavy). It may be necessary to change the carbon range of alkanes and alkenes in the light hydrocarbon product mixture and increase the yield according to the desired product.

[0073] The first separator may have a water outlet (which may also be referred to herein as a wastewater outlet), C6 and higher (“C…”). 6+ Hydrocarbon exports and CO2, H, C 1-5 Hydrocarbon outlet. The first separator can be configured to separate the light hydrocarbon product mixture into a recycle stream and a stream containing one or more C44S hydrocarbons. 1-5 A mixture of residual light hydrocarbon products from alkanes and / or alkenes. The recycle stream may contain one or more C464-carbon hydrocarbons. 1-3 Hydrocarbons, CO2, CO, and / or H2, and may be combined with a first reducing gas and / or carbon source gas before contact with the reducing catalyst. The recycle stream may further contain oxygen-containing compounds, such as C. 1-3 alcohol.

[0074] The second separator may be configured to separate the heavy hydrocarbon product mixture from the medium hydrocarbon product mixture. The oligomerizing reactor has an oligomer outlet and may be configured to receive at least a portion of the light hydrocarbon product mixture from the first separator, and the oligomerizing reactor may be configured to receive the medium hydrocarbon product mixture from the second separator. The third separator may be configured to receive the heavy hydrocarbon product mixture from the second separator and may be configured to provide a mixture containing one or more C... 17+The heavy olefin product mixture of alkanes and / or alkenes is isolated from containing one or more C44 groups. 10-16 A mixture of target olefin products.

[0075] In this embodiment, the mixture of medium-quality hydrocarbon products may contain one or more C4 ...545444445454444454545454545454 5-8 Alkanes and / or alkenes. In some embodiments, the mixture of medium-quality hydrocarbon products may contain one or more C44 groups. 5-8 Alkanes and / or alkenes, while in other embodiments, the mixture of medium-quality hydrocarbon products may contain one or more C44 hydrocarbons. 6-9 Alkanes and / or alkenes. The parameters of the separator can be adjusted as readily understood by one of ordinary skill in the art to change the carbon range of the separated stream (e.g., light, medium, heavy). It may be necessary to change the carbon range of alkanes and alkenes in the medium hydrocarbon product mixture and increase the yield according to the desired product.

[0076] The oligomer reactor can be configured to process C 2-5 Olefin conversion (also known as dimerization) to C 4-8 Alkenes, and optionally C 6-10 Alkenes, then C 4-8 Olefin conversion (also known as dimerization) to C 10-16 Olefins. The oligomerization reactor may include two sections, each containing an oligomerization catalyst. The oligomerization catalysts in each or more sections may be the same or different. An intermediate quencher may be included between the two sections of the oligomerization reactor. The intermediate quencher may be supplied by a first separator, a third separator, or both a first separator and a third separator. The oligomerization reactor may be a stacked bed reactor.

[0077] The oligomer reactor may include two separate oligomer reactors connected in series, each containing an oligomer catalyst.

[0078] The system may further include a hydrogenator coupled to a third separator, configured to receive and hydrogenate a mixture of target olefin products to produce alkane kerosene. The hydrogenator may be coupled to an additional reducing gas feed.

[0079] In one embodiment, a hydrogenator and a separator can be used instead of a third separator, such that both the heavy hydrocarbon product mixture and the oligomer product mixture are separated into a target product mixture (e.g., C). 10-16 ) and mixtures of heavy products (e.g., C 17+ It was previously hydrogenated.

[0080] The system may include a fourth separator connected to the third separator to remove naphtha from the heavy hydrocarbon product mixture. The system may also include a fourth separator connected to a hydrogenator to remove naphtha from the target olefin product mixture.

[0081] Aviation fuel production methods

[0082] As described below, this disclosure provides various methods for converting carbon source gases into aviation fuels. This disclosure includes exemplary process conditions (e.g., temperature, pressure, space velocity, etc.) that provide certain advantages within the context of the systems and methods disclosed herein. However, any suitable conditions can be used, and those skilled in the art will understand how to modify the conditions of any particular process described herein to obtain results and fine-tune, as needed for a particular application, such as the product distribution considered.

[0083] This disclosure provides a variety of catalysts that can be used to prepare alkanes, alkenes, and mixtures thereof. Those skilled in the art will recognize that any suitable catalyst or catalyst mixture can be used in the methods and systems of this disclosure to provide the desired proportions of alkanes and alkenes provided herein.

[0084] This document provides a method for producing aviation fuel. The method may include: (i) contacting a first reducing gas and a first carbon source gas with a reducing catalyst to provide: a light hydrocarbon product mixture; and a target hydrocarbon product mixture; (ii) contacting the light hydrocarbon product mixture, optionally a second reducing gas, and optionally a second carbon source gas with an oligomerizing catalyst to provide an oligomerizing product mixture; (iv) hydrogenating the target hydrocarbon product mixture and the oligomerizing product mixture to provide a hydrogenated alkane product mixture, the hydrogenated alkane product mixture comprising: one or more C... 6-9 A mixture of medium-grade alkanes and alkanes containing one or more C44 groups. 10-16 (v) A target alkane product mixture; (v) contacting a medium-grade alkane product mixture with a reforming catalyst to provide a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture. The light hydrocarbon product mixture may contain one or more C4 ... 1-5 Alkanes and / or alkenes. Mixtures of hydrogenated alkane products may contain: one or more C... 1-5 A mixture of light alkane products containing one or more C44 groups. 6-9 A mixture of medium-grade alkanes and alkanes containing one or more C44 groups. 10-16 A target alkane product mixture. The method may further include the step of alkylating the light aromatic product mixture and the light hydrocarbon product mixture by contacting them with an alkylation catalyst to provide a target aromatic product mixture. The method may further include the step of hydrogenating at least a portion of the target aromatic product mixture to provide a target cycloalkane product mixture.

[0085] Another step may include combining a target aromatic product mixture and a target alkane product mixture to produce aviation fuel. The method may include combining a target aromatic product mixture, a target cycloalkane product mixture, and a target alkane product mixture to produce aviation fuel. The target hydrocarbon product mixture may contain: one or more C... 10-16 A mixture of medium-quality hydrocarbon products of alkanes and / or alkenes, and optionally containing one or more C44 groups. 17-40 A mixture of heavy hydrocarbon products of alkanes and / or alkenes.

[0086] In some embodiments, the contact between the first reducing gas and the first carbon source gas and the reduction catalyst occurs at an alkane temperature that may be at least 80°C, at least 100°C, or at least 120°C. The alkane temperature may be 550°C or lower, or 600°C or lower, or 650°C or lower. The alkane temperature may be from about 100°C to about 600°C. The alkane temperature may be from about 200°C to about 500°C, or about 350°C.

[0087] In some embodiments, the contact between the first reducing gas and the first carbon source gas and the reducing catalyst occurs at an alkane pressure of about 50 psi to about 4000 psi.

[0088] Alkane pressure can be from about 75 psi to about 500 psi. Alkane pressure can be about 75 psi, about 500 psi, about 325 psi, about 350 psi, about 375 psi, about 400 psi or about 450 psi.

[0089] In some embodiments, each of the light hydrocarbon product mixture, the middle hydrocarbon product mixture, the heavy hydrocarbon product mixture, and / or the target hydrocarbon product mixture comprises olefins and alkanes. In further embodiments, the ratio of olefins to alkanes in each of the light hydrocarbon product mixture, the middle hydrocarbon product mixture, the heavy hydrocarbon product mixture, and / or the target hydrocarbon product mixture is at least about 0.5:1. The ratio of olefins to alkanes in each of the light hydrocarbon product mixture and the middle hydrocarbon product mixture may be at least about 2:1, at least about 3:1, at least about 4:1, at least about 5:1, at least about 6:1, at least about 7:1, at least about 8:1, at least about 9:1, or at least about 10:1. The ratio of olefins to alkanes in each of the light hydrocarbon product mixture and the middle hydrocarbon product mixture may be about 1:1 to about 20:1, about 5:1 to about 20:1, or about 5:1 to about 15:1.

[0090] In some embodiments, contacting the first reducing gas and the carbon source gas with the reduction catalyst further provides a mixture containing one or more C atoms. 2-5 A mixture of light hydrocarbon products, including alkanes and / or olefins. In some embodiments, the light hydrocarbon product mixture contains C... 2-5Alkenes and C 2-5 The ratio of alkanes is at least about 5:1. In a further embodiment, the C content in the light hydrocarbon product mixture is... 2-5 Alkenes and C 2-5 The ratio of alkanes is at least about 8:1. In some embodiments, the C content in the light hydrocarbon product mixture is... 2-5 Alkenes and C 2-5 The ratio of alkanes is from about 5:1 to about 15:1, or from about 8:1 to about 10:1. In some embodiments, the C content in the light hydrocarbon product mixture is... 2-5 Alkenes and C 2-5 The ratio of alkanes is approximately 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0091] In some embodiments, the medium hydrocarbon product mixture contains one or more C 6-9 Alkanes and alkenes. In some embodiments, the C content in the medium-quality hydrocarbon product mixture is... 6-9 Alkenes and C 6-9 The ratio of alkanes is at least about 3:1, or at least about 5:1. In some embodiments, the C content in the medium-quality hydrocarbon product mixture is... 6-9 Olefins and C 6-9 The ratio of alkanes is from about 3:1 to about 12:1. In some embodiments, the C content in the medium-quality hydrocarbon product mixture is... 6-9 Alkenes and C 6-9 The ratio of alkanes is approximately 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1.

[0092] In some embodiments, the methods of this disclosure involve mixtures comprising aromatic compounds. These aromatic compounds can be described by their carbon number, for example, "C". X-Y "Aromatic compounds." As those skilled in the art will understand, the carbon number refers to the total number of carbon atoms in the molecule and does not necessarily refer to the number of ring atoms. For example, the term "C..." 10 The group of compounds described under "aromatic compounds" may include naphthalene (C 10 H8), butylbenzene (C 10 H 14 )wait.

[0093] In some embodiments, the contact between the intermediate alkane product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the reforming catalyst occurs at an aromatic temperature of about 200°C to about 650°C, about 400°C to about 650°C, or about 500°C to about 600°C. In some embodiments, the contact between the intermediate alkane product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the reforming catalyst occurs at an aromatic pressure of about 20 psi to about 800 psi, about 20 psi to about 1000 psi, about 20 psi to about 500 psi, or about 20 psi to about 200 psi.

[0094] The method disclosed herein may further include passing a mixture of light hydrocarbon products through an adsorbent bed or a distillation column before contacting it with an oligomerizing catalyst.

[0095] The method disclosed herein may further include passing a mixture of medium-quality alkane products through an adsorbent bed or a distillation column before contacting it with a reforming catalyst.

[0096] The medium-chain alkane product mixture can be split into streams, wherein the first stream is contacted with the reforming catalyst and the second stream is combined with the target hydrocarbon product mixture to undergo hydrogenation again.

[0097] In some embodiments, contacting the medium-chain alkane product mixture with a reforming catalyst further provides a product containing one or more C44 groups. 6-8 A mixture of light aromatic compound products. The method may then further include contacting the light aromatic product mixture with an oligomerization catalyst, an alkylation catalyst, or both in a single oligomerization step to provide alkylated aromatic compounds in the oligomerization product mixture. When the light aromatic product is supplied to an oligoalkylation reactor, it can form a mixture optionally containing one or more C... 9-14 Alkylation of aromatic compounds and their introduction into mixtures of oligomers.

[0098] The method disclosed herein may include contacting a mixture of light hydrocarbon products with an oligomerizing catalyst to provide an oligomerizing product mixture. The method further includes applying an intermediate quenching agent to the step of contacting the light hydrocarbon product mixture with the oligomerizing catalyst. The intermediate quenching agent may be a mixture of light aromatic products. The intermediate quenching agent may be a portion of the light hydrocarbon product mixture and / or the light aromatic product mixture.

[0099] In some embodiments, it is desirable to oligomerize olefins produced by the methods of this disclosure based on CO2 in the presence of an oligomerization catalyst to produce a mixture of high-carbon olefins and optionally aromatic compounds. As used herein, the modifier “high-carbon” for hydrocarbons (e.g., alkanes) or olefins will refer to hydrocarbons (e.g., alkanes) or olefins with a higher carbon number than the precursor. Exemplary high-carbon hydrocarbons (e.g., alkanes) and olefins include, but are not limited to, C8-C. 16 Hydrocarbons (e.g., alkanes) and / or olefins. The oligomerization process can be carried out in a fixed-bed flow reactor or any other suitable reactor type.

[0100] Depending on the requirements, the range of temperatures at which this oligomerization can be carried out can be from about 50°C to about 400°C, to customize the degree of oligomerization based on the desired product length and distribution. Oligomerization temperatures can be from about 40°C to about 400°C, from about 30°C to about 300°C, from about 50°C to about 250°C, from about 100°C to about 250°C, or from about 120°C to about 250°C. Oligomerization temperatures can be from about 50°C, about 100°C, about 110°C, about 120°C, about 150°C, about 180°C, about 190°C, about 200°C, about 220°C, about 230°C, or about 250°C. When the oligomerization reactor has a top section and a bottom section, the top section and the bottom section may each have the same or different oligomerization temperatures.

[0101] Depending on the requirements, the pressure range for this oligomerization can be from approximately 0 psi to approximately 2000 psi, tailored to the desired product length and distribution. Oligomerization pressures can be from approximately 0 psi to approximately 2000 psi, from approximately 500 psi to approximately 2000 psi, from approximately 0 psi to approximately 1000 psi, from approximately 100 psi to approximately 1000 psi, or from approximately 300 psi to approximately 1500 psi. Oligomerization pressures can be from approximately 0 psi, approximately 30 psi, approximately 250 psi, approximately 500 psi, approximately 750 psi, approximately 1000 psi, approximately 1250 psi, approximately 1500 psi, approximately 1750 psi, or approximately 2000 psi.

[0102] The method disclosed herein may further include passing a mixture of light hydrocarbon products through an adsorbent bed before contacting it with an oligomerization catalyst, an alkylation catalyst, or both of the aforementioned catalysts.

[0103] The method disclosed herein may further include removing impurities from the light hydrocarbon product mixture prior to contact with an oligomerizing catalyst. Impurities can be removed by any means known in the art, including, for example, by reaction chemistry, absorption, or other treatments. Impurities may comprise oxygen-containing compounds, sulfur, metals, or combinations thereof.

[0104] In some embodiments, contacting a mixture of light hydrocarbon products and / or a mixture of light aromatic products with an oligomerizing catalyst further provides an oligomerizing product mixture comprising: one or more C... 6-9 A mixture of medium-quality oligomers of hydrocarbons, containing one or more C44 groups. 10-16 Target oligomer mixtures of alkanes and / or olefins, and containing one or more C 17-40 A mixture of heavy oligomers of alkanes and / or olefins.

[0105] In some embodiments, contacting the light hydrocarbon product mixture with an oligomer catalyst further provides a product containing one or more C... 6-9 A mixture of medium-quality oligomers of hydrocarbons.

[0106] The method disclosed herein may further include combining a mixture of light hydrocarbon products with a mixture of medium-weight oligomers prior to contact with an oligomer catalyst.

[0107] In some embodiments, contacting the light hydrocarbon product mixture with an oligomer catalyst further provides a product containing one or more C... 17-40 A mixture of heavy oligomers of alkanes and / or olefins.

[0108] Oligomeric product mixtures may include: containing one or more C 1-2 A mixture of light oligomers of hydrocarbons, containing one or more C 3-7 Mixtures of medium and low molecular weight hydrocarbons, containing one or more C4 ... 8-16 Target oligomer mixtures of hydrocarbons, and / or containing one or more C 17-25 A mixture of heavy oligomers of alkanes and / or olefins. The oligomer mixture may include a blend of target products containing one or more C44 groups. 9-14 Aromatic compounds and one or more C 10-16 Alkanes and / or alkenes.

[0109] The method disclosed herein may further include contacting a mixture of light hydrocarbon products and a mixture of light aromatic compound products with an alkylation catalyst to provide a target alkylaromatic product mixture comprising one or more alkylated aromatic compounds. In some such embodiments, the contacting of the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst may be carried out with any suitable catalyst under any suitable conditions. In some embodiments, the contacting of the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst occurs at an alkylation temperature. The alkylation temperature may be from about 50°C to about 500°C, from about 50°C to about 400°C, or from about 100°C to about 350°C. The alkylation temperature may be from about 50°C, from about 100°C, from about 150°C, from about 200°C, from about 250°C, from about 300°C, from about 350°C, or from about 400°C.

