Systems, methods, and catalysts for producing sustainable aviation fuels

Abstract

Provided herein are systems and methods for converting CO2 and a reducing gas, such as H2 or a hydrocarbon, into a mixture of alkanes and aromatics for use as aviation fuel using a reduction catalyst and an aromatic catalyst. The reduction catalyst and aromatic catalyst, and systems and methods using them, provide advantages over other methods in the art in terms of improved yield, catalyst stability, and lifetime.

Description

[0001] Cross-reference to related applications

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

[0003] With the increasing concentration of carbon dioxide in the atmosphere, it is advantageous to develop technologies to remove or mitigate carbon dioxide emissions. Therefore, developing transportation technologies that provide reduced CO2 emissions, such as electric vehicles, has become a priority. However, the development of electric aircraft, especially commercial electric aircraft, faces challenges 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 aromatics refined from crude oil. To produce a saline fuel oil (SAF) that can directly replace Jet-A, the SAF must match the current composition of crude oil-derived Jet-A. Current technologies for SAF production involve obtaining SAF from vegetable oils, animal fats, and waste oils. However, SAF produced by these methods primarily contains alkanes and lacks sufficient cycloalkanes and aromatics to directly replace crude oil-derived Jet-A. Therefore, a technology is needed to produce an SAF that can directly replace crude oil-derived Jet-A.

[0005] Furthermore, some methods for producing alkanes and aromatics from CO2 involve the 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, there is a need for methods for producing aromatics and alkanes from CO2 (e.g., to prepare insertable SAF compositions) that reduce these zeolite deactivation pathways. Summary of the Invention

[0006] This document discloses a method for producing aviation fuel. The method may include: (a) contacting a first reducing gas and a first carbon source gas with a reducing catalyst to obtain: a fuel containing one or more C... 5-9 A mixture of medium-hydrocarbon products of alkanes and / or alkenes; and containing one or more C44 hydrocarbons. 10-16 (a) a target hydrocarbon product mixture of alkanes and / or olefins; and (b) contacting the hydrocarbon product mixture with an aromatic catalyst to obtain a mixture containing one or more C4 ... 9-14The target aromatic product mixture. The step of contacting the intermediate product mixture with an aromatic catalyst may further include providing a second reducing gas and / or a second carbon source gas to obtain a mixture containing one or more C atoms. 9-14 A mixture of target aromatic products.

[0007] The method may further include: contacting the mixture of intermediate hydrocarbon products with the aromatic catalyst to further obtain a product containing one or more C atoms. 6-8 A mixture of light aromatic products; and / or contacting the light aromatic product mixture and said light aromatic product mixture with an alkylation catalyst to obtain a target alkyl aromatic product mixture containing one or more alkylated aromatics; and / or contacting the light aromatic product mixture with an oligomerization catalyst to obtain a product containing one or more C 10-16 A mixture of target oligomers of alkanes and / or olefins.

[0008] The method may further include: contacting the light hydrocarbon product mixture with the oligomerizing catalyst to further obtain a product containing one or more C atoms. 1-2 A mixture of light oligomers of hydrocarbons; and optionally, the carbon source gas is combined with the mixture of light oligomers before contact with the reduction catalyst.

[0009] 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 reducing catalyst; and (iv) an aromatics reactor containing an aromatics catalyst. The system may also include a second reducing gas feed and / or a second carbon source gas feed. The reduction reactor may have a first reducing gas feed inlet, a first carbon source gas feed inlet, a target hydrocarbon outlet, and a middle 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 aromatics reactor may have a middle hydrocarbon inlet, an optional second reducing gas feed inlet, an optional second carbon source gas feed inlet, and a target aromatics product outlet. The middle hydrocarbon inlet may be connected to the middle hydrocarbon outlet on the reduction reactor. 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.