[0110] The mixture of light hydrocarbon products and the mixture of light aromatic products can be contacted with the alkylation catalyst before or simultaneously with the oligomerization catalyst. The alkylation catalyst and the oligomerization catalyst can be mixed or separated within the oligoalkylation reactor.

[0111] In some embodiments, the contact between the light hydrocarbon product mixture and the light aromatic product mixture and the alkylation catalyst occurs under alkylation pressure. The alkylation pressure can be from about 50 psig to about 1000 psig.

[0112] The methods disclosed herein may include hydrogenating a target hydrocarbon product mixture and an oligomer to provide a hydrogenated alkane product mixture comprising a light alkane product mixture, a medium alkane product mixture, and a target alkane product mixture. Hydrogenating the target hydrocarbon product mixture and the oligomer may also provide a heavy alkane product mixture. In some embodiments, the light alkane product mixture comprises one or more C... 1-5 Alkanes, and mixtures of medium-quality alkane products containing one or more C44 groups. 6-9 Alkanes, the target alkane product mixture contains one or more C 10-16 Alkanes, and mixtures of heavy alkane products contain one or more C44 groups. 17+ Alkanes. The mixture of hydrogenated alkane products may further contain less than about 10%, or less than about 5%, of aromatic compounds.

[0113] This method may include separating a mixture of light alkane products, a mixture of medium alkane products, and a mixture of target alkane products. The method may include separating the target alkane product mixture from the heavy alkane product mixture. Once separated from the remainder of the products, the light alkane product mixture may be recycled and reintroduced into the system by hydrogenating the light alkane product mixture to prepare a hydrogenated alkane product mixture. Optionally, the light alkane product mixture may be contacted with a fourth reducing gas prior to hydrogenation.

[0114] The method of this disclosure may further include contacting a mixture of light hydrocarbon products and a mixture of light aromatic products with an oligomerization catalyst and optionally an alkylation catalyst to provide an oligomerization mixture. The method of this disclosure may further include two steps of contacting the mixture of light hydrocarbon products and the mixture of light aromatic products with an oligomerization catalyst and optionally an alkylation catalyst to provide an oligomerization mixture, wherein each step includes dimerizing an olefin present in the stream contacted with the oligomerization catalyst.

[0115] In one embodiment, the light hydrocarbon product mixture can be separated into two parts, whereby a first part of the light hydrocarbon product mixture is contacted twice with an oligomerizing catalyst, causing the olefins present in the mixture to dimerize twice. In this embodiment, a second part of the light hydrocarbon product mixture is contacted once with the oligomerizing catalyst, causing the olefins present in the mixture to dimerize once. Therefore, the method may include contacting the light hydrocarbon product mixture with an oligomerizing catalyst, the method may include two steps: contacting one or more C4 ... 2-5 Olefin dimerization to prepare C 4-10 Alkenes; then make C 4-10 Olefin dimerization to prepare C 10-20 Olefins. When the contact between the light hydrocarbon product mixture and the oligomerization catalyst involves two steps, the oligomerization temperature in each step may be the same or different, with each oligomerization temperature ranging from about 120°C to about 250°C.

[0116] In some embodiments, the medium hydrocarbon product mixture may be partially or completely contacted with an oligomerizing catalyst. 6-9 Olefin dimerization to prepare C 12-18 Olefins.

[0117] In some embodiments, contacting the first reducing gas and the carbon source gas with the reducing catalyst further provides a mixture containing one or more C atoms. 17-40 A mixture of heavy hydrocarbon products of alkanes and / or alkenes.

[0118] The method disclosed herein may further include contacting a third reducing gas and a mixture of heavy oligomers and / or a mixture of heavy hydrocarbon products with a hydrocracking catalyst to provide a product containing one or more C 1-18 A mixture of hydrocracking products of alkanes and / or olefins.

[0119] In some embodiments, the contact between the third reducing gas and the mixture of heavy oligomers and / or the mixture of heavy hydrocarbon products with the hydrocracking catalyst occurs at a hydrocracking temperature of about 250°C to about 450°C.

[0120] In some embodiments, the contact between the third reducing gas and the mixture of heavy oligomers and / or heavy hydrocarbon products and the hydrocracking catalyst is carried out at a hydrocracking pressure of less than about 1000 psig. In some embodiments, the hydrocracking pressure is from 0 psig to about 1000 psig.

[0121] The method disclosed herein may further include hydrogenating a mixture of light aromatic products, for example, to prepare cycloalkanes. Optionally, this may further include contacting the mixture of light aromatic products with a fourth reducing gas prior to hydrogenation.

[0122] Production methods of alkane kerosene

[0123] This invention discloses a method for producing alkane kerosene for aviation fuel. The method includes: contacting a first reducing gas and a first carbon source gas with a reduction catalyst to provide: [a product containing one or more C244 carbon atoms]. 2-4 A mixture of light hydrocarbon products, a mixture of heavy hydrocarbon products, and a mixture of medium hydrocarbon products. The next step may be to contact the light and medium hydrocarbon product mixtures with an oligomerizing catalyst in an oligomerizing reactor to provide an oligomerizing product mixture, and to combine the heavy hydrocarbon product mixture and the oligomerizing product mixture to provide a combined product mixture. The method further includes separating the combined product mixture into those containing one or more C atoms. 10-16 Target olefin product mixtures and containing one or more C 17+ A mixture of heavy olefins, including alkanes and / or alkenes. The target olefin product mixture may contain one or more C44 groups. 10-16 Alkanes and one or more C 10-16 Alkenes. Subsequently, one or more C24 groups can be added. 17+ Hydrogenation of a heavy olefin mixture of alkanes and / or olefins. In one embodiment, the combined product mixture undergoes hydrogenation and separation in a merging step. The next step includes hydrogenating the target olefin product mixture to provide alkane kerosene. In another embodiment, the target olefin product mixture and the heavy olefin mixture can be combined and saturated with olefins in a hydrogenation reactor containing a hydrogenation catalyst. The saturated hydrogenation product can be separated into alkane kerosene and products containing one or more C44 groups. 17-25 A mixture of heavy alkanes that can be recycled and processed as diesel fuel.

[0124] The alkane kerosene prepared by the process described herein may contain approximately 30 wt% to approximately 60 wt% C. 10-16 n-chain alkanes, approximately 30 wt% to approximately 60 wt% of C 10-16 The product contains isoparaffins, less than about 5 wt% cycloalkanes, and less than about 1 wt% aromatic compounds. The alkane kerosene prepared by the process described herein may contain about 35 wt% to about 55 wt% C. 10-16 n-chain alkanes, approximately 35 wt% to approximately 55 wt% C 10-16 It contains isoparaffins, less than about 5 wt% cycloalkanes, and less than about 1 wt% aromatic compounds. Alkane kerosene may contain about 0 wt% aromatic compounds. Alkane kerosene may contain less than about 1 wt% cycloalkanes. Alkane kerosene may contain about 40 wt% to about 50 wt% C. 10-16 n-chain alkanes, approximately 40 wt% to approximately 50 wt% C 10-16Isoalkanes. Alkane kerosene may contain approximately 40 wt% to approximately 50 wt% C. 10-16 n-chain alkanes, approximately 40 wt% to approximately 50 wt% C 10-16 Isoalkanes, about 0 wt% aromatic compounds and less than about 1 wt% cycloalkanes.

[0125] The step of contacting a mixture of light hydrocarbon products with an oligomer catalyst may include two steps: reacting one or more C atoms in the light hydrocarbon product mixture with an oligomer catalyst. 2-4 Dimerization of alkanes and / or olefins to prepare one or more C 4-8 Alkanes and / or alkenes; then C 4-8 Dimerization of alkanes and / or olefins to prepare C 10-16 Alkanes and / or olefins. The step of contacting a mixture of medium-quality hydrocarbon products with an oligomer catalyst may include: introducing one or more C... 5-8 Dimerization of alkanes and / or olefins to prepare C 10-16 Alkanes and / or alkenes. Target and heavy alkanes and / or alkenes may constitute the majority (i.e., more than 50 wt%) of the oligomer mixture. The oligomer mixture may contain from about 0 wt% to about 8 wt% of C-containing compounds. 1-5 A mixture of light oligomers of hydrocarbons, comprising approximately 0 wt% to approximately 8 wt% of C 6-9 A mixture of medium-quality oligomers of hydrocarbons, comprising approximately 10 wt% to approximately 50 wt% of C 17+ A mixture of heavy oligomers of hydrocarbons and approximately 30 wt% to approximately 80 wt% of C 10 -C 16 The target oligomer mixture of hydrocarbons. The selectivity of the oligomerizing catalyst can vary depending on the residence time in the reactor, as will be readily understood by those skilled in the art. For example, a longer residence time will result in higher selectivity for heavy oligomer mixtures.

[0126] An oligomerization reactor may contain two or more sections within a single reactor, each containing an oligomerization catalyst. The oligomerization catalysts in the different sections of the oligomerization reactor may be the same or different. An intermediate quencher may be supplied between the sections of the oligomerization reactor to lower the temperature in the bottom section of the reactor. In one embodiment, the method further includes applying the intermediate quencher in the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst.

[0127] Although the oligomer reactor is depicted in the figure as a single reactor with two sections, it can also be replaced by two separate oligomer reactors arranged in series.

[0128] Depending on the requirements, the range of temperatures at which this oligomerization can be carried out can be from about 50°C to about 400°C, to customize the degree of oligomerization based on the desired product length and distribution. Oligomerization temperatures can be from about 40°C to about 400°C, from about 30°C to about 300°C, from about 50°C to about 250°C, from about 100°C to about 250°C, or from about 120°C to about 250°C. Oligomerization temperatures can be from about 50°C, about 100°C, about 110°C, about 120°C, about 150°C, about 180°C, about 190°C, about 200°C, about 220°C, about 230°C, or about 250°C. When the oligomerization reactor has a top section and a bottom section, the top section and the bottom section may each have the same or different oligomerization temperatures.

[0129] Depending on the requirements, the pressure range for this oligomerization can be from approximately 0 psi to approximately 2000 psi, tailored to the desired product length and distribution. Oligomerization pressures can be from approximately 0 psi to approximately 2000 psi, from approximately 500 psi to approximately 2000 psi, from approximately 0 psi to approximately 1000 psi, from approximately 100 psi to approximately 1000 psi, or from approximately 300 psi to approximately 1500 psi. Oligomerization pressures can be from approximately 0 psi, approximately 30 psi, approximately 250 psi, approximately 500 psi, approximately 750 psi, approximately 1000 psi, approximately 1250 psi, approximately 1500 psi, approximately 1750 psi, or approximately 2000 psi.

[0130] The method may further include removing impurities from the light hydrocarbon product mixture prior to contact with the oligomerizing catalyst. Impurities can be removed by any means known in the art, including, for example, by reaction chemistry, absorption, or other treatments. Impurities may contain oxygen-containing compounds, sulfur, or combinations thereof.

[0131] Catalysts used to convert carbon sources into olefins and alkanes

[0132] The systems and methods disclosed herein may include the use of a reduction catalyst. The conversion of carbon dioxide and mixtures containing carbon dioxide can be achieved by catalytic carbon dioxide conversion, in which a reduction catalyst plays a crucial role. The reduction catalyst used herein can also be understood as a carbon dioxide hydrogenation catalyst, which enhances the activation and conversion of carbon dioxide and also controls the selectivity of the hydrogenation products. The reduction catalyst is active in converting carbon source gases (such as CO2) into hydrocarbons containing olefins and / or alkanes.

[0133] According to this disclosure, any suitable reduction catalyst can be used.

[0134] Transition metal catalysts, particularly base metals, are particularly effective as reduction catalysts due to their high electron density, diverse oxidation states, and abundant spectrum of cermet materials. They can enhance the activation of carbon dioxide and flexibly modulate the conversion pathway. In addition to the metal element, reduction catalysts may also contain one or more additional materials, such as binders, lubricants, and / or support materials. These materials can be added to optimize the catalyst formation process, metal dispersion, and other chemical and physical properties.

[0135] The reduction catalyst disclosed herein may comprise copper, iron, zinc, cobalt, or combinations thereof. The reduction catalyst may include copper. Copper catalysts are considered among the most efficient reduction catalysts, producing oxygen-containing compounds as the primary product. Such catalysts may comprise copper as the main catalytic component and one or more additional metal promoters, including but not limited to zinc, zirconium, aluminum, chromium, alkali metals, and alkaline earth metals. These additional components of the catalyst (including additional metal promoters, metal alloys, and / or metal oxides) provide electronic and structural support to better tune the reactivity and selectivity of carbon dioxide hydrogenation.

[0136] The reduction catalyst disclosed herein may comprise iron and / or cobalt. Iron and cobalt catalysts are widely used in carbon dioxide hydrogenation, particularly in Fischer-Tropsch processes, for example, to form long-chain hydrocarbons and oxygen-containing products. Similar to copper-containing catalysts, iron and cobalt-containing catalysts may comprise one or more additional metal promoters to improve the selectivity of carbon dioxide adsorption and hydrogenation. The one or more additional metal promoters may be selected from zinc, manganese, molybdenum, copper, nickel, alkali metals, and alkaline earth metals.

[0137] The reduction catalysts disclosed herein may comprise and / or be derived from a specific metal oxide or a combination of multiple metal oxides. Those skilled in the art will understand that during various catalyst preparation and activation methods known in the art, and in those methods exemplified herein, some or all of the oxygen atoms in the metal oxide may bond to other atoms in the catalyst mixture, and / or may be partially or entirely removed from the catalyst mixture during the activation step (e.g., converted to CO2 and removed). Furthermore, those skilled in the art should understand that for such catalysts, such as the reduction catalysts and / or alkane catalysts described below, the molar ratio of oxygen relative to the total composition may vary. Moreover, as will be understood, when defining catalysts made from metal oxides, the molar ratio of one metal to another is defined based on the metal (not the metal oxide).

[0138] The reduction catalyst can be an alkane catalyst or an olefin catalyst. As used herein, the term "alkane catalyst" refers to a catalyst used to convert a carbon source and reducing gas primarily to alkanes, but it does not necessarily contain alkanes itself. Alkane catalysts can be selected when the desired product is an alkane. Alkane catalysts can be used to convert a carbon source and reducing gas primarily to alkanes, and small amounts of olefins and / or other hydrocarbons. As used herein, the term "olefin catalyst" refers to a catalyst used to convert a carbon source and reducing gas primarily to olefins, but it does not necessarily contain olefins itself. Olefin catalysts can be selected when the desired product is an olefin. Olefin catalysts can be used to convert a carbon source and reducing gas primarily to olefins, and small amounts of alkanes and / or other hydrocarbons.

[0139] The reduction catalyst may contain: zinc; one or more first elements selected from iron or cobalt; and oxygen, carbon, or nitrogen. The reduction catalyst may also contain: copper; zinc; one or more first elements selected from iron or cobalt; and oxygen, carbon, or nitrogen. The reduction catalyst may also contain aluminum. The reduction catalyst may also contain one or more second elements selected from Group V, VI, VII, VIII, IX, X, and XI metals (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may also contain one or more Group IA and IIA metals.

[0140] The reduction catalyst may comprise: zinc; one or more first elements selected from iron or cobalt; oxygen, carbon, or nitrogen; and aluminum. The reduction catalyst of the present invention may comprise: zinc; one or more first elements selected from iron or cobalt; oxygen, carbon, or nitrogen; aluminum; and one or more second elements selected from Group V, VI, VII, VIII, IX, X, and XI metals (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may comprise: zinc; one or more first elements selected from iron or cobalt; oxygen, carbon, or nitrogen; aluminum; and one or more Group IA and IIA metals.

[0141] The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; oxygen or carbon or nitrogen; and aluminum. The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; oxygen or carbon or nitrogen; aluminum; and one or more second elements selected from Group V, VI, VII, VIII, IX, X, and XI metals (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; oxygen or carbon or nitrogen; aluminum; and one or more Group IA and IIA metals.

[0142] One or more of the first element may be present in amounts of about 0.5 to about 40 wt%, about 1 to about 40 wt%, about 0.5 to about 20 wt%, about 5 to about 30 wt%, about 1 to about 10 wt%, about 10 to about 20 wt%, about 20 to about 30 wt%, about 25 to about 40 wt%, about 25 to about 30 wt%, about 22 to about 24 wt%, about 30 to about 40 wt%, or about 35 to about 40 wt%.

[0143] The reduction catalyst may comprise a cobalt-intercalated interconnect matrix of reduced copper nanoparticles and alumina-modified zinc oxide. In some embodiments, cobalt is present in the form of cobalt oxide. In some embodiments, copper is present in the form of copper oxide. In some embodiments, the molar ratio of cobalt to copper to zinc (Co:Cu:Zn) is about 0.1-100 based on cobalt, about 0.05-4 based on copper, and about 0.05-2 based on zinc. In some embodiments, the Co:Cu:Zn ratio is in the range of 1 to 2 based on cobalt, 1 to 3 based on copper, and 0.5 to 1 based on zinc. In some embodiments, the Co:Cu:Zn ratio is about 1:2.5:1. In some embodiments, the molar content of zinc is preferably 0.3 to 1 times the molar content of copper. In some embodiments, the molar content of cobalt is preferably 0.1 to 1 times the molar content of copper.

[0144] The reduction catalyst may comprise a reduced copper nanoparticle and an alumina-modified zinc oxide intercalation matrix containing embedded iron interconnects. In some embodiments, the iron is present in the form of iron oxide. In some embodiments, the iron oxide is magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof. In a further embodiment, the iron oxide is magnetite (Fe3O4). In yet another embodiment, the iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3).

[0145] In some embodiments, copper is present in the form of copper oxide. In some embodiments, the molar ratio of iron to copper to zinc (Fe:Cu:Zn) is from about 0.1 to about 100 based on iron, from about 0.05 to about 4 based on copper, and from about 0.05 to about 4 based on zinc. In some embodiments, the Fe:Cu:Zn ratio is in the range of from about 0.4 to about 2 based on iron, from about 1 to about 3 based on copper, and from about 0.5 to about 3 based on zinc. In some embodiments, the Fe:Cu:Zn ratio is about 1:2.3:2.3. In some embodiments, the molar content of zinc is preferably from about 0.3 to about 1 times the molar content of copper. In some embodiments, the molar content of iron is from about 0.5 to about 5 times the molar content of copper.

[0146] In addition to one or more of the first elements mentioned above, the reduction catalyst may also contain elements selected from transition metals ( For example The reduction catalyst comprises one or more second elements selected from Group VI, VII, VIII, IX, X, or XI metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group VI metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group VII metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group VIII metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group IX metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group X metals. In some embodiments, the reduction catalyst comprises one or more second elements selected from Group XI metals.

[0147] One or more second elements may include manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. One or more second elements may include nickel. One or more second elements may include silver. One or more second elements may include palladium. One or more second elements may include niobium. One or more second elements may include manganese. One or more second elements may include zirconium. One or more second elements may include molybdenum.

[0148] In some embodiments, the reduction catalyst comprises one or more second elements in a molar ratio to one or more first elements of about 0.05 to about 4, about 0.05 to about 3, about 0.05 to about 1, about 0.05 to about 0.75, about 0.05 to about 0.5, or about 0.05 to about 0.25.

[0149] In some embodiments, the reduction catalyst comprises copper in a molar ratio to one or more first elements of about 0.5 to about 10, about 1 to about 10, about 0.5 to about 5, about 0.5 to about 2, about 1 to about 5, about 2 to about 9, about 2 to about 6, about 2 to about 4, or about 2.3 to about 8.4.

[0150] In some embodiments, the reduction catalyst comprises zinc in a molar ratio to copper of about 0.3 to about 3, about 1 to about 2.5, or about 0.4 to about 1.

[0151] The reduction catalyst may comprise one or more Group IA or IIA metals. In some embodiments, the one or more Group IA or IIA metals comprise magnesium, calcium, potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals are composed of magnesium, calcium, potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals comprise sodium and / or cesium. In some embodiments, the one or more Group IA or IIA metals comprise sodium and cesium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In some embodiments, the one or more Group IA or IIA metals comprise cesium. In some embodiments, the one or more Group IA or IIA metals are composed of sodium and / or cesium. In some embodiments, the one or more Group IA or IIA metals are composed of sodium and cesium. In some embodiments, the one or more Group IA or IIA metals are composed of sodium. In some embodiments, the one or more Group IA or IIA metals are composed of cesium.

[0152] In some embodiments, the reduction catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.01 to about 1.0 relative to copper, about 0.05 to about 0.50 relative to copper, about 0.10 to about 0.30 relative to copper, about 0.20 to about 0.50 relative to copper, about 0.30 to about 0.50 relative to copper, or about 0.40 to about 0.50 relative to copper.

[0153] In some embodiments, the reduction catalyst comprises one or more Group IA metals. The one or more Group IA or IIA metals may comprise potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals are composed of potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals comprise potassium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In some embodiments, the one or more Group IA or IIA metals comprise cesium.

[0154] In some embodiments, the reduction catalyst comprises potassium in a molar ratio to copper of about 0.05 to about 0.5, about 0.05 to about 0.1, about 0.09 to about 0.4, about 0.1 to about 0.3, or about 0.08 to about 1.0.

[0155] In some embodiments, the reduction catalyst comprises aluminum in a molar ratio to copper of about 0.1 to about 10, about 0.1 to about 1, about 0.1 to about 0.2, or about 0.5 to about 1.

[0156] The reduction catalyst may contain one or more metal oxides selected from the group consisting of: zinc oxide, copper oxide,

[0157] Cobalt oxide,

[0158] Iron oxide, nickel oxide, and any combination thereof

[0159] The reduction catalyst may contain alumina.

[0160] In some embodiments, the reduction catalyst comprises alumina (Al₂O₃), wherein aluminum is present in a molar ratio relative to copper of about 0.01 to about 100, about 0.1 to about 0.8, about 10 to about 50, about 30 to about 50, about 30 to about 80, about 10 to about 80, or about 5 to about 20. In some embodiments, alumina may be added as a support to increase the surface area of ​​copper and zinc, or introduced in situ, for example, as a component of the reduction catalyst during catalyst formation, such as by co-precipitation of aluminum nitrate with the first element, copper, and zinc precursors.

[0161] In some embodiments, the reduction catalyst comprises copper, zinc oxide, cobalt, and aluminum oxide. In some embodiments, the reduction catalyst comprises copper, zinc oxide, nickel, and aluminum oxide. In some embodiments, the reduction catalyst comprises copper, zinc oxide, iron, and aluminum oxide. In some embodiments, the reduction catalyst comprises copper, zinc oxide, cobalt, aluminum oxide, and a Group IA metal. In some embodiments, the reduction catalyst comprises copper, zinc oxide, nickel, aluminum oxide, and a Group IA metal. In some embodiments, the reduction catalyst comprises copper, zinc oxide, iron, aluminum oxide, and a Group IA metal. The molar ratio of the aforementioned components can be as described above.

[0162] The reduction catalyst may contain Cu, Zn, Al, and O. The reduction catalyst may contain Cu, Zn, Al, O, and alkali metals, and optionally also contain Ni, Fe, Co, Nb, Mo, In, Se, or any combination thereof.

[0163] The elemental composition of the reduction catalyst material can be Cu(ZnO)CoA / Al2O3, Cu(ZnO)CoFeA / Al2O3, Cu(ZnO)CoNbA / Al2O3, Cu(ZnO)CoNiA / Al2O3, Cu(ZnO)CoMoA / Al2O3, where A is an alkali metal and the relative amounts of the elemental components are as described above.

[0164] The elemental composition of the reduction catalyst material can be Cu(ZnO)Co / Al2O3, Cu(ZnO)CoFe / Al2O3, Cu(ZnO)CoNb / Al2O3, Cu(ZnO)CoNi / Al2O3, or Cu(ZnO)CoMo / Al2O3, wherein the relative amounts of the elemental components are as described above.

[0165] The elemental composition of the reduction catalyst material can be CuO(ZnO), Cu(ZnO)Co, Cu(ZnO)CoK, Cu(ZnO)CoFe, Cu(ZnO)CoFeK, Cu(ZnO)CoNi, Cu(ZnO)CoNiK, Cu(ZnO)CoNb, Cu(ZnO)CoNbK, Cu(ZnO)CoMo, Cu(ZnO)CoMoK on Al2O3, wherein the relative amounts of the elemental components are as described above.

[0166] In a further aspect, this document provides a reduction catalyst comprising:

[0167] One or more metals;

[0168] Optionally selected from one or more second elements, such as copper and zinc;

[0169] Optionally, one or more Group VI, VII, VIII, IX, X or XI metal additives;

[0170] Group IA or IIA metals that optionally act as promoters.

[0171] One or more metals may be selected from cobalt, iron, nickel, indium, yttrium, lanthanum, and combinations thereof. In some embodiments, one or more metals are cobalt. In other embodiments, one or more metals are iron. In still further embodiments, one or more metals are a combination of iron and cobalt.

[0172] One or more elements may exist in the form of oxides, nitrides, or carbides. In some embodiments, one or more metals exist in the form of iron oxide.

[0173] In a further embodiment, one or more of the second elements are copper. In yet another embodiment, one or more of the second elements are zinc. In still a further embodiment, one or more of the second elements are copper and zinc. In some embodiments, one or more of the second elements are present in the form of oxides, nitrides, or carbides. In yet another further embodiment, one or more of the second elements are zinc oxide.

[0174] In some embodiments, one or more Group VI, VII, VIII, IX, X, or XI metal additives (in the presence) are selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. In further embodiments, Group IA or IIA metals (in the presence) are Group IA elements. In still further embodiments, one or more Group IA or IIA metals (in the presence) are magnesium, calcium, lithium, sodium, potassium, or cesium. In still further embodiments, Group IA or IIA metals (in the presence) are lithium, sodium, potassium, or cesium. In still further embodiments, one or more second elements are present in an amount from about 0.5 wt% to about 40 wt% of the total amount of one or more metals, the second element, optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives, and optionally Group IA or IIA metals.

[0175] In some embodiments, the reduction catalyst comprises one or more Group VI or VII metals, such as manganese (Mn), chromium (Cr), or combinations thereof. In some embodiments, the reduction catalyst comprises one or more Group VI or VII metals in a molar ratio to copper or cobalt of about 0.01 to about 1.0, about 0.05 to about 0.50, about 0.1 to about 0.2, about 0.20 to about 0.50, about 0.30 to about 0.50, or about 0.40 to about 0.50.

[0176] In some aspects, the reduction catalyst comprises: one or more alkane metal oxides; optionally a support; and optionally one or more metal additives. The one or more alkane metal oxides may be selected from cobalt oxide, iron oxide, nickel oxide, indium oxide, yttrium oxide, lanthanide oxides, and combinations thereof. The support (when present) may comprise carbon, silicon dioxide, zeolite, alumina, zirconium oxide, titanium oxide, or silicon carbide. The one or more metal additives (when present) may be selected from Group IA or IIA elements, palladium, platinum, ruthenium, or combinations thereof.

[0177] In some aspects, this disclosure provides a catalytic composition comprising one or more of a reduction catalyst and a reduction catalyst support. The reduction catalyst support can be any suitable material that can be used as a catalyst support.

[0178] The reduction catalyst support may comprise one or more materials selected from the following: oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some embodiments, the reduction catalyst support comprises γ-alumina. In some embodiments, the reduction catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silicon carbide. In some embodiments, the reduction catalyst support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite. In some embodiments, the reduction catalyst support is alumina formed in situ as part of a reduction catalyst. In some embodiments, the reduction catalyst support is selected from, but not limited to, MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, and TiO2. In some embodiments, the reduction catalyst support is selected from MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silicon carbide, and TiO2.

[0179] In some embodiments, the reduction catalyst support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0180] In some embodiments, the reduction catalyst support is selected from SiAlO x SO4-ZrO2, zirconium tungstate, tungstate titanium dioxide, and anatase (SiO2-Al2O3, SiO2-TiO2). In further embodiments, the reduction catalyst support is an aluminum-based material, such as alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite.

[0181] In some embodiments, the reduction catalyst support is a zeolite, such as Y-type zeolite, β-zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), L-type zeolite (LTL), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, and combinations thereof. In some embodiments, the reduction catalyst support is MCM-49. In further embodiments, the zeolite contains additional metals, such as Zn, Ga, Fe, or other transition metals. In still further embodiments, the additional metals are present in the form of metals supported on the zeolite or isomorphous substitution within the zeolite framework.

[0182] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine and / or sulfur.

[0183] In some embodiments, the carrier is a high surface area scaffold. In some embodiments, the carrier comprises a carbon allotrope. In some embodiments, the carrier comprises a mesoporous material, such as mesoporous silica. In such embodiments, as will be understood by those skilled in the art, the physical properties of the mesoporous material, such as mesopore volume and surface area, can be measured using standard gas absorption measurement techniques known in the art, including, for example, the Barrett-Joyner-Halenda (BJH) method for determining pore size distribution and pore volume, and the Brunauer, Emmett, and Teller (BET) method for obtaining specific surface area (hereinafter "surface area").

[0184] In some embodiments, the mesopore volume of the reduction catalyst support is from about 0.01 to about 3.0 cc / g.

[0185] In some embodiments, the surface area of ​​the reduction catalyst support is approximately 10 m². 2 / g to approximately 1000 m 2 / g. In some embodiments, the surface area of ​​the catalytic composition comprising a reduction catalyst support and a catalyst disclosed herein is about 10 m². 2 / g to approximately 1000 m 2 / g.

[0186] The catalytic composition may be in particulate form and have an average size of about 10 nm to about 5 μm, about 20 nm to about 5 μm, about 50 nm to about 1 μm, about 100 nm to about 500 nm, or about 50 nm to about 300 nm.

[0187] The catalytic composition may contain about 5 wt% to about 80 wt%, about 5 wt% to about 70 wt%, about 20 wt% to about 70 wt%, or about 30 wt% to about 70 wt% of a reduction catalyst.

[0188] In some embodiments, the reduction catalyst is a nanoparticle catalyst. The particle size of the reduction catalyst on the scaffold surface may be from about 1 nm to about 5 nm, from about 5 nm to about 100 nm, or from about 100 nm to about 500 nm. In some embodiments, the particle size of the unagglomerated particles is from about 100 nm to about 500 nm.

[0189] In some embodiments described throughout this disclosure, the reduction catalyst comprises iron. In such embodiments, the iron is preferably in the form of iron oxide. In some such embodiments, the iron oxide is magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof. In further such embodiments, the iron oxide is magnetite (Fe3O4). In still further such embodiments, the iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3).

[0190] The reduction catalyst may comprise: iron; optionally alumina; a first element optionally selected from copper, zinc, cobalt, manganese, chromium, or combinations thereof; and one or more second elements optionally selected from Group IA and IIA metals.

[0191] In some embodiments, the reduction catalyst further comprises an additive mixture containing potassium, manganese, ruthenium, and MgO. In further embodiments, the reduction catalyst comprises about 1% to about 10% by weight of the additive mixture.

[0192] The reduction catalyst may contain a first element selected from copper, zinc, cobalt, or combinations thereof. The first element may be copper. The first element may be zinc. The first element may be cobalt. The first element may be a combination of copper, zinc, and / or cobalt.

[0193] The reduction catalyst may contain one or more Group IA or IIA metals. One or more Group IA or IIA metals may contain magnesium, calcium, potassium, sodium, or cesium. One or more Group IA or IIA metals may be composed of magnesium, calcium, potassium, sodium, or cesium. One or more Group IA or IIA metals may contain magnesium. One or more Group IA or IIA metals may contain calcium. One or more Group IA or IIA metals may contain potassium. One or more Group IA or IIA metals may contain sodium. One or more Group IA or IIA metals may be composed of magnesium. One or more Group IA or IIA metals may be composed of calcium. One or more Group IA or IIA metals may be composed of potassium. One or more Group IA or IIA metals may be composed of sodium. One or more Group IA or IIA metals may be composed of cesium.

[0194] The reduction catalyst may comprise: iron; a first element selected from K, Li, Zr, Cs, Mg, Rh, Ca or combinations thereof; one or more second elements selected from Au, Cu, Na, Cr, Al, Ga, Mn, Co, Ru, Ni or combinations thereof; and optionally alumina.

[0195] The reduction catalyst may comprise: iron; K, Li, Zr, Cs, Mg, Rh, Ca or combinations thereof in a molar ratio of 0 to about 0.20 relative to iron; Au, Cu, Na, Cr, Al, Ga, Mn or combinations thereof in a molar ratio of 0 to about 0.60 relative to iron; and Zn in a molar ratio of 0 to about 0.50 relative to iron.

[0196] In some embodiments, the catalyst comprises K in a molar ratio of 0 to about 0.20 relative to iron, and / or Na in a molar ratio of 0 to about 0.60 relative to iron.