[0010] The aromatics reactor may further include a light aromatics product outlet, thereby optionally further comprising an alkylation reactor containing an alkylation catalyst. The alkylation reactor may include a light hydrocarbon inlet, a light aromatics product inlet, and an alkyl aromatics product outlet. The light hydrocarbon inlet may be connected to a light hydrocarbon outlet on a reduction reactor, and the light aromatics product inlet may be connected to a light aromatics product outlet on an aromatics reactor. The system may further include an oligomerization reactor or an oligomerization-alkylation reactor containing an oligomerization catalyst. The oligomerization reactor or oligomerization-alkylation reactor may include a light hydrocarbon inlet and a target oligomer product outlet; wherein the light hydrocarbon inlet is connected to a light hydrocarbon outlet on a reduction reactor. The oligomerization reactor, alkylation reactor, and / or oligomerization-alkylation reactor may further include a medium oligomer product inlet, wherein the medium oligomer product inlet is connected to a medium oligomer product outlet on the oligomerization reactor and / or the oligomerization-alkylation reactor.

[0011] A reduction catalyst is also disclosed, comprising: iron; a first element selected from copper, zinc, cobalt, or combinations thereof; and one or more second elements selected from Group IA and Group IIA metals. The reduction catalyst exhibits selectivity for the conversion of CO2 to methane of less than about 11 mol% or less than about 10 mol%. The first element may be zinc, optionally with a molar ratio of iron to zinc of about 1:1 to about 7:1. One or more second elements may be magnesium, calcium, potassium, sodium, cesium, or combinations thereof. One or more second elements may be present in an amount of about 0.2% to about 1.5% of the total weight of iron plus the first element.

[0012] An aromatic catalyst comprising optionally modified zeolite is also disclosed. The zeolite may be selected from Y-type zeolite, β-zeolite, ZSM-type zeolite, SAPO-type zeolite, L-zeolite (LTL), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. The aromatic catalyst may have selectivity for aromatics exceeding about 50 mol% C, exceeding about 55 mol% C, or exceeding about 60 mol% C; and / or selectivity for methane less than about 8 mol% C, or less than about 5 mol% C. The zeolite may be ZSM-5, and / or have a silica-alumina ratio (SAR) of about 30 to about 400. The zeolite contains a modifier optionally selected from Ga, Fe, Mn, Zn, P, Pt, or combinations thereof, and / or present in an amount of about 0 wt% to about 10 wt% of the total aromatic catalyst. The aromatic catalyst is selective for C 9-14 Aromatic hydrocarbons can have a selectivity of about 5 mol% to about 20 mol%.

[0013] An oligomerization-alkylation catalyst is also disclosed for converting a mixture of light aromatic products into compounds containing one or more C atoms. 9-14 Aromatics and one or more C 10-16A mixture of target products of alkanes, wherein the oligomerization-alkylation catalyst comprises: a liquid acid; solid phosphoric acid (SPA); a Friedel-Crafts alkylation catalyst (e.g., HF / AlCl3); an amorphous heterogeneous acid catalyst; a heterogeneous acid catalyst, such as zeolite or molecular sieve; and combinations thereof. The oligomerization-alkylation catalyst may be an amorphous or crystalline aluminosilicate molecular sieve. Attached Figure Description

[0014] Figure 1 This is a process flow diagram of the system disclosed herein, in which an adsorbent bed is used to suppress the migration of metals from the reducing catalyst.

[0015] Figure 2 This is a process flow diagram of the system disclosed herein, wherein an adsorbent bed is used to suppress metal migration from a reducing catalyst, and wherein additional carbon source gas and reducing gas are fed into an aromatics reactor.

[0016] Figure 3 This is a process flow diagram of the system disclosed herein, in which aromatic alkylation and olefin oligomerization are carried out in separate reactors.

[0017] Figure 4 This is a process flow diagram of the system disclosed herein, in which aromatic alkylation and olefin oligomerization are carried out in separate reactors, wherein additional carbon source gas and reducing gas are fed into the aromatic reactor.

[0018] Figure 5 This is a process flow diagram of the system disclosed herein, in which aromatic alkylation and olefin oligomerization are carried out in the same reactor.

[0019] Figure 6 This is a process flow diagram of the system disclosed herein, in which aromatic alkylation and olefin oligomerization are carried out in the same reactor, wherein additional carbon source gas and reducing gas are fed into the aromatic reactor.