[0197] In some embodiments, the reduction catalyst comprises:

[0198] iron;

[0199] K, Cs, Mg, Rh, Ca or combinations thereof having a molar ratio to iron of 0 to about 0.20;

[0200] Na, Cu, Cr, Mn or combinations thereof having a molar ratio to iron of 0 to about 0.60;

[0201] Co, Ru, Ni, or combinations thereof having a molar ratio to iron of 0 to about 0.50.

[0202] In some embodiments, the reduction catalyst comprises Co in a molar ratio of about 0 to about 0.50, or about 0.1 to about 0.2, relative to iron. In some embodiments, the reduction catalyst comprises Co in a molar ratio of about 0.14, relative to iron, and K in a molar ratio of about 0.01, relative to iron.

[0203] Iron can be in metallic form, iron oxide form, or a combination thereof. In some embodiments, iron is in the form of iron oxide. Iron oxide can be FeO, magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof. In some embodiments, iron oxide is magnetite (Fe3O4). In other embodiments, iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3). In still other embodiments, iron oxide is a combination of FeO, magnetite (Fe3O4), and hematite (Fe2O3).

[0204] The reduction catalyst may contain: iron; a first element selected from copper, zinc, cobalt, or combinations thereof; and one or more second elements optionally selected from Group IA and IIA metals.

[0205] The reduction catalyst may also contain one or more third elements selected from group V, VI, VII, VIII, IX, X and XI metals (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum or nickel).

[0206] The reduction catalyst may contain: iron; and zinc as the primary element. One or both of iron and zinc may exist in oxide or carbide form. Iron oxide may be in the form of FeO, Fe2O3 (hematite), Fe3O4 (magnetite), or combinations thereof. Iron oxide may be substantially (e.g., more than about 80%, or more than about 90%) in the form of Fe2O3. Iron oxide may be substantially (e.g., more than about 80%, or more than about 90%) in the form of Fe3O4.

[0207] The reduction catalyst may comprise zinc in a molar ratio of about 0.2 to about 3, or about 0.3 to about 3, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.2 to about 1, or about 0.4 to about 1, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 1.5, relative to iron. In other embodiments, the reduction catalyst comprises zinc in a molar ratio of about 1.0, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.75, about 0.6, about 0.5, about 0.4, about 0.3, or about 0.25, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.5, relative to iron.

[0208] The reduction catalyst may contain an iron to zinc molar ratio of about 1:1 to about 7:1, about 1:1 to about 6:1, about 2:2 to about 6:1, about 1:1 to about 4:1, about 1:1 to about 3:1, or about 2:1 to about 3:1. The reduction catalyst may contain an iron to zinc molar ratio of about 1:1 to about 4.5:1, about 1.5:1 to about 3.5:1, about 1.5:1 to about 3:1, or about 1.5:1 to about 2.5:1. The reduction catalyst may contain an iron to zinc molar ratio of about 2:1.

[0209] In some embodiments, the reduction catalyst comprises: iron; zinc in a molar ratio of about 0.2 to about 3 relative to iron; and one or more Group IA or IIA metals.

[0210] One or more Group IA or IIA metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn in a molar ratio of 0 to about 0.50 relative to iron.

[0211] The reduction catalyst may comprise K, Na, Cs, Rh, or combinations thereof in a molar ratio to iron of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4. In other embodiments, the reduction catalyst comprises Na in a molar ratio to iron of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4.

[0212] The reduction catalyst may contain K, Na, Cs, Rh, or combinations thereof in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron and the first element. In some embodiments, the reduction catalyst contains Na in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron and the first element. In other embodiments, when the first element is zinc, the reduction catalyst may contain Na in an amount of about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron and zinc.

[0213] Another reduction catalyst may comprise: iron and zinc, one or more second elements selected from Group IA, IIA, and X metals, and a binder. When the reduction catalyst includes a binder, it may also be referred to as a shaped reduction catalyst. The reduction catalyst may comprise: iron and zinc; optionally alumina; a first element optionally selected from copper, cobalt, manganese, chromium, or combinations thereof; one or more second elements optionally selected from Group IA, IIA, and X metals; and a binder.

[0214] The reduction catalyst may contain a first element selected from copper, cobalt, or combinations thereof. The first element may be copper. The first element may be cobalt. The first element may be a combination of copper and / or cobalt. The reduction catalyst may not contain a first element selected from copper, cobalt, or combinations thereof.

[0215] The reduction catalyst may contain a second element selected from one or more Group IA or IIA metals. One or more Group IA or IIA metals may contain magnesium, calcium, potassium, sodium, cesium, rubidium, or any combination thereof. One or more Group IA or IIA metals may be composed of magnesium, calcium, potassium, sodium, cesium, or rubidium. One or more Group IA or IIA metals may contain magnesium. One or more Group IA or IIA metals may contain calcium. One or more Group IA or IIA metals may contain potassium. One or more Group IA or IIA metals may contain sodium. One or more Group IA or IIA metals may contain cesium. One or more Group IA or IIA metals may contain rubidium. One or more Group IA or IIA metals may be composed of magnesium. One or more Group IA or IIA metals may be composed of calcium. One or more Group IA or IIA metals may be composed of potassium. One or more Group IA or IIA metals may be composed of sodium. One or more Group IA or IIA metals may be composed of cesium. One or more Group IA or IIA metals may be composed of rubidium.

[0216] The reduction catalyst may contain a second element as a Group X metal. The Group X metal may be selected from palladium, platinum, iridium, nickel, and rhodium. The Group X metal may be platinum. The Group X metal may be palladium. The Group X metal may be nickel.

[0217] The reduction catalyst may also contain one or more third elements selected from Group V, VI, VII, VIII, IX, and XI metals (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium). The reduction catalyst may contain manganese. The reduction catalyst may contain silver. The reduction catalyst may not contain a third element selected from Group V, VI, VII, VIII, IX, and XI metals.

[0218] The reduction catalyst may comprise from about 0.1 wt% to about 60 wt% of Group IA, IIA, or X metals by weight of total iron, zinc, and Group IA, IIA, or X metals. The reduction catalyst may comprise from about 0.1 wt% to about 20 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 2 wt%, from about 0.4 wt% to about 1.5 wt%, or from about 0.5 wt% to about 1.5 wt% of Group IA, IIA, or X metals by weight of total iron, zinc, and Group IA, IIA, or X metals. The reduction catalyst may comprise from about 0.1 wt% to about 60 wt% of Group IA metals by weight of total iron, zinc, and Group IA metals. The reduction catalyst may comprise about 0.1 wt% to about 20 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 2 wt%, about 0.4 wt% to about 1.5 wt%, or about 0.5 wt% to about 1.5 wt% of Group IA metals by total weight of iron, zinc, and Group IA metals.

[0219] (1) The reduction catalyst may comprise Na, Mn, K, Cs, Li, or Rb in a molar ratio of 0 to about 0.60 relative to iron. In some embodiments, the reduction catalyst comprises: iron; K, Cs, Mg, Rh, Ca, or combinations thereof in a molar ratio of 0 to about 0.20 relative to iron; Na, Cu, Cr, Mn, or combinations thereof in a molar ratio of 0 to about 0.60 relative to iron; and / or Co, Ru, Ni, or combinations thereof in a molar ratio of 0 to about 0.50 relative to iron.

[0220] Iron can be in metallic form, iron oxide form, or a combination thereof. In some embodiments, iron is in the form of iron oxide. Iron oxide can be FeO, magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof. In some embodiments, iron oxide is magnetite (Fe3O4). In other embodiments, iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3). In still other embodiments, iron oxide is a combination of FeO, magnetite (Fe3O4), and hematite (Fe2O3).

[0221] The reduction catalyst may comprise: iron; zinc; a first element selected from copper, cobalt, or combinations thereof; one or more second elements optionally selected from Group IA, IIA, and X metals; and a binder.

[0222] The reduction catalyst may comprise iron and zinc, wherein one or both of iron and zinc are present in the form of oxides or carbides. Iron oxide may be in the form of FeO, Fe2O3 (hematite), Fe3O4 (magnetite), or combinations thereof. Iron oxide may be substantially (e.g., more than about 80%, or more than about 90%) in the form of Fe2O3. Iron oxide may be substantially (e.g., more than about 80%, or more than about 90%) in the form of Fe3O4.

[0223] The reduction catalyst may comprise zinc in a molar ratio of about 0.2 to about 3, or about 0.3 to about 3, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.2 to about 1, or about 0.4 to about 1, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 1.5, relative to iron. In other embodiments, the reduction catalyst comprises zinc in a molar ratio of about 1.0, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.75, about 0.6, about 0.5, about 0.4, about 0.3, or about 0.25, relative to iron. In some embodiments, the reduction catalyst comprises zinc in a molar ratio of about 0.5, relative to iron.

[0224] (2) The reduction catalyst may contain an iron to zinc molar ratio of about 1:1 to about 7:1, about 1:1 to about 6:1, about 2:2 to about 6:1, about 1:1 to about 4:1, about 1:1 to about 3:1, or about 2:1 to about 3:1. The reduction catalyst may contain an iron to zinc molar ratio of about 1:1 to about 4.5:1, about 1.5:1 to about 3.5:1, about 1.5:1 to about 3:1, or about 1.5:1 to about 2.5:1. The reduction catalyst may contain an iron to zinc molar ratio of about 2:1.

[0225] (3) In some embodiments, the reduction catalyst comprises: iron; zinc in a molar ratio of about 0.2 to about 6 relative to iron; and one or more Group IA and IIA metals. One or more Group IA and IIA metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn in a molar ratio of 0 to about 0.50 relative to iron. In some embodiments, the reduction catalyst comprises: iron; zinc in a molar ratio of about 0.2 to about 6 relative to iron; and one or more Group IA, IIA, and X metals. One or more Group IA, IIA, and X metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn in a molar ratio of 0.2 to about 3 relative to iron.

[0226] The reduction catalyst may comprise K, Na, Cs, Rh, Rb, Mn, Li, Pt, Pd, Ru, Cu, Mo, Ce, or combinations thereof in a molar ratio to iron of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4. In other embodiments, the reduction catalyst comprises Na or K in a molar ratio to iron of about 0.01 to about 0.20, about 0.01 to about 0.10, about 0.01 to about 0.08, about 0.01 to about 0.05, or about 0.02 to about 0.4.

[0227] The reduction catalyst may contain K, Na, Cs, Rh, Rb, Mn, Li, Pt, Pd, Ru, Cu, Mo, Ce, or combinations thereof in amounts of about 0.1 wt% to about 10 wt%, about 0.2% to about 10%, about 0.1% to about 2%, about 0.5% to about 5%, about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron and zinc. In some embodiments, the reduction catalyst contains Na or K in amounts of about 0.2% to about 10%, about 0.5% to about 5%, about 0.5% to about 3%, about 0.5% to about 1%, or about 1% to about 5% of the total weight of iron and zinc. In other embodiments, the reduction catalyst may contain Na in amounts of about 0.2% to about 10%, about 0.5% to about 5%, about 0.5% to about 3%, about 0.5% to about 1%, or about 1% to about 5% of the total weight of iron and zinc.

[0228] The reduction catalyst may comprise iron, zinc, and one or more Group IA or IIA metals, wherein the molar ratio of iron to zinc is from about 1:1 to about 4.5:1, from about 1.5:1 to about 3.5:1, from about 1.5:1 to about 3:1, or from about 1.5:1 to about 2.5:1; and one or more Group IA or IIA metals present in about 0.5% to about 1.0% of the total weight of iron and zinc.

[0229] The reduction catalyst may comprise iron, zinc, and one or more Group IA, IIA, or X metals, namely sodium, lithium, platinum, cesium, rubidium, manganese, or potassium, wherein the molar ratio of iron to zinc is from about 1.5:1 to about 2.5:1; and Na, Li, Rb, Mn, Cs, Pt, or K present in about 0.5% to about 1.0% of the total weight of iron and zinc.

[0230] In some respects, the reduction catalyst further comprises a reduction catalyst support. The reduction catalyst support can be any suitable material that can be used as a catalyst support.

[0231] Methane is typically an undesirable byproduct of carbon dioxide conversion. Therefore, methane yield is a factor in catalyst effectiveness because it is undesirable. Consequently, the lower the methane yield (also referred to herein as methane selectivity, SC1, defined in Equation 1), the better the catalyst. Referring to Equation 1, Cmol.CH4 represents the mole fraction of methane in the product stream, and Cmol.CO 2进料 This represents the mole fraction of CO2 in the feed stream, and Cmol.CO 2产物 This indicates the mole fraction of CO2 in the product stream.

[0232] Equation 1: Selectivity of methane (SC1) = [Cmol.CH4 / (Cmol.CO)] 2进料 - Cmol.CO 2产物 )]

[0233] The reduction catalysts disclosed herein may have methane selectivity (SC1) of less than about 15 mol% C, less than about 11 mol% C, or less than about 10 mol% C. The reduction catalysts may have methane selectivity of about 2 to about 15, about 4 to about 15, about 5 to about 12, about 5 to about 11, about 6 to about 11, or about 8 to about 11 mol% C. The reduction catalysts described herein may have selectivity for C2 to C4 hydrocarbons (SC2-C4) of greater than about 15, greater than about 20, greater than about 25, greater than about 30, greater than about 35, or greater than about 35 mol% C. The reduction catalysts described herein may have SC2-C4 selectivity of about 15 to about 50, about 20 to about 45, or about 25 to about 45 mol% C. The reduction catalysts described herein may have SC2-C4 selectivity of about 28, about 35, about 38, about 39, or about 45 mol% C. 2-4 The selectivity is determined by adding (selectivity of C2) + (selectivity of C3) + (selectivity of C4), with each selectivity value calculated according to Equation 2. Refer to Equation 2: C x Represents a hydrocarbon with x carbon atoms; Cmol.C x Indicates C in the product stream x mole fraction; Cmol.CO 2进料 This indicates the mole fraction of CO2 in the feed stream; and Cmol.CO 2产物 This indicates the mole fraction of CO2 in the product stream.

[0234] Equation 2: Hydrocarbon C x Selectivity C x (SC x ) = [Cmol.C x / (Cmol.CO 2进料 – Cmol.CO 2产物 )]

[0235] The reduction catalysts disclosed herein may have a C molarity greater than about 20, greater than about 22, greater than about 25, greater than about 28, greater than about 30, greater than about 32, or greater than about 34. 5+ Hydrocarbons (SC) 5+ C 5+ This refers to the selectivity of any hydrocarbon with 5 or more carbon atoms. The reduction catalysts disclosed herein may have a C molarity of about 20 to about 45, about 22 to about 43, about 25 to about 43, about 28 to about 43, or about 30 to about 40. 5+ Hydrocarbons (SC) 5+ The selectivity of the reduction catalysts disclosed herein can be about 29, about 31, about 33, about 34, about 35, or about 43 mol% C. 5+ Hydrocarbons (SC) 5+ The selectivity of C. 5+ The higher the selectivity of hydrocarbons, the better the catalyst performance of the carbon dioxide conversion process disclosed in this paper.

[0236] Oxygen-containing compounds are often undesirable byproducts of carbon dioxide conversion. The reduction catalysts disclosed herein may have oxygen-containing compound selectivity (Soxy) of less than about 20, less than about 16, less than about 14, or less than about 15 mol% of carbon. The reduction catalysts may have oxygen-containing compound selectivity of about 2 to about 20, about 4 to about 18, or about 4 to about 16 mol% of carbon.

[0237] Metal leaching can be a problem associated with the use of metal-containing catalysts. Metal leaching of catalysts can lead to several issues, including: i) product contamination: metal ions from the catalyst dissolve into the liquid, contaminating the product stream and potentially requiring extensive downstream treatment to remove the metal; ii) system corrosion: metal leaching can cause system corrosion; and iii) catalyst deactivation: metal leaching results in the loss of active material from the catalyst, as well as a loss of activity and selectivity. Higher leaching rates lead to faster catalyst deactivation.

[0238] Compared to other catalysts, including unsupported metal catalysts, the reduction catalyst disclosed herein offers a significant improvement in metal leaching. The shaped reduction catalyst disclosed herein (i.e., a catalyst including a binder) significantly reduces metal leaching compared to the same catalyst in powder form (i.e., without a binder). When comparing the powder catalyst with the shaped catalyst, the amount of metal leached can be reduced by more than about 50%, more than about 70%, more than about 80%, or more than about 90%.