[0020] Figure 7 This is a process flow diagram of the system disclosed herein, which incorporates two downstream hydrogenation systems for converting olefins and aromatics.

[0021] Figure 8 This is a graph showing the stability and selectivity of the aromatic catalyst during an operating period of approximately 8 hours to approximately 50 hours. Detailed Implementation

[0022] Aviation fuels typically contain four classes of hydrocarbons: n-alkanes (straight-chain), isoalkanes (branched-chain), cycloalkanes, and aromatics. The most commonly used Jet A and Jet A-1 fuels are blended to have a composition that allows them to meet the specifications defined by ASTM International (formerly the American Society for Testing and Materials) standard D1655. The ASTM D1655 standard specification for aviation turbine fuels includes tests for the physical and chemical properties that Jet A or Jet A-1 used in aircraft must meet. The standard also includes concentration limits for acidic and sulfur-containing compounds, as well as minimum and maximum concentrations of aromatics, and refers to ASTM standard tests for those limits. Aromatics are necessary for compatibility with O-ring materials in existing turbine engines, but are lacking in the blending components of most synthetically produced aviation fuels.

[0023] Among aromatic hydrocarbons, monocyclic and bicyclic aromatic compounds (meaning compounds containing two fused aromatic rings) are essentially indistinguishable in their effectiveness in O-ring compatibility, and petroleum-derived jet fuels typically contain both. ASTM D1655 also fails to differentiate them. However, polycyclic aromatic hydrocarbons (meaning 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, n-butylbenzene produces approximately 62% naphthalene soot upon combustion. Therefore, it is advantageous to synthesize Jet A containing monocyclic aromatic hydrocarbons rather than polycyclic aromatic hydrocarbons.

[0024] In the process of synthesizing synthetic blending components for sustainable aviation fuels, Fischer-Tropsch (FT) synthesis is commonly used because it is a proven process that has been used since the early 20th century to convert syngas (a mixture of carbon monoxide and hydrogen) into alkanes. The product liquid from FT, Fischer-Tropsch Hydroprocessed Synthesized Paraffinic Kerosene (FT-SPK), is the subject of Annex A1 of ASTM D7566, the first approved annexe to a SAF synthetic blending component. This alkane kerosene primarily contains n-alkanes and isoalkanes, with virtually no cycloalkanes or aromatics. Therefore, FT-SPK must be blended with the corresponding conventional Jet A to achieve the cyclic compound concentration required to meet ASTM D1655 specifications. An additional annexe to ASTM D7566, using the ASTM D4054 method, has been approved for the formation of synthetic blending components for fully formulated Jet A.

[0025] In some respects, this disclosure describes a fully formulated Jet A synthesized from carbon dioxide. Fully formulated Jet A is ready for immediate use, meaning that its chemical and physical characteristics are nearly identical to those of conventional jet fuels, and it can be safely blended with conventional jet fuels to varying degrees, using the same supply infrastructure and without requiring adaptation to the aircraft or engine. As described herein, the production method involves assembling carbon dioxide into aromatic compounds. This bottom-up approach significantly reduces the accessibility of synthesizing larger molecules. Therefore, the synthetic Jet A disclosed herein contains fewer polycyclic aromatic hydrocarbons (PAHs) than Jet A produced from petroleum-derived components. In some embodiments, the synthetic Jet A of this disclosure contains less than about 1 wt% PAHs.

[0026] The compositions described herein also contain significantly less sulfur than comparable fossil fuels, less than 1 ppm in some embodiments. This is achieved through the thermochemical synthesis of jet fuels from CO2 and H2.

[0027] The characteristics of the fuels described in this article (low polycyclic aromatic hydrocarbons and sulfur content) are difficult or impossible to achieve with petroleum-derived fuels because those fuels, when prepared by conventional methods, ultimately retain a variety of characteristic compounds from the petroleum source, such as sulfurous substances and polycyclic aromatic hydrocarbons, which are either too costly or impossible to completely remove from the final fuel products.

[0028] This article also provides systems and methods for producing SAFs, which in some embodiments can directly replace Jet-A made from petroleum-derived components, CO2, and renewable electricity.