[0239] Once the reaction reaches a steady state, the total metal leaching in the effluent can be measured by: i) separating the water and oil portions of the effluent; and ii) analyzing a sample of the water portion by ICP-MS to obtain the concentration of leached metals in the water sample. The method for measuring metal leaching may further include: iii) dissolving the oil portion in an acid (such as nitrohydrochloric acid); iv) analyzing a sample of the dissolved oil portion by ICP-MS to obtain the concentration of metals in the oil sample; and v) adding the metal concentrations in the oil sample to the metal concentrations in the water sample to obtain the total metal leaching. After reaching a steady state, the oil sample typically contains less than about 1 ppm of leached metals. Before reaching a steady state, loose powder from the catalyst migrates into the effluent and dissolves in the oil portion of the effluent, which can be tested if necessary. As the run continues, the loose powder from the catalyst is eliminated, and thus the metal concentration in the oil portion of the effluent decreases to zero.

[0240] A steady state of the reaction can be reached after operating time resulting in a second element concentration (ppm) of about 10 ppm or less, about 8 ppm or less, or about 6 ppm or less. A steady state of the reaction can be reached after operating time resulting in a second element concentration (ppm) of about 0 ppm to about 10 ppm, about 0 ppm to about 8 ppm, about 0 ppm to about 6 ppm, or greater than about 0 ppm to about 6 ppm. A steady state can be reached after operating time of about 100 hours to about 1000 hours, about 200 hours to about 800 hours, or about 200 hours to about 600 hours. The steady state of the reaction can be determined by the concentration of the second element, because the second element is leached in greater quantities than the active metal and is present in lower amounts in the catalyst. When the reduction catalyst is in contact with a continuous fluid flow, the total concentration of iron, zinc, and one or more second elements in the effluent under steady state can be less than about 50 ppm, less than about 40 ppm, less than about 20 ppm, or less than about 15 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent under steady-state conditions can be less than about 50 ppm, less than about 40 ppm, less than about 20 ppm, less than about 15 ppm, less than about 10 ppm, or less than about 5 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent tested under steady-state conditions can be from about 0 ppm to about 50 ppm, greater than about 0 ppm to about 40 ppm, about 1 ppm to about 30 ppm, or about 1 ppm to about 20 ppm. The total concentration of iron, zinc, and one or more secondary elements can also be understood as metal leaching in the reactor effluent after a period of operation or under steady-state conditions.

[0241] The total concentration of one or more second elements in the effluent under steady-state conditions can be less than about 10 ppm, less than about 8 ppm, less than about 6 ppm, less than about 5 ppm, less than about 4 ppm, less than about 3 ppm, or less than about 2 ppm. The total concentration of one or more second elements in the effluent tested under steady-state conditions can be from about 0 ppm to about 10 ppm, from about 0 ppm to about 8 ppm, from about 0 ppm to about 6 ppm, or greater than about 0 ppm to about 6 ppm. When the second element is sodium, the total concentration of sodium in the effluent under steady-state conditions (also understood as the concentration of sodium leached from the shaped catalyst) can be less than about 6 ppm, less than about 5 ppm, less than about 4 ppm, less than about 3 ppm, or less than about 2 ppm. The total concentration of sodium in the effluent tested under steady-state conditions can be from about 0 ppm to about 6 ppm, or greater than about 0 ppm to about 6 ppm.

[0242] The total concentration of iron, zinc, and one or more secondary elements in the effluent tested after approximately 200 to approximately 400 hours of operation may be less than approximately 50 ppm, less than approximately 40 ppm, less than approximately 20 ppm, or less than approximately 15 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent tested after approximately 400 hours of operation may be less than approximately 50 ppm, less than approximately 40 ppm, less than approximately 20 ppm, less than approximately 15 ppm, less than approximately 10 ppm, or less than approximately 5 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent tested after approximately 400 hours of operation may be approximately 0 ppm to approximately 50 ppm, greater than approximately 0 ppm to approximately 40 ppm, approximately 1 ppm to approximately 30 ppm, or approximately 1 ppm to approximately 20 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent tested after approximately 200 hours of operation may be less than approximately 50 ppm, less than approximately 40 ppm, less than approximately 20 ppm, or less than approximately 15 ppm. The total concentration of iron, zinc, and one or more secondary elements in the effluent tested after approximately 200 hours of operation may be approximately 0 ppm to approximately 50 ppm, approximately 1 ppm to approximately 40 ppm, approximately 1 ppm to approximately 20 ppm, or approximately 1 ppm to approximately 15 ppm. Metal leaching refers to the total amount (i.e., concentration) of iron, zinc, and secondary elements selected from Group IA, IIA, and / or X metal ions present in the effluent tested after a period of operation.

[0243] Because the second element present in the catalyst may be less than that of iron or zinc, reducing the leaching of the second element may be particularly important for maintaining catalyst lifetime. The leaching amount of the second element (e.g., Na, K) of the formed catalyst in the effluent tested after approximately 200 to approximately 400 hours of operation can be less than approximately 10 ppm, less than approximately 8 ppm, less than approximately 5 ppm, or less than approximately 2 ppm. The leaching amount of the second element of the formed catalyst in the effluent tested after approximately 400 hours of operation can be less than approximately 10 ppm, less than approximately 8 ppm, less than approximately 5 ppm, or less than approximately 2 ppm. The leaching amount of the second element of the formed catalyst in the effluent tested after approximately 400 hours of operation can be approximately 0 ppm to approximately 10 ppm, approximately 0 ppm to approximately 8 ppm, approximately 0 ppm to approximately 6 ppm, approximately 0.1 ppm to approximately 5 ppm, or approximately 1 ppm to approximately 4 ppm.

[0244] The leaching amount of the second element of the formed catalyst in the effluent tested after approximately 200 hours of operation can be less than about 10 ppm, less than about 8 ppm, less than about 5 ppm, or less than about 4 ppm. The leaching amount of the second element of the formed catalyst in the effluent tested after approximately 200 hours of operation can be from about 1 ppm to about 10 ppm, from about 1 ppm to about 8 ppm, from about 1 ppm to about 5 ppm, or from about 1 ppm to about 4 ppm.

[0245] The shaped reduction catalyst referred to herein includes a binder and a shape formed by any means known in the art, such as, but not limited to, extrusion, compression, granulation of powder into pellets, tablets, or other shaped forms. The shaped catalyst (as an extrudate or pellet) may have a crushing strength greater than about 20 N / mm, greater than about 25 N / mm, greater than about 30 N / mm, or greater than about 40 N / mm. The shaped catalyst (as an extrudate, pellet, or tablet) may have a crushing strength of about 20 N / mm to about 100 N / mm, about 20 N / mm to about 80 N / mm, about 20 N / mm to about 65 N / mm, about 30 N / mm to about 65 N / mm, about 35 N / mm to about 60 N / mm, or about 40 N / mm to about 55 N / mm.

[0246] Due to reduced metal leaching, the reduction catalysts disclosed herein exhibit a longer lifetime (i.e., before deactivation) than other catalysts. The reduction catalysts disclosed herein can maintain activity for more than about one year, more than about 18 months, more than about 20 months, more than about 36 months, or more than about 48 months. The reduction catalysts disclosed herein can maintain activity for about 1 year to about 5 years, about 2 years to about 5 years, about 3 years to about 5 years, or about 4 years to about 5 years. The term "maintain activity" means that the catalyst's activity in converting CO2 to hydrocarbons remains at more than about 75% of its initial activity.

[0247] In some aspects, the reduction catalyst further comprises a reduction catalyst support. The reduction catalyst support can be any suitable material that can serve as a catalyst support, or any reduction catalyst support disclosed above.

[0248] In some embodiments, the reduction catalyst comprising the reduction catalyst support is in particulate form with an average size of about 10 nm to about 5 μm, about 20 nm to about 5 μm, about 50 nm to about 1 μm, about 100 nm to about 500 nm, or about 50 nm to about 300 nm.

[0249] In some embodiments, the reduction catalyst comprising the reduction catalyst support comprises about 5 wt% to about 80 wt%, about 5 wt% to about 70 wt%, about 20 wt% to about 70 wt%, or about 30 wt% to about 70 wt% of the reduction catalyst.

[0250] In some embodiments, the reduction catalyst support is a high surface area scaffold. In a further embodiment, the reduction catalyst support comprises mesoporous silica. In yet another embodiment, the reduction catalyst support comprises a carbon allotrope.

[0251] In some embodiments, the reduction catalyst is a nanoparticle catalyst. In further embodiments, the particle size of the reduction catalyst on the scaffold surface is about 1 nm to about 5 nm, about 5 nm to about 100 nm, or about 100 nm to about 500 nm. In some embodiments, the particle size of the unagglomerated particles is 100 nm to 500 nm.

[0252] In some embodiments, the reduction catalyst is pretreated with syngas. In yet another embodiment, the reduction catalyst is pretreated with hydrogen. In still a further embodiment, the reduction catalyst is heated with an inert gas (including, but not limited to, nitrogen and / or argon) prior to production.

[0253] The reduction catalyst may contain a binder. The binder may be any binder known in the art. The binder may be freely chosen from the group consisting of boehmite (e.g., PURAL). ®TH 100, PURAL ® TH 80, PURAL ® TH 200, PURAL ® 200), silica-alumina hydrate (e.g., SIRAL) ® 1. SIRAL ® 5. SIRAL ® 10. SIRAL ® 20. SIRAL ® 40) Aluminates (e.g., sodium aluminate), silica (e.g., silicates, such as potassium silicate and sodium silicate, LUDOX) ® ), pseudoboehmite alumina (e.g., VERSAL) ® V-250), bentonite, montmorillonite clay, tungsten, zirconate, or any combination thereof.

[0254] The binder may be present in an amount of about 0.1 wt% to about 60 wt%, about 5 wt% to about 40 wt%, or about 10 wt% to about 30 wt% of the total catalyst composition by weight. In some embodiments, the binder is present in amounts of about 0.1% to about 30%, about 0.1% to about 20%, about 1% to about 30%, about 1% to about 20%, about 5% to about 25%, about 5% to about 20%, about 10% to about 20%, about 5% to about 15%, or about 15% to about 25% by weight of the total catalyst composition.

[0255] The binder may contain a promoter element selected from Na, K, Cs, Li, Rb, or combinations thereof. Studies have found that promoters in the binder can improve catalyst performance, such as activity, selectivity, and stability, by maintaining a constant promoter level on the active metal component. In particular, the benefits of doped binders include:

[0256] ●Improve methane selectivity;

[0257] ● Acidity increases hydrocarbon production rate;

[0258] ●By making the shaped catalyst mesoporous, this can improve product selectivity; and

[0259] ● Reduce metal leaching.

[0260] The adhesive can be a heterogeneous, amorphous, or microporous material. In some embodiments, the adhesive can be selected from the group consisting of sodium aluminate, potassium silicate, sodium silicate, and any combination thereof. The adhesive can be selected from sodium aluminate, potassium aluminate, sodium silicate, potassium silicate, sodium zirconate, potassium zirconate, sodium tungstate, potassium tungstate, or combinations thereof.

[0261] When accelerators are added to binders, the performance of the catalyst (e.g., regarding SC1 and SC) is affected. 5+ (In terms of) the performance of a catalyst with a binder without a promoter, SC1 may be significantly improved. When comparing the performance of a catalyst with the same catalyst and a binder with a promoter, SC1 can be improved (i.e., reduced) by about 20% to about 65%, about 30% to about 55%, about 30% to about 40%, or about 45% to about 55%. When comparing the performance of a catalyst with a binder without a promoter to the performance of the same catalyst and a binder with a promoter, SC1 can be improved (i.e., reduced) by about 20% to about 65%, about 30% to about 55%, about 30% to about 40%, or about 45% to about 55%. 5+ It can be improved (i.e., increased) by about 25% to about 75%, about 30% to about 50%, about 50% to about 75%, or about 55% to about 65%. For example, the foregoing comparison can be between undoped silicate binders and doped (with accelerator) silicate binders, or between undoped alumina binders and doped (with accelerator) silicate binders.

[0262] Binders that minimize or eliminate strong metal-support interactions with the active metal are preferred, as such interactions would inhibit the catalytic properties of the active metal. Preferred binders can bond small active metal particles together to form fairly large extrusions / pellets (1 mm to 5 mm). These extrusions / pellets are suitable for use in industrial reactors. They also offer better handling properties and avoid pressure drop in large reactors.

[0263] The binder disclosed herein reduces metal leaching, which improves catalyst lifetime. For powders, the surface area is very large, and therefore, by forming extrudates with the binder, thermal shock in large reactors can be reduced.

[0264] In some embodiments, when the reduction catalyst comprises iron oxide and zinc oxide, as well as Group IA or IIA metals, and when a first carbon source gas and a first reducing gas are fed into the reduction reactor, the iron oxide reacts in an active form selected from the group consisting of: Fe x O y Fe x C y And any combination thereof, where x is 1 to 3 and y is 0 to 4. The active form is used to convert CO2 into hydrocarbons selected from the group consisting of: alkenes, alkanes, oxygen-containing compounds, and any combination thereof.

[0265] Catalysts used to convert carbon sources into aromatic compounds

[0266] The systems and methods disclosed herein may include reforming catalysts. As used herein, the term "reforming catalyst" refers to a catalyst used to convert a carbon source into aromatic compounds (such as benzene, toluene, and xylene (collectively referred to as "BTX") and heavy aromatic compounds), but does not necessarily contain aromatic compounds itself. Using a reforming catalyst may also produce smaller amounts of other hydrocarbons.

[0267] Reforming catalysts can convert cycloalkanes into aromatic compounds. Naphtha feedstocks contain five- and six-membered cycloalkanes (cyclopentane, alkylcyclopentane, cyclohexane, and alkylcyclohexane). For example, six-membered cyclohexane can be directly dehydrogenated to produce aromatic compounds and hydrogen at a metal site. This is a very fast reaction, generating significant endotherm in the dominant reactor due to the typically high content of six-membered cycloalkanes in the naphtha feedstock. Under reforming conditions, the reaction is thermodynamically very favorable for aromatic compounds. To convert five-membered alkylcyclopentanes into aromatic compounds, they are first hydroisomerized to give a cyclohexane intermediate, which is then dehydrogenated to the aromatic compound. The conversion of alkylcyclopentane rings to aromatic compounds requires two reactions to occur in series, thus necessitating the acid and metal functions of the reforming catalyst. Alkanes are dehydrogenated at platinum sites to form alkenes, which can then be isomerized under the acid function of the catalyst to provide branched alkanes with higher octane numbers. Within a given carbon number range, the concentrations of normal-chain alkanes, branched alkanes, and their corresponding olefins tend to be at or near equilibrium at the reactor outlet. Although the content of olefins in reforming products is generally relatively low, they also contribute positively to the octane number compared to alkanes. Another function of reforming catalysts is to cyclize alkanes to cyclohexane and cyclopentane (dehydrogenation cyclization).

[0268] Reforming catalysts may include metal sites for dehydrogenation reactions and acid sites for isomerization and cyclization reactions. Reforming catalysts may contain platinum supported on an optionally modified alumina support, such as alumina chloride. Reforming catalysts may also contain additional metal components to modify acidic or metal sites. Reforming catalysts can be modified and used with fixed beds and are semi-regenerative, cyclic, or continuously regenerating reformers. The support for the reforming catalyst may be high-surface-area γ (γ) alumina with the molecular formula Al₂O₃·nH₂O, having a porous structure that forms a complex network of interconnected channels. Reforming catalysts are explained in detail in Egolf, B. et al., “The Honeywell UOP CCR ​​Platforming™ Process for BTX Production (CaseStudy)”, Industrial Aromatics Chemistry, Chapter 10, 2023, pp. 269–294, the entire contents of which are incorporated herein by reference.

[0269] Reforming catalysts may contain molecular sieves. Reforming catalysts may contain zeolites. Reforming catalysts may include any such catalysts known in the art for this purpose, such as those developed and marketed by UOP, including but not limited to UOP R-560, UOP R-364, and any combination thereof.

[0270] Reforming catalysts may contain platinum (Pt), palladium (Pd), or combinations thereof. Reforming catalysts may contain platinum and optionally modified supports. Reforming catalysts may contain platinum, optionally modified alumina supports, and additional metal components. Reforming catalysts may contain platinum, alumina chloride supports, and additional metal components. Reforming catalysts may contain a bimetallic formulation of Pt supported on alumina (Al₂O₃) with iridium or rhenium.

[0271] In some embodiments, the reforming catalysts of this disclosure (such as those described above) are active in converting carbon source gases (such as CO2 or naphtha) into aromatic compounds (such as BTX).

[0272] Catalysts for hydrocracking

[0273] The systems and methods disclosed herein can be used with any suitable hydrocracking catalyst, including those known in the art. In some embodiments, catalysts similar to those described in the hydrogenation and isomerization steps (above) are also used for hydrocracking.