[0029] The above method can produce aviation fuel that can directly replace Jet-A derived from crude oil because the ratio of isoalkanes to n-alkanes and the ratio of aromatics to cycloalkanes can be controlled in the isomerization / hydrogenation reactor, and the ratio of alkane to aromatics can be adjusted by controlling the relative sizes of reactor 1 and reactor 2. Those skilled in the art will appreciate that the flexibility of this system design allows these ratios to be adjusted as needed for other applications. A particular advantage of the system and method of the present invention is that aromatics and alkanes can be combined prior to purification, thereby significantly reducing capital expenditure.

[0030] fuel composition

[0031] In some respects, this disclosure provides systems and methods for producing fuel compositions from carbon source gases (e.g., CO2) and reducing gases (e.g., H2). The 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 low total sulfur content because they (or their major components) are produced synthetically from CO2. As another example, the systems and methods disclosed herein for preparing aromatic components are highly favorable for the formation of monocyclic aromatic hydrocarbons (PAHs) and unfavorable for the formation of polycyclic aromatic hydrocarbons (PAHs). These compositional characteristics (e.g., low sulfur content and low PAH content) produced by the systems and methods described herein are advantageous compared to conventional (petroleum-derived) fuels.

[0032] In some respects, this document provides fuel compositions comprising: monocyclic aromatic hydrocarbons; cycloalkanes; n-alkanes; and isoalkanes. The composition may contain less than about 1 wt% of polycyclic aromatic hydrocarbons.

[0033] The fuel composition may contain less than about 5 wt% tetrahydronaphthalene and indane, or less than about 1 wt% tetrahydronaphthalene and indane. In some embodiments, the fuel composition contains 0 wt% to about 5 wt% tetrahydronaphthalene and indane, or 0 wt% to about 1 wt% tetrahydronaphthalene and indane. In some embodiments, the composition substantially does not contain tetrahydronaphthalene and indane.

[0034] The fuel composition may contain less than about 0.5 wt% of polycyclic aromatic hydrocarbons (PAHs). The fuel composition may contain about 0 wt% to about 0.5 wt% of PAHs, or about 0.1 wt% to about 1 wt% of PAHs. 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 PAHs. In some embodiments, the fuel composition is substantially free of PAHs, for example, as determined by GC-MS.

[0035] In some embodiments, substantially all aromatic compounds present in the fuel compositions of this disclosure are monocyclic aromatic hydrocarbons.

[0036] The fuel composition may contain about 5 wt% to about 25 wt% of monocyclic aromatic hydrocarbons. The fuel composition may contain about 8 wt% to about 15 wt% of monocyclic aromatic hydrocarbons. 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 monocyclic aromatic hydrocarbons. The fuel composition may contain about 14.5 wt% of monocyclic aromatic hydrocarbons.

[0037] 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.

[0038] The fuel composition may contain about 5 wt% to about 40 wt% of isoalkanes. The fuel composition may contain about 5 wt% to about 15 wt% of isoalkanes. The fuel composition may contain about 5 wt%, about 7 wt%, about 9 wt%, about 11 wt%, about 13 wt%, or about 15 wt% of isoalkanes. The fuel composition may contain about 8.8 wt% of isoalkanes.

[0039] The fuel composition may conform to ASTM D4054-Class 1 standards.

[0040] The fuel composition may have a total acidity of less than about 0.10 mg KOH / g. In some embodiments, the total acidity of the composition is about 0.05 mg KOH / g to about 0.10 mg KOH / g. In other embodiments, the total acidity of the composition is 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 total acidity of the composition is about 0.07 mg KOH / g.

[0041] In some embodiments, such as those measured by ASTM D2622, the composition contains less than about 0.3 wt% total sulfur. 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% thiols. In other embodiments, such as those measured by ASTM D3227, the composition contains about 0 wt% thiols.

[0042] The fuel composition may have a flash point of at least about 38°C. In some embodiments, the flash point of the composition is from about 38°C to about 370°C, or from about 38°C to about 100°C. In other embodiments, the composition has a flash point from about 38°C to about 50°C. In still other embodiments, the flash point of the composition is 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.