[0274] Any suitable hydrocracking catalyst known in the art can be used in these processes. However, the specific examples described below are intended both to illustrate the use of such catalysts and to identify catalysts particularly suitable for use in conjunction with other features of the systems and methods disclosed herein.

[0275] In a further embodiment, the hydrocracking catalyst comprises a hydrocracking metal, such as Pd, Pt, Ni, Co, Co-W, Ni-W, and Ni-Mo, and a hydrocracking support. The hydrocracking support can be any suitable material that can be used as a catalyst support.

[0276] The hydrocracking support comprises one or more materials selected from the following: oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some embodiments, the hydrocracking support comprises γ-alumina. In some embodiments, the hydrocracking support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silicon carbide. In some embodiments, the hydrocracking support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite. In some embodiments, the hydrocracking support is alumina formed in situ as part of a reduction catalyst. In some embodiments, the hydrocracking support is selected from, but not limited to, MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, and TiO2. In some embodiments, the hydrocracking support is selected from MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silicon carbide, and TiO2.

[0277] In some embodiments, the hydrocracking support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0278] In some embodiments, the hydrocracking support is selected from SiAlO. x SO4-ZrO2, zirconium tungstate, tungstate-treated titanium dioxide, and anatase (SiO2-Al2O3, SiO2-TiO2). In further embodiments, the hydrocracking support is an aluminum-based material, such as alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite.

[0279] In some embodiments, the hydrocracking support is a zeolite, such as Y-type zeolite, β-zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), L-type zeolite (LTL), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, and combinations thereof. In further embodiments, the zeolite contains a modifier, such as Zn, Ga, Fe, or other transition metals. In still further embodiments, the modifier is present in the form of isomorphous substitution within the metal supported on the zeolite or within the zeolite framework.

[0280] In some embodiments, the hydrocracking support is modified with molybdenum, chlorine and / or sulfur.

[0281] In some embodiments, the hydrocracking metal comprises about 0.5 wt% to about 40 wt% of a hydrocracking catalyst. In a further embodiment, the hydrocracking metal comprises about 0.5 wt% of a hydrocracking catalyst. In yet another further embodiment, the hydrocracking metal comprises about 1 wt% of a hydrocracking catalyst. In still a further embodiment, the hydrocracking metal comprises about 10 wt% of a hydrocracking catalyst. In some embodiments, the hydrocracking metal comprises about 20 wt% of a hydrocracking catalyst. In a further embodiment, the hydrocracking metal comprises about 30 wt% of a hydrocracking catalyst. In yet another further embodiment, the hydrocracking metal comprises about 40 wt% of a hydrocracking catalyst.

[0282] Optional features of the present invention relating to the above-described hydrocracking catalyst may also constitute optional features related to catalysts for converting carbon sources into alkanes, catalysts for converting carbon source gas and reducing gas into straight-chain α-olefins, catalysts for converting carbon source and reducing gas into aromatic compounds, or catalysts for hydrogenation and isomerization, and vice versa.

[0283] Aromatic compound alkylation catalysts

[0284] The alkylation step can be carried out using any suitable catalyst. In some embodiments, the alkylation catalyst is a liquid acid, such as HF, SPA (solid phosphoric acid), Friedel-Cleffold alkylation catalyst (e.g., HF / AlCl3), tungsten, platinum, or zeolite. In further embodiments, the alkylation catalyst is a zeolite, such as acidic zeolite. In still further embodiments, the zeolite is selected from Y-type zeolites, β-zeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO-11, SAPO-5, SAPO-31, SAPO-41), L-type zeolites (LTL), mordenite, MWW structure type zeolites such as MCM-22, MCM-36, MCM-49, PSH-3 and MCM-56, DA-114, USY zeolite, and combinations thereof. In some embodiments, the zeolite is MCM-22, MCM-49, PSH-3, mordenite, Y-type zeolite, or β-zeolite.

[0285] Weight-based space velocity (WHV) is measured as the mass of reactant per unit time per unit mass of catalyst. The weight-based WHV range for alkylation catalysts is from about 0.1 g reactant / g catalyst per hour (0.1 h⁻¹) to about 50 h⁻¹, or from about 0.5 h⁻¹ to about 20 h⁻¹.

[0286] oligomerization catalyst

[0287] The oligomerization catalyst can be a heterogeneous acid catalyst, such as zeolite or molecular sieve. The oligomerization catalyst can be an amorphous or crystalline aluminosilicate molecular sieve. The oligomerization catalyst can be a zeolite. The oligomerization catalyst can be an aluminosilicate zeolite. The oligomerization catalyst can be selected from ZSM-5, ZSM-11, ZSM-22, θ-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, β-zeolite, octahedral zeolite, mordenite, SAPO-5, SAPO-11, and MWW structure-type zeolites, such as MCM-22, MCM-36, MCM-49, and MCM-56, and any combination thereof. The oligomerization catalyst can be ZSM-5, β-zeolite, MCM-22, MCM-49, mordenite, SAPO-5, or combinations thereof. The oligomerization catalyst can be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, MCM-49, PSH-3, and any combination thereof. The oligomerization catalyst can be ZSM-5.

[0288] Weight-based space velocity (WHV) is measured as the mass of reactant per unit time per unit mass of catalyst. The WHV range for oligomer catalysts is approximately 0.1 g reactant per 1 g catalyst per hour (0.1 h). -1 (approximately 50 h) -1 Approximately 0.5 hours -1 approximately 20 h -1 or about 0.5 h -1 approximately 5 hours -1 .

[0289] When the oligomerization reactor has two oligomerization sections, the top section contains the same or a different oligomerization catalyst as the bottom section. In one embodiment, the top section of the oligomerization reactor contains a first oligomerization catalyst, wherein light hydrocarbons supplied therein are dimerized, and then the dimerized hydrocarbon mixture is contacted with a second oligomerization catalyst in the bottom section of the oligomerization reactor for further dimerization to produce olefins and alkanes in the jet fuel range (i.e., C40, C50, C6 ... 10-16 The first oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-12, ZSM-57, ZSM-35, or combinations thereof. The first oligomerization catalyst may be selected from ZSM-11, ZSM-12, ZSM-57, or combinations thereof. The second oligomerization catalyst may be selected from zeolites of the MWW structure type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

[0290] When two oligomerization reactors are used sequentially, the first reactor may contain the same or different oligomerization catalyst as the one in the second reactor. The first reactor, i.e., the reactor upstream of the second reactor, may contain a first oligomerization catalyst selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-12, ZSM-57, ZSM-35, or combinations thereof. The first reactor may contain a first oligomerization catalyst selected from ZSM-11, ZSM-12, ZSM-57, or combinations thereof. The second reactor may contain a second oligomerization catalyst selected from zeolites of the MWW structure type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combinations thereof.

[0291] When an oligoalkylation reactor is used in the systems and methods described herein, one or more alkylation catalysts and one or more oligomeric catalysts may be stacked, mixed, or otherwise combined within the oligoalkylation reactor. One or more alkylation catalysts and one or more oligomeric catalysts may be mixed and layered within the reactor, optionally with an intermediate quencher. When using an oligoalkylation reactor with two separate sections, the top section contains an oligomeric catalyst, and the bottom section contains an alkylation catalyst, as well as an oligomeric catalyst that may be the same as or different from the oligomeric catalyst in the top section. In one embodiment, the top section of the oligoalkylation reactor contains a first oligomeric catalyst, wherein light hydrocarbons supplied therein are dimerized, and then in the bottom section, the dimerized hydrocarbon mixture is contacted with a second oligomeric catalyst for further dimerization to produce olefins and alkanes in the jet fuel range (i.e., C14). 10-16 ), and the mixture of light aromatic products is contacted with an alkylation catalyst to produce alkylated aromatic compounds (e.g., C ), and 9-14 ).

[0292] In other embodiments, oligoalkylation catalysts may be used. These catalysts may be liquid acids, such as HF, SPA (solid phosphoric acid), Friedel-Cleffold alkylation catalysts (e.g., HF / AlCl3), amorphous heterogeneous acid catalysts, such as tungsten oxide / Zr, heterogeneous acid catalysts, such as zeolites or molecular sieves, and combinations thereof. In some embodiments, the oligoalkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve. In other embodiments, the oligoalkylation catalyst is selected from the group consisting of: ZSM-5, ZSM-11, ZSM-22, θ-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, zeolite β, octahedral zeolite, mordenite, SAPO-5, SAPO-11, MWW structure type zeolites, such as MCM-22, MCM-36, MCM-49, and MCM-56, and any combination thereof. In a further embodiment, the oligoalkylation catalyst is ZSM-5, β-zeolite, MCM-22, MCM-49, PSH-3, mordenite, SAPO-5, or any combination thereof.

[0293] Reducing gas, carbon source gas and their ratio

[0294] The systems and methods disclosed herein can be designed to utilize any combination of a suitable reducing gas and a suitable carbon source gas. In some embodiments, the carbon source gas and reducing gas can be provided separately to the necessary reaction vessel, or in some embodiments, they can be pre-mixed (e.g., in some embodiments, a first reducing gas feed and a first carbon source gas feed can refer to the same physical characteristics, and a second reducing gas feed and a second carbon source gas feed can also refer to the same physical characteristics) to provide a single feed stream comprising both the carbon source gas and the reducing gas, the single feed stream being coupled to a suitable reactor.

[0295] In addition, a single gas feed comprising a first reducing gas feed, a first carbon source gas feed, a second reducing gas feed, and a second carbon source gas feed can be premixed to provide a single feed stream comprising both carbon source gas and reducing gas, the single feed stream being connected to both the aromatic reactor and the reduction reactor.

[0296] In some embodiments, the single gas feed may comprise CO2, H2, CO, C2, C3, CH4, and any combination thereof. The feed stream may contain about 10% to about 95% H2 / CO2, and about 0% to about 65% each of CO, C2, C3, and CH4. The source of CO, C2, C3, and / or CH4 may be from the recirculated stream or may be introduced into the fresh feed stream.

[0297] In some embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and the fourth reducing gas are independently selected from H2, hydrocarbons, synthesis gases (CO / H2), or gases that are or are derived from flare gas, exhaust gas, or natural gas.

[0298] In some embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is H2. In further embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is a synthesis gas. In still further embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In still further embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is or is derived from flare gas, exhaust gas, or natural gas. In some embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is CH4.

[0299] In some embodiments, the first carbon source gas and / or the second carbon source gas is CO2. In further embodiments, the first carbon source gas and / or the second carbon source gas contains CO2. In still further embodiments, the first carbon source gas and / or the second carbon source gas is CO. In still further embodiments, the first carbon source gas and / or the second carbon source gas contains CO.

[0300] As those skilled in the art will understand, the flow rate of the carbon source gas and / or reducing gas or various product mixtures through the alkane and / or aromatic reactor (or other parts of the disclosed systems and methods) can be adjusted as needed to obtain the desired product output characteristics.

[0301] Furthermore, as those skilled in the art will understand, the carbon source gas and reducing gas can be provided in any suitable ratio to obtain the desired product output characteristics. In some embodiments, the molar ratio of the first reducing gas to the first carbon source gas is about 10:1 to about 1:10. In further embodiments, the molar ratio of the first reducing gas to the first carbon source gas is about 5:1 to about 0.5:1. In still further embodiments, the molar ratio of the second reducing gas to the second carbon source gas is about 10:1 to about 1:10. In still further embodiments, the molar ratio of the second reducing gas to the second carbon source gas is about 5:1 to about 0.5:1.

[0302] definition

[0303] Unless otherwise defined herein, the scientific and technical terms used in this application shall have the meanings commonly understood by one of ordinary skill in the art. Generally, the nomenclature and techniques used in conjunction with those described herein in the fields of chemistry, cell and tissue culture, molecular biology, cell and cancer biology, neurobiology, neurochemistry, virology, immunology, microbiology, pharmacology, genetics, and protein and nucleic acid chemistry are those well-known and commonly used in the art.

[0304] Unless otherwise stated, the methods and techniques disclosed herein are generally performed according to conventional methods known in the art and as described in the various general and more specific references cited and discussed throughout this specification. See, for example, “Principles of Neural Science”, McGraw-Hill Medical, New York, NY (2000); Motulsky, “Intuitive Biostatistics”, Oxford University Press, Inc. (1995); Lodish et al., “Molecular Cell Biology, 4th Edition”, WH Freeman & Co., New York (2000); Griffiths et al., “Introduction to Genetic Analysis, 7th Edition”, WH Freeman & Co., NY (1999); and Gilbert et al., “Developmental Biology, 6th Edition”, Sinauer Associates, Inc., Sunderland, MA (2000).

[0305] Unless otherwise defined herein, chemical terms used herein are used in accordance with their conventional usage in the art, as illustrated below: “The McGraw-Hill Dictionary of Chemical Terms”, Parker S., editor, McGraw-Hill, San Francisco, CA (1985).

[0306] All the foregoing references in this application, as well as any other publications, patents, and published patent applications, are specifically incorporated herein by reference. In the event of any conflict, this specification (including its specific definitions) shall prevail.

[0307] As used herein, the terms “logarithm of solubility,” “LogS,” or “logS” are used in the art to quantify the water solubility of a compound. The water solubility of a compound significantly affects its absorption and distribution characteristics. Low solubility is generally accompanied by poor absorption. The LogS value is the unit stripping logarithm (base 10) of solubility measured in moles per liter.

[0308] As used herein, the term "monocyclic aromatic compound" refers to a compound containing only one aromatic ring, which may be substituted or unsubstituted (e.g., alkylbenzene) and may optionally be fused with a non-aromatic ring (e.g., tetrahydronaphthalene and dihydroindene).

[0309] As used herein, the term "polycyclic aromatic compound" refers to a compound comprising at least two aromatic rings, which may be fused (e.g., two distinct rings sharing two adjacent ring atoms). As a non-limiting example, the term "polycyclic aromatic compound" may be used to refer to a group of compounds comprising naphthalene and / or naphthalene derivatives.

[0310] As used herein, the term “petroleum-derived” refers to compounds and compositions extracted from petroleum feedstocks through physical and chemical processes, but excludes compounds and compositions whose carbon is derived from carbon dioxide or carbon monoxide, even if the carbon dioxide or carbon monoxide is produced from petroleum feedstocks (e.g., by burning petroleum).

[0311] When the amount of impurities is specified as "about 0", those skilled in the art will understand that, based on the relevant detection methods used, such measurements are accurate to a certain number of significant figures.

[0312] As used herein, certain components, fractions, and feeds are defined based on the number of carbons (e.g., C) in the components, fractions, feeds, etc. X-Y These descriptions are used to describe the possible (non-limiting) number of carbons in the hydrocarbons present in the component, but do not require the presence of every and every number of carbons within that range. For example, a description containing C 9-15 The hydrocarbon feed must contain at least one component that falls within the listed carbon number range.

[0313] As used herein, the term "oligomery" and its grammatical variations will be understood by those skilled in the art to refer to processes involving dimerization, trimerization, tetramerization, pentamerization, hexamerization, heptomerization, octamerization, nonamerization, decamerization, higher-order oligomerization, and combinations thereof. The degree of oligomerization in a particular reaction will determine the composition of the product stream and depends on various aspects of the reaction stream and the reaction conditions.

[0314] As used herein, the term "selectivity" and its grammatical variations refer to how selective a particular process or catalyst is for the production of a particular product. The term refers to an exemplary value of selectivity observed in a reaction carried out with suitable reagents under conditions chosen by a person skilled in the art to maximize or minimize the yield of a given product of interest. A selectivity value may refer to the proportion of the product of interest produced relative to other products (which may not be of interest), or the proportion of other products produced relative to the product of interest. Selectivity may be a function of the catalyst used in the process, and / or may be a function of process design or parameters (e.g., temperature, pressure, reagent concentration, GHSV, etc.), as will be understood by a person skilled in the art. Those skilled in the art are familiar with how to calculate the selectivity of a given product. However, in the cases where explicit calculations of selectivity are provided herein, the method of calculation is controlled.

[0315] Example

[0316] The invention described herein in general will be more readily understood by referring to the following examples, which are included only for the purpose of illustrating certain aspects and embodiments of the invention and are not intended to limit the invention.

[0317] Example 1: A system for producing aviation fuel

[0318] According to Figure 1 The flowchart in the diagram illustrates the system construction. When CO2 and H2 are supplied to the system, CO2 is converted into SAF (C 10-16 The carbon selectivity (of the mixture of alkanes and aromatic compounds) was calculated to be 67 wt%. Table 1 shows the calculated molar flow rates for each of the reactions and molecular transformations in the system.

[0319] Table 1

[0320]

[0321] Example 2: A system for producing alkane kerosene

[0322] According to Figure 3 The flowchart in the system describes the process of constructing a system. When CO2 and H2 are supplied to the system, the CO2 is converted into alkane kerosene (C2O3). 10-16 The carbon selectivity of the mixture of alkanes was calculated to be approximately 70 wt%. Table 2 shows the calculated molar flow rates for each of the reactions and molecular transformations in the system.

[0323] Table 2

[0324]

[0325] Example 3: Preparation of Fe / Zn-Na reduction catalyst.

[0326] Solutions of Fe and Zn metals were prepared using metal nitrates as precursors. A 0.5 M alkaline solution containing 2.4 molar equivalents of sodium carbonate relative to the metal nitrate was prepared. Sufficient water was added to a 2 L round-bottom flask to submerge the stirrer, and the flask was heated to 343 K while continuously stirring. The metal solution and alkaline solution were transferred to the round-bottom flask via a peristaltic pump, added in parallel at the target flow rate, ensuring that the metal solution and half of the alkaline solution were completely added within approximately 1 hour. The temperature was then raised to 353 K, and the mixture was aged for 1 hour. After one hour, the mixture was cooled to room temperature and then reheated to 343 K. The remaining alkaline solution was added within one hour, and the resulting slurry was aged again at 353 K for one hour.

[0327] The precipitate was vacuum filtered using a 0.25 μm microfilter. The product was then washed three times and mixed with approximately 300 mL of water, and filtered at each step to remove excess sodium to below 0.1%. The resulting precipitate was dried at 393 K for 4 hours, then ground into a fine powder and calcined at 623 K for 6 hours. The resulting catalyst was FeZn containing 0.5% Na. The ratio of iron to zinc components can be adjusted as readily understood by those skilled in the art. For example, catalysts with the following Fe:Zn ratios of 1:1, 2:1, 3:1, 4:1, 6:1 and 0.5 wt% Na have been synthesized according to the above method.

[0328] Example 4 Evaluation of catalysts for CO2 hydrogenation.

[0329] The catalyst was prepared using the method described in Example 3, FeZn, where the molar ratio of iron to zinc was approximately 6:1, but different metal promoters were used, namely Na, Rh, or Cs. The catalyst was granulated to a size of 40 to 60 mesh and pretreated with H2 at 623 K, 150 PSIG, and GHSV 1200 for 5 hours. It was then adjusted with syngas (H2 / CO = 2) at GHSV 600 and 623 K. The CO2 hydrogenation of the catalyst was then tested to produce a product containing C. 10 -C 16 A target hydrocarbon product mixture of alkanes and / or olefins. In a fixed-bed reactor at 623 K, GHSV 1500, and 450 PSIG, using feed gases H2 = 72 mol%, CO2 = 24 mol%, and N2 = 4 mol% as internal standards, the CO2 to C conversion rate was measured for each different catalyst. 10 -C 16 The case of alkanes and / or alkenes.

[0330] Table 3: Product distribution of FeZn catalysts containing Group IA or IIA metals

[0331]

[0332] Methane yield is a factor in catalyst effectiveness because it is undesirable. Therefore, the lower the methane yield (SC1), the better the catalyst. O / P is the ratio of olefins to alkanes produced by the reaction of the feedstock with the catalyst. In this case, compared to FeZnRh and FeZnCs catalysts, the FeZnNa catalyst provides a product stream with less methane, a higher olefin to alkanes ratio, and more C5+ products.

[0333] Although this embodiment uses a FeZnNa catalyst with a molar ratio of approximately 6Fe:1Zn, other experiments have shown that adjusting the molar ratio of iron to zinc from 1:1 to approximately 7:1 does not significantly affect the product distribution.

[0334] After selecting FeZn-0.5%Na as the catalyst, the Fe:Zn molar ratio was adjusted to 2.25:1, and the partial pressure of the hydrogen feed was adjusted to determine the impact on methane production and O / P selectivity.

[0335] Table 4: Product distribution as H2 partial pressure decreases

[0336]

[0337] The results showed that reducing the H2 / CO2 ratio from 3 to 2 improved both the methane selectivity (SC1) and the O / P ratio. Furthermore, tests indicated no significant difference in product selectivity between 6Fe:1Zn and 2.25Fe:1Zn.

[0338] Example 5: Evaluation of catalysts for CO2 hydrogenation using olefin-rich and CH4-rich feedstocks

[0339] The catalyst prepared by the method in Example 3 involved granulating FeZnNa to a size of 40-60 mesh and pretreating it with H2 at 623 K, 150 PSIG, and GHSV 1200 for 5 hours. It was then adjusted with syngas (H2 / CO = 2) at GHSV 600 and 623 K. The catalyst's CO2 hydrogenation was then tested to produce a product containing C. 10 -C 16A target hydrocarbon product mixture of alkanes and / or olefins. In a fixed-bed reactor at 623 K, GHSV 1500, and 450 PSIG, using feed gas H2 = 47 mol%, CO2 = 23.8 mol%, CO = 3 mol%, CH4 = 15 mol%, C2H4 = 2.2 mol%, C2H6 = 2.4 mol%, C3H6 = 2.3 mol%, C3H8 = 0.3%, and N2 = 4 mol% as internal standards, the measured CO2 was converted to C... 10 -C 16 Alkanes and / or alkenes. Expected C 5+ The production of alkanes and / or olefins will increase, while the production of methane will decrease.

[0340] Table 5: Expected Product Distribution of Mixed Hydrocarbon Feed

[0341]

[0342] Example 6: Extrudate Synthesis Method - Sodium Aluminate Binder

[0343] Using a nutri-bullet, combine 80g of powdered catalyst (FeZnNa) from Example 3, 20g of sodium aluminate, and 1g of STEROTEX. ® Mix to form a well-mixed dry powder. Nitric acid is added dropwise to 15.7951 g of deionized water to form solution A. Solution A is added dropwise to the powder under constant stirring rate. An additional 10.2 g of deionized water is added to the slurry to obtain an extrudable dough. The prepared dough is extruded at 45 Hz into extrudates with a diameter of 1.6 mm. The first batch of extrudates is discarded. Successful extrudates are collected separately. The extrudates are dried at 120 °C for 2 hours and then calcined at 350 °C for 4 hours to prepare the shaped catalyst.

[0344] Example 7: Extrusion synthesis method - Sodium silicate binder

[0345] Using a nutri-bullet, combine 80g of powdered catalyst (FeZnNa) from Example 3, 20g of sodium silicate, and 1g of STEROTEX. ® Mix to form a well-mixed dry powder. Nitric acid is added dropwise to 16.0213 g of deionized water to form solution A. Solution A is added dropwise to the powder at a constant stirring rate. An additional 9.3138 g of deionized water is added to the slurry to obtain an extrudable dough. The prepared dough is extruded at 45 Hz into extrudates with a diameter of 1.6 mm. The first batch of extrudates is discarded. Successful extrudates are collected separately. The extrudates are dried at 120 °C for 2 h and calcined at 350 °C for 4 h to prepare the shaped catalyst.

[0346] Example 8: Detailed Methods for Extrusion Synthesis - Potassium Silicate Binder

[0347] Using a nutri-bullet, combine 80g of powdered catalyst (FeZnNa) from Example 3, 20g of potassium silicate, and 1g of STEROTEX. ® Mix to form a well-mixed dry powder. Nitric acid is added dropwise to 30.3788 g of deionized water to form solution A. Solution A is added dropwise to the powder under constant stirring rate. An additional 10.2 g of deionized water is added to the slurry to obtain an extrudable dough. The prepared dough is extruded at 45 Hz into extrudates with a diameter of 1.6 mm. The first batch of extrudates is discarded. Successful extrudates are collected separately. The extrudates are dried at 120 °C for 2 hours and then calcined at 350 °C for 4 hours to prepare the shaped catalyst.

[0348] Example 9 Catalyst evaluation for CO2 hydrogenation

[0349] Powdered catalyst samples were prepared according to the procedure described in Example 3, resulting in a final composition with a molar ratio of Fe:Zn = 2:1 and 0.61 wt% Na. The powdered catalyst was separated and completed according to the procedure in Example 2, the difference being the incorporation of different binders to prepare the extrudates. Sample 2 was prepared using undoped alumina binder. Sample 3 was prepared using Na-doped alumina binder. Sample 4 was prepared using K-doped alumina binder. Sample 5 was prepared using undoped silica binder (LUDOX). ® Sample 6 was made using undoped silica binder (Hi-Sil). Sample 7 was made using Na-doped silica binder. Sample 8 was made using K-doped silica binder.

[0350] Once a steady state is reached, the effluent or liquid product from the conversion reaction is collected. The steady state can be measured by run time (TOS), or it can be determined by collecting samples approximately every 24 hours and testing the metal concentration in the samples. In a typical experiment, liquid products (hydrocarbons and aqueous phase) are collected every 24 hours and trace amounts of Fe, Zn, and Na are analyzed. In this example, after 200 hours of TOS, the effluent is collected and separated into aqueous and oil (hydrocarbon) products. The oil product is dissolved in aqua regia and then analyzed using ICP-MS. Separately, a sample of the aqueous product is injected into the instrument, where plasma ionizes the sample to provide a mass spectrometry reading. The metal concentration in the MS data is analyzed, and the amount calculated for each sample is added to the total concentration. The total concentration of metals in the aqueous and oil phases is added and reported as the total metal leaching in Table 6.

[0351] Table 6: Examples of the influence of binders on the performance of active metal catalysts

[0352]

[0353] The results were compared between shaped catalyst samples with different binder compositions. The performance of sample 2, with no binder, was compared with that of sample 3, with a sodium aluminate binder. The methane selectivity and C2O2 were compared after binder doping. 5+ The selectivity for hydrocarbons was significantly improved. Specifically, between samples 2 and 3, SC1 decreased by 37.5%, and SC... 5+ It increased by 61%.

[0354] The performance of samples 4 and 5 with undoped binders was compared with that of samples 6 and 7 with Na silicate and K silicate binders. After doping with binders, methane selectivity and C... 5+ Hydrocarbon selectivity was significantly improved. Specifically, between undoped sample 4 and doped samples 6 and 7, SC1 decreased by 49%, and SC... 5+ These increased by 36% and 38% respectively. In other words, between undoped sample 5 and doped samples 6 and 7, SC1 decreased by 53% and 52% respectively, while SC... 5+ They increased by 70% and 72% respectively.

[0355] Example 10: Leaching rates of different metals during operation time

[0356] Leaching rates were tested after different run times for the final composition from Example 3 with a molar ratio of Fe:Zn = 2:1 and 0.61 wt% Na, the powdered catalyst, and the shaped catalyst extrudate from Example 3. Metal leaching of the catalysts was analyzed using ICP-MS. Liquid products (hydrocarbon / oil phase and aqueous phase) were collected at different time intervals, separated into oil and water fractions, and trace amounts of Fe, Zn, and Na were analyzed. For the shaped catalyst, the effluent was separated into aqueous and oil fractions, and metal leaching was analyzed only for the water fraction, as the reaction had reached a steady state and the metal content in the oil fraction would be less than 1 ppm. Table 7 shows the metal leaching rates for the powdered catalyst, and Table 8 shows the metal leaching rates for the shaped catalyst. The introduction of a binder indicated a decrease in the metal leaching rate compared to similar run times.

[0357] Table 7: FeZn = 2 molar ratio, 1% wt Na powder catalyst

[0358]

[0359] Table 8: FeZn = 2 molar ratio, 1% wt Na and sodium aluminate binder extruder

[0360]

[0361] By incorporating via reference

[0362] All publications and patents mentioned herein are hereby incorporated in their entirety by reference as if each individual publication or patent were specifically and individually indicated by reference. In the event of conflict, all definitions contained herein shall prevail.

[0363] equivalent

[0364] While specific embodiments of the invention have been discussed, the foregoing description is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon reading this specification and the following claims. The full scope of the invention should be determined by reference to the full scope of the claims and their equivalents, the specification, and these variations.

Claims

1. A method for preparing aviation fuel, comprising: The first reducing gas and the first carbon source gas are contacted with the reduction catalyst to provide: Mixture of light hydrocarbon products; as well as A target hydrocarbon product mixture comprising a mixture of heavy hydrocarbon products and a mixture of medium hydrocarbon products; and The light hydrocarbon product mixture is contacted with an oligomerizing catalyst to provide an oligomerizing product mixture; The target hydrocarbon product mixture and the oligomer mixture are hydrogenated to provide a hydrogenated alkane product mixture comprising a light alkane product mixture, a medium alkane product and a target alkane product mixture; The medium-chain alkane product mixture is contacted with a reforming catalyst to provide a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture; and The target aromatic product mixture is combined with the target alkane product mixture to produce aviation fuel.

2. The method of claim 1, further comprising separating a recycle stream from the light hydrocarbon product mixture.

3. The method of claim 2, wherein the recirculation stream comprises one or more C 1-3 Hydrocarbons, CO2, CO and / or H2.

4. The method of claim 3, further comprising: The recirculated stream is combined with the first reducing gas and / or the carbon source gas before contacting the reducing catalyst.

5. The method according to any one of the preceding claims, wherein the light hydrocarbon product mixture comprises one or more C... 1-5 Alkanes and / or alkenes; The mixture of medium-quality hydrocarbon products contains one or more C444 compounds. 6-9 Alkanes and / or alkenes; and The heavy hydrocarbon product mixture contains one or more C 8-16 Alkanes and / or alkenes.

6. The method according to any one of the preceding claims, wherein the light alkane product mixture comprises one or more C... 1-5 Alkanes, The mixture of medium-strength alkane products contains one or more C44 groups. 6-9 Alkanes, and The target chain alkane product mixture contains one or more C 10-16 Alkanes.

7. The method according to any one of the preceding claims, further comprising: Separating the light alkane product mixture from the hydrogenated alkane product mixture, and The mixture of light alkane products is hydrogenated.

8. The method of claim 7, further comprising contacting the light alkane product mixture with a fourth reducing gas prior to hydrogenation.

9. The method according to any one of the preceding claims, further comprising contacting the light aromatic product mixture with the oligomerizing catalyst to provide the oligomerizing product mixture.

10. The method according to any one of the preceding claims, wherein contacting the light hydrocarbon product mixture with the oligomerizing catalyst comprises two steps: One or more C atoms in the mixture of light hydrocarbon products 2-5 Dimerization of alkanes and / or olefins to prepare one or more C 4-10 Alkanes and / or alkenes; Then make one or more C 4-10 Dimerization of alkanes and / or olefins to prepare C 10-20 Alkanes and / or alkenes.

11. The method according to any one of the preceding claims, wherein the step of contacting the light hydrocarbon product mixture and optionally the light aromatic product mixture with the oligomerization catalyst further comprises: The mixture of light hydrocarbon products and optionally the mixture of light aromatic products are contacted with the alkylation catalyst before, after, or simultaneously with the oligomerization catalyst.

12. The method according to any one of the preceding claims, wherein the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst further comprises applying an intermediate quenching agent.

13. The method of claim 12, wherein the intermediate quenching agent is part of the light aromatic product mixture and / or the light hydrocarbon product mixture.

14. The method according to any one of the preceding claims, wherein the contact between the first reducing gas and the first carbon source gas and the reducing catalyst occurs at an alkane temperature of about 100°C to about 600°C.

15. The method according to any one of the preceding claims, wherein the contact between the first reducing gas and the first carbon source gas and the reducing catalyst occurs at an alkane pressure of about 50 psi to about 4000 psi.

16. The method according to any one of the preceding claims, wherein the reforming catalyst comprises platinum, palladium, or a combination thereof.

17. The method of claim 16, wherein the reforming catalyst further comprises optionally modified alumina support or zeolite.

18. The method according to any one of the preceding claims, wherein the contact between the medium-quality alkane product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the reforming catalyst occurs at an aromatic temperature of about 200°C to about 650°C.

19. The method according to any one of the preceding claims, wherein the contact between the medium-quality alkane product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the reforming catalyst occurs at an aromatic pressure of about 20 psi to about 800 psi.

20. The method according to any one of the preceding claims, comprising passing the medium-chain alkane product mixture through an adsorbent bed prior to contact with the reforming catalyst.

21. The method according to any one of the preceding claims, wherein the hydrogenated alkane product mixture further comprises a heavy alkane product mixture, the heavy alkane product mixture comprising one or more C... 17-25 Alkanes.