[0043] The fuel composition can have approximately 775 kg / m³ at 15°C. 3 Approximately 840 kg / m 3 The density. In some embodiments, the composition has a density of about 775 kg / m³ at 15°C. 3 Approximately 785 kg / m 3 The density. In some embodiments, the composition has approximately 775 kg / m³ at 15°C. 3 Approximately 778 kg / m 3 Approximately 780 kg / m 3 Approximately 782 kg / m 3 Or approximately 785 kg / m 3 The density. In other embodiments, the composition has approximately 780 kg / m³ at 15°C. 3 The density.

[0044] The fuel composition may have a freezing point less than about -40°C. In some embodiments, the composition has a freezing point from about -70°C to about -40°C. In other embodiments, the freezing point of the composition is 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 freezing point of the composition is about -51°C.

[0045] The fuel composition may have a viscosity below about 8.0 cSt at -20°C. In some embodiments, the viscosity of the composition at -40°C is less than about 12 mm. 2 / s. In some embodiments, the viscosity of the composition at -20°C is about 3.2 mm. 2 / s.

[0046] 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 other 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.

[0047] 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 other embodiments, the composition has a smoke point of about 25 mm to about 45 mm. In still other 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.

[0048] The fuel composition may have a filter pressure drop of less than about 25 mm Hg. In some embodiments, the composition produces a filter pressure drop of 0 mm Hg to about 25 mm Hg. In some embodiments, the composition produces a filter pressure drop of about 0 mm Hg.

[0049] The fuel composition may have a tube deposition grade of less than about 3, with substantially no peacock-colored or aberrantly colored deposits. In some embodiments, the composition has a tube deposition grade of 1 VTR color code.

[0050] 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.

[0051] The fuel composition may conform to ASTM D1655.

[0052] In some embodiments, the monocyclic aromatic hydrocarbons are not petroleum-derived. In some embodiments, the monocyclic aromatic hydrocarbons are derived from CO2. In some embodiments, the monocyclic aromatic hydrocarbons, cycloalkanes, n-alkanes, and isoalkanes are not petroleum-derived. In some embodiments, the monocyclic aromatic hydrocarbons, cycloalkanes, n-alkanes, and isoalkanes are derived from CO2.

[0053] The fuel composition may further comprise at least one fuel additive. The fuel additive can be any such additive known to be used in the art. For example, fuel additives may be incorporated to impart certain desired characteristics or properties to the fuel.

[0054] Aviation fuel production system

[0055] 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. As will be understood, the term “interconnected” as used herein describes components that are operatively linked to each other, but does not exclude the presence of intermediate components between those interconnected components. Additionally, as will be understood, various system components are described as “having” certain features. 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 an alkane product outlet

[27] . This description does not exclude and specifically considers 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 suitably combined into a single inlet or outlet. Those skilled in the art will recognize that once the key features and operating conditions of systems such as those described herein are understood, detailed design and operation of such systems involve many choices, such as specific reagent flow rates, separation steps, etc. While this disclosure provides several specific embodiments, any suitable combination of these design choices may be made.

[0056] Furthermore, the various systems and methods disclosed herein sometimes refer to having a specific carbon number (e.g., C10). X-Y The fractions are those containing carbons. 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 number. Separators capable of producing these fractions are well known in the art and can be adjusted as needed to obtain a suitable product mixture as disclosed herein, or as otherwise required by the operator. Certain components of the system are designated by numbers in parentheses (i.e.,

[10] ).

[0057] This document 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 reducing catalyst; and an aromatics reactor containing an aromatics catalyst.

[0058] The reduction reactor may have a first reducing gas inlet, a first carbon source inlet, a target hydrocarbon outlet, and a middle 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.

[0059] The aromatics reactor may include a middle hydrocarbon inlet, an optional second reducing gas feed inlet, an optional second carbon source gas feed inlet, and a target aromatics product outlet. The middle hydrocarbon inlet may be connected to the middle hydrocarbon outlet on a reduction reactor, the second reducing gas feed inlet may be connected to a second reducing gas feed if present, and the second carbon source gas feed inlet may be connected to a second carbon source gas feed if present. The aromatics reactor may further include a light aromatics product outlet.