22. The method of claim 21, further comprising: The third reducing gas and the heavy alkane product mixture are contacted with a hydrocracking catalyst to provide a product containing one or more C atoms. 1-18 A mixture of hydrocracking products of alkanes and / or olefins.

23. The method according to any one of the preceding claims, wherein the reduction catalyst comprises: iron; The first element optionally selected from copper, zinc, cobalt, or combinations thereof; and Optionally selected from one or more second elements of Group IA and IIA metals.

24. The method of claim 23, wherein the reduction catalyst comprises the first element, and wherein the first element is copper, zinc, or a combination thereof.

25. The method of claim 23, wherein the first element is zinc; and wherein the catalyst is free of copper or cobalt.

26. The method according to any one of claims 23 to 25, wherein the molar ratio of iron to the first element is about 1:1 to about 7:

1.

27. The method according to any one of claims 23 to 27, wherein the molar ratio of iron to the first element is about 2:1 to about 6:

1.

28. The method according to any one of claims 23 to 27, wherein the reduction catalyst comprises one or more Group IA or IIA metals; and the one or more Group IA or IIA metals are selected from magnesium, calcium, potassium, sodium, cesium, or combinations thereof.

29. The method of claim 28, wherein the one or more Group IA or IIA metals are present in an amount of about 0.2% to about 1.5% of the total weight of iron plus the first element.

30. The method of claim 28, wherein the reduction catalyst comprises K in a molar ratio of 0 to about 0.20 relative to iron, and / or Na in a molar ratio of 0 to about 0.60 relative to iron.

31. The method according to any one of claims 23 to 30, wherein the iron is in the form of iron oxide, and the iron oxide comprises magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof.

32. The method according to any one of claims 23 to 31, wherein the iron is in the form of iron oxide, and the iron oxide is magnetite (Fe3O4).

33. The method according to any one of claims 23 to 32, wherein the iron is in the form of iron oxide, and the iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3).

34. The method according to any one of claims 25 to 33, wherein the reduction catalyst has a methane selectivity of less than about 11 mol% of carbon.

35. The method of claim 34, wherein the reduction catalyst has a methane selectivity of less than about 10 mol% of carbon.

36. The method according to any one of the preceding claims, further comprising: The mixture of medium-quality alkane products is divided into a first stream and a second stream; The first stream of the medium-chain alkane product mixture is brought into contact with the reforming catalyst; as well as The second stream of the medium-quality alkane product mixture is combined with the target hydrocarbon product mixture.

37. The method according to any one of the preceding claims, wherein the hydrogenated alkane product mixture further comprises an aromatic compound.

38. The method according to any one of the preceding claims, wherein the oligomerizing catalyst is a zeolite, optionally selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, PSH-3 and MCM-49.

39. The method according to any one of the preceding claims, wherein the oligomerizing catalyst is aluminosilicate zeolite.

40. The method according to any one of the preceding claims, wherein the contact between the light hydrocarbon product mixture and the oligomerization catalyst occurs at an oligomerization temperature of about 50°C to about 400°C.

41. The method according to any one of the preceding claims, wherein the contact between the light hydrocarbon product mixture and the oligomerization catalyst occurs at an oligomerization pressure of about 0 psi to about 2000 psi.

42. The method of claim 11, wherein the alkylation catalyst is an acid (e.g., HF or SPA), a Friedel-Cleffold alkylation catalyst (e.g., HF / AlCl3), tungsten, platinum, or zeolite.

43. The method of claim 42, wherein the alkylation catalyst is a zeolite, optionally selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, PSH-3 and MCM-49.

44. The method according to any one of the preceding claims, further comprising passing the light hydrocarbon product mixture and / or the light aromatic product mixture (if present) through an adsorbent bed prior to contact with the oligomerization catalyst.

45. The method according to any one of the preceding claims, further comprising capturing carbon source gas from the gas feed stream.

46. ​​The method according to any one of the preceding claims, wherein the first reducing gas, the second reducing gas, the third reducing gas (if present), and the fourth reducing gas (if present) are independently selected from H2, hydrocarbons, synthesis gases (CO / H2), or gases that are or are derived from flare gas, exhaust gas, or natural gas.

47. The method according to any one of claims 1 to 46, wherein the first reducing gas, the second reducing gas, the third reducing gas and the fourth reducing gas comprise hydrocarbons, such as CH4, ethane, propane or butane.

48. The method according to any one of claims 1 to 46, wherein the first reducing gas, the second reducing gas, the third reducing gas and the fourth reducing gas are derived from or originate from flare gas, waste gas or natural gas.

49. The method according to any one of the preceding claims, wherein the first carbon source gas and / or the second carbon source gas comprises CO2.

50. The method according to any one of claims 1 to 48, wherein the first carbon source gas and / or the second carbon source gas comprises CO.

51. The method according to any one of the preceding claims, wherein the molar ratio of the first reducing gas to the first carbon source gas is about 10:1 to about 1:

10.

52. The method according to any one of the preceding claims, wherein the molar ratio of the first reducing gas to the first carbon source gas is about 5:1 to about 0.5:

1.

53. The method according to any one of the preceding claims, wherein the molar ratio of the second reducing gas to the second carbon source gas is about 10:1 to about 1:

10.

54. The method according to any one of the preceding claims, wherein the molar ratio of the second reducing gas to the second carbon source gas is about 5:1 to about 0.5:

1.

55. A system for producing aviation fuel, comprising: First reducing gas feed; First carbon source gas feed; A reduction reactor comprising a reduction catalyst, the reduction reactor having a first reducing gas inlet, a first carbon source inlet, and a mixed hydrocarbon outlet; wherein the first reducing gas inlet is connected to a first reducing gas feed, and the first carbon source gas inlet is connected to a first carbon source gas feed; Optional second reducing gas feed; Optionally, a second carbon source gas can be fed; as well as A first separator having a mixed hydrocarbon inlet, a light hydrocarbon product outlet, and a target hydrocarbon outlet, wherein the mixed hydrocarbon inlet is connected to the mixed hydrocarbon outlet on the reduction reactor; An oligomerization reactor comprising an oligomerization catalyst, the oligomerization reactor having a light hydrocarbon product inlet and an oligomerization product outlet, wherein the light hydrocarbon product inlet is connected to the light hydrocarbon product outlet on the first separator; A hydrogenator having an oligomer inlet and a hydrogenated alkane product outlet, wherein the oligomer inlet is connected to the oligomer outlet on the oligomer reactor; A second separator having a hydrogenated alkane product inlet, a medium-quality alkane outlet, and a target alkane outlet, wherein the hydrogenated alkane product inlet is connected to the hydrogenated alkane product outlet on the hydrogenator. as well as An aromatic reactor comprising a reforming catalyst, the aromatic reactor having a medium-chain alkane inlet, a second reducing agent optionally serving as a feed inlet, a second carbon source gas feed inlet optionally serving as a carbon source gas feed inlet, and a mixed aromatic product outlet; wherein the medium-chain alkane inlet is coupled to the medium-chain alkane outlet on a second separator, the second reducing gas feed inlet (if present) is coupled to a second reducing gas feed, and the second carbon source gas feed inlet (if present) is coupled to a second carbon source gas feed.

56. The system of claim 55, wherein the second separator further comprises a light alkane outlet, wherein the light alkane outlet is coupled to the oligomer inlet on the hydrogenator.

57. The system of claim 55 or 56, further comprising a third separator having a mixed aromatic product inlet, a light aromatic product outlet and a target aromatic product outlet, wherein the mixed aromatic product inlet is coupled to the mixed aromatic product outlet on the aromatic reactor.

58. The system of claim 57, further comprising a mixer having a target alkane inlet connected to the target alkane outlet of the second separator, and a target aromatic product inlet connected to the target aromatic product outlet of the third separator.

59. The system of claim 57 or 58, wherein the oligomer reactor further comprises a light aromatic product inlet, wherein the light aromatic product inlet is coupled to the light aromatic product outlet on the third separator.

60. The system according to any one of claims 55 to 59, wherein the oligomerization reactor is an oligomerization alkylation reactor comprising the oligomerization catalyst and the alkylation catalyst.

61. The system of claim 60, wherein the alkylation catalyst and the oligomerization catalyst are mixed or stratified within the oligoalkylation reactor.

62. The system according to any one of claims 55 to 59, wherein the oligomer reactor comprises two sections, each section containing the oligomer catalyst, and wherein the oligomer reactor contains an intermediate quenching agent between the sections.

63. The system of claim 55, further comprising: A first adsorbent bed with a second medium-chain alkane inlet and a light hydrocarbon outlet; The second medium-chain alkane inlet is connected to the medium-chain alkane outlet on the second separator, and the light hydrocarbon outlet is connected to the mixed hydrocarbon inlet on the first separator.

64. The system of claim 63, wherein the first adsorbent bed further comprises: It is connected to the recirculation outlet of the first carbon source gas feed.

65. The system according to any one of claims 55 to 64, further comprising: An oligomeric alkylation reactor comprising at least one catalyst selected from the group consisting of: oligomeric alkylation catalysts, alkylation catalysts, said oligomeric catalysts, or combinations thereof. The oligoalkylation reactor is coupled to the oligomer outlet of the oligomer reactor and configured to receive the oligomer mixture from the oligomer reactor and provide a further dimerized oligomer mixture to the hydrogenator.

66. The system according to any one of claims 55 to 64, further comprising: A fourth separator having a target alkane inlet and a heavy alkane product outlet, wherein the target alkane inlet is connected to the target alkane outlet on the second separator.

67. The system of claim 66, further comprising: Third reducing gas feed; A hydrocracking reactor comprising a hydrocracking catalyst, the hydrocracking reactor having a third reducing gas inlet, a heavy alkane product inlet and / or a heavy hydrocarbon inlet, and a hydrocracking product outlet; wherein the third reducing gas inlet is connected to the third reducing gas feed, the heavy alkane product inlet (if present) is connected to the heavy alkane product outlet on the fourth separator, and the heavy hydrocarbon inlet (if present) is connected to the heavy hydrocarbon outlet on the first separator.

68. The system according to any one of claims 55 to 67, wherein the reduction reactor further includes a reducing gas outlet, wherein the reducing gas outlet is coupled to the first carbon source gas feed and / or the first reducing gas feed.

69. The system according to any one of claims 55 to 68, wherein the reforming catalyst comprises platinum, palladium, or a combination thereof.

70. The system of claim 69, wherein the reforming catalyst further comprises optionally modified alumina support or zeolite.

71. The system according to any one of claims 55 to 70, wherein the oligomerizing catalyst is a zeolite, optionally selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, PSH-3 and MCM-49.

72. The system according to any one of claims 55 to 71, wherein the oligomerizing catalyst is aluminosilicate zeolite.

73. The system according to claim 60 or 65, wherein the alkylation catalyst is an acid (e.g., HF or SPA), a Friedel-Cleffold alkylation catalyst (e.g., HF / AlCl3), tungsten, platinum, or zeolite.

74. The system of claim 73, wherein the alkylation catalyst is a zeolite, optionally selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, PSH-3 and MCM-49.

75. A method for manufacturing alkane kerosene for aviation fuel, comprising: The first reducing gas and the first carbon source gas are contacted with the reduction catalyst to provide: Mixture of light hydrocarbon products; Mixture of medium-quality hydrocarbon products; as well as Mixtures of heavy hydrocarbon products; and The light hydrocarbon product mixture and the medium hydrocarbon product mixture are contacted with an oligomerization catalyst in an oligomerization reactor to provide an oligomerization product mixture; The heavy hydrocarbon product mixture and the oligomer product mixture are combined to provide a combined product mixture; Separate the combined product mixture into groups containing one or more Cs. 10-16 Target olefin product mixtures and containing one or more C 17+ Mixtures of heavy olefin products of alkanes and / or alkenes; and The target olefin product mixture is hydrogenated to provide alkane kerosene.

76. The method of claim 75, further comprising separating the light hydrocarbon product mixture into a recycle stream and a stream containing one or more C... 3-4 A mixture of residual light hydrocarbon products from alkanes and / or alkenes.

77. The method of claim 76, wherein the recirculation stream comprises one or more C 1-2 Hydrocarbons, CO2, CO and / or H2.

78. The method according to any one of claims 75 to 77, wherein the light hydrocarbon product comprises one or more C... 1-4 Alkanes and / or alkenes; the intermediate hydrocarbon product comprises one or more C44 groups. 5-8 Alkanes and / or alkenes; and the heavy hydrocarbon product mixture contains one or more C444-carbon compounds. 9-16 Alkanes and / or alkenes.

79. The method according to any one of claims 75 to 78, wherein the step of contacting the light hydrocarbon product mixture with the oligomerizing catalyst comprises two steps: One or more C 2-4 Alkanes and / or olefins dimerize to C 4-8 Alkanes and / or alkenes; and C 4-8 Alkanes and / or olefins dimerize to C 10-16 Alkanes and / or alkenes.

80. The method according to any one of claims 75 to 79, wherein the step of contacting the medium hydrocarbon product mixture with the oligomerizing catalyst comprises adding one or more C... 4-8 Alkane and / or olefin dimerization C 10-16 Alkanes and / or alkenes.

81. The method of claim 80, wherein the oligomer reactor comprises two or more sections within the reactor, each section containing the oligomer catalyst.

82. The method of claim 81, further comprising applying an intermediate quenching agent to the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst.

83. The method of claim 82, wherein the mixture of medium-quality hydrocarbon products is supplied as an intermediate quenching agent between the two or more sections within the reactor.

84. The method according to any one of claims 75 to 83, wherein the alkane kerosene comprises: C from approximately 35 wt% to approximately 55 wt% 10-16 n-chain alkanes, C from approximately 35 wt% to approximately 55 wt% 10-16 Isoalkanes, Less than about 5 wt% of cycloalkanes, and Aromatic compounds less than about 1 wt%.

85. The method of claim 84, wherein the alkane kerosene comprises: Approximately 40 wt% to approximately 50 wt% C 10-16 n-chain alkanes, and Approximately 40 wt% to approximately 50 wt% C 10-16 Isoalkanes.

86. The method according to any one of claims 75 to 85, wherein the conversion of the carbon gas source to alkane kerosene has a carbon selectivity of more than about 64 wt%.

87. A system for producing alkane kerosene for aviation fuel, comprising: First reducing gas feed; First carbon source gas feed; A reduction reactor comprising a reduction catalyst, the reduction reactor having a first reducing gas inlet, a first carbon source inlet, and a mixed hydrocarbon outlet; wherein the first reducing gas inlet is connected to a first reducing gas feed, and the first carbon source gas inlet is connected to a first carbon source gas feed; A first separator is connected to the reduction reactor and has a mixed hydrocarbon inlet connected to the mixed hydrocarbon outlet of the reduction reactor, wherein the first separator is configured to separate a light hydrocarbon product mixture from a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture. A second separator is connected to the first separator, wherein the second separator is configured to separate the heavy hydrocarbon product mixture from the medium hydrocarbon product mixture; An oligomerization reactor, comprising an oligomerization catalyst, having an oligomerization product outlet. The oligomer reactor is connected to the first separator and the second separator, and The oligomerization reactor is configured to receive at least a portion of the light hydrocarbon product mixture from the first separator, and the oligomerization reactor is configured to receive the medium hydrocarbon product mixture from the second separator; as well as A third separator having an oligomer inlet connected to the oligomer outlet, wherein the third separator is configured to receive the heavy hydrocarbon product mixture from the second separator, and wherein the third separator is configured to receive a mixture containing one or more C... 10-16 Target olefin product mixtures containing one or more C 17+ Separation of heavy olefin product mixtures of alkanes and / or alkenes.

88. The system of claim 87, further comprising a hydrogenator coupled to the third separator, the hydrogenator being configured to receive the target olefin product mixture and convert it into alkane kerosene.

89. The system of claim 87 or 88, wherein the oligomer reactor comprises two sections, each section containing the oligomer catalyst; and wherein the oligomer reactor comprises an intermediate quenching agent located between the two sections.

90. The system of claim 87 or 88, wherein the oligomer reactor comprises two separate oligomer reactors connected in series.

91. The system according to any one of claims 87 to 90, wherein the oligomerizing catalyst is a zeolite, optionally selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, MCM-22, PSH-3 and MCM-49.

92. The system according to any one of claims 87 to 91, wherein the light hydrocarbon product comprises one or more C... 1-4 Alkanes and / or alkenes; the intermediate hydrocarbon product comprises one or more C44 groups. 5-8 Alkanes and / or alkenes; and the heavy hydrocarbon product mixture contains one or more C444-carbon compounds. 9-16 Alkanes and / or alkenes.

Images