[0060] The system may also include a second reducing gas feed. The system may also include a second carbon source gas feed.

[0061] The system disclosed herein may include a first adsorbent bed having a middle hydrocarbon inlet and a middle hydrocarbon outlet. The middle hydrocarbon inlet may be connected to a middle hydrocarbon outlet on a reduction reactor, and the middle hydrocarbon outlet may be connected to a middle hydrocarbon inlet on an aromatics reactor.

[0062] The system disclosed herein may include an alkylation reactor containing an alkylation catalyst. The alkylation reactor may include a light hydrocarbon inlet, a light aromatic hydrocarbon product inlet, and an alkyl aromatic hydrocarbon product outlet. The light hydrocarbon inlet may be connected to a light hydrocarbon outlet on a reduction reactor, and the light aromatic hydrocarbon product inlet may be connected to a light aromatic hydrocarbon product outlet on an aromatic hydrocarbon reactor.

[0063] The system disclosed herein may include an oligomerization reactor containing an oligomerization catalyst. The oligomerization reactor may have a light hydrocarbon inlet and a target oligomer product outlet. The light hydrocarbon inlet may be coupled to a light hydrocarbon outlet on a reduction reactor.

[0064] The system disclosed herein may include an oligomerization-alkylation reactor comprising an oligomerization catalyst and an alkylation catalyst. The oligomerization-alkylation reactor may have a light hydrocarbon inlet, a light aromatic product inlet, and a mixed target product outlet. The light hydrocarbon inlet may be connected to a light hydrocarbon outlet on a reduction reactor, and the light aromatic product inlet may be connected to a light aromatic product outlet on an aromatics reactor.

[0065] The system disclosed herein may include a second adsorbent bed having a light hydrocarbon inlet and / or a light aromatic hydrocarbon product inlet and a light hydrocarbon outlet and / or a light aromatic hydrocarbon product outlet. The light hydrocarbon inlet, if present, may be coupled to the light hydrocarbon outlet on a reduction reactor; the light aromatic hydrocarbon product inlet, if present, may be coupled to the light aromatic hydrocarbon product outlet on an aromatic hydrocarbon reactor; the light hydrocarbon outlet, if present, may be coupled to the light hydrocarbon inlet on an alkylation reactor; and / or the oligomerization reactor or oligomerization-alkylation reactor and the light aromatic hydrocarbon product outlet, if present, may be coupled to the light aromatic hydrocarbon product inlet on an alkylation reactor or oligomerization-alkylation reactor.

[0066] The oligomerization reactor and / or oligo-alkylation reactor may include a light oligomer product outlet. In some embodiments, the light oligomer product outlet on the oligomerization reactor and / or oligo-alkylation reactor is coupled to a first carbon source gas feed and / or a second carbon source gas feed.

[0067] In some embodiments, the oligomerization reactor and / or the oligo-alkylation reactor further include an outlet for the intermediate oligomer product.

[0068] In some embodiments, the oligomerization reactor, alkylation reactor, and / or oligo-alkylation reactor further includes a medium oligomer inlet, wherein the medium oligomer inlet is connected to a medium oligomer outlet on the oligomerization reactor and / or oligo-alkylation reactor.

[0069] In some embodiments, the oligomerization reactor and / or the oligo-alkylation reactor further include a heavy oligomer product outlet.

[0070] In some embodiments, the reduction reactor further includes a heavy hydrocarbon outlet.

[0071] 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 oligomer inlet and / or a heavy hydrocarbon inlet, and a hydrocracking product outlet. The reducing gas inlet may be connected to the third reducing gas feed; the heavy oligomer inlet, if present, may be connected to the heavy oligomer outlet on an oligomerizing reactor and / or an oligomer-alkylation reactor; and the heavy hydrocarbon inlet, if present, may be connected to the heavy hydrocarbon outlet on a reducing reactor.

[0072] 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.

[0073] The system disclosed herein may further include: a blender having a target hydrocarbon product inlet, a target aromatic product inlet, an alkyl aromatic product inlet, a target oligomer product inlet, and / or a mixed target product inlet and an aviation fuel outlet. The target hydrocarbon inlet, if present, may be connected to a target hydrocarbon outlet on a reduction reactor; the target aromatic product inlet, if present, may be connected to a target aromatic product outlet on an aromatics reactor; the alkyl aromatic product inlet, if present, may be connected to an alkyl aromatic product outlet on an alkylation reactor; the target oligomer product inlet, if present, may be connected to a target oligomer product outlet on an oligomerization reactor; and the mixed target product inlet, if present, may be connected to a mixed target product outlet on an oligomerization-alkylation reactor.

[0074] Aviation fuel production methods

[0075] 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, airspeed, 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 how to adjust the product distribution as intended for a particular application.

[0076] This disclosure provides a number 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 obtain the desired ratios of alkanes and alkenes provided herein.

[0077] 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 obtain: a fuel containing one or more C... 5-9 A mixture of medium-hydrocarbon products of alkanes and / or alkenes; and containing one or more C44 hydrocarbons. 10-16 (ii) a target hydrocarbon product mixture comprising alkanes and / or olefins; and (ii) contacting the hydrocarbon product mixture, an optional second reducing gas, and an optional second carbon source gas with an aromatic catalyst to obtain a mixture containing one or more C4 ... 9-14 A mixture of target aromatic products.

[0078] In some embodiments, contacting the first reducing gas and the first carbon source gas with the reduction catalyst is carried out at an alkane temperature that may be at least 80°C, or 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.

[0079] In some embodiments, contacting the first reducing gas and the first carbon source gas with the reducing catalyst is carried out at an alkane pressure of about 50 psi to about 4000 psi. The alkane pressure can be about 75 psi to about 225 psi. The alkane pressure can be about 75 psi, about 100 psi, about 125 psi, about 150 psi, about 175 psi, about 200 psi, or about 225 psi.

[0080] In some embodiments, each of the light hydrocarbon product mixture, the middle product mixture, and / or the target hydrocarbon product mixture comprises olefins and alkanes. In other embodiments, the olefin-to-alkane ratio in each of the light hydrocarbon product mixture, the middle product mixture, and / or the target hydrocarbon product mixture is at least about 1:1, wherein the amount of olefin is about equal to or greater than the amount of alkanes present therein. The olefin-to-alkane ratio in each of the light hydrocarbon product mixture, the middle product mixture, and / or the target 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 olefin-to-alkane ratio in each of the light hydrocarbon product mixture, the middle product mixture, and / or the target 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.

[0081] In some embodiments, contacting the first reducing gas and the carbon source gas with the reducing catalyst further yields a mixture containing one or more C atoms. 2-4 A mixture of light hydrocarbon products, including alkanes and / or olefins. In some embodiments, the light hydrocarbon product mixture contains C2... 2-4 Alkenes and C 2-4 The ratio of alkanes is at least about 5:1. In other embodiments, the C content in the light hydrocarbon product mixture is... 2-4 Alkenes and C 2-4 The alkane ratio is preferably at least about 8:1. In some embodiments, the C content in the light hydrocarbon product mixture is... 2-4 Alkenes and C 2-4 The alkane ratio 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... 2-4 Alkenes and C 2-4 The ratio of alkanes is approximately 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0082] In some embodiments, the mixture of hydrocarbon products contains one or more C 5-9 Alkanes and alkenes. In some embodiments, the C1 content in the mixture of hydrocarbon products is... 5-9 Alkenes and C 5-9 The alkane ratio is at least about 3:1, or at least about 5:1. In some embodiments, the C content in the hydrocarbon product mixture is... 5-9 Alkenes and C 5-9 The ratio of alkanes is from about 3:1 to about 12:1. In some embodiments, the C content in the mixture of hydrocarbon products is... 5-9 Alkenes and C 5-9 The ratio of alkanes is approximately 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1.

[0083] In some embodiments, the methods disclosed herein involve mixtures comprising aromatic hydrocarbons. These aromatic hydrocarbons can be described according to their carbon number, for example, "C". X-Y "Aromatic hydrocarbons." As those skilled in the art should understand, this carbon number refers to the total number of carbon atoms in the molecule and not necessarily the number of ring atoms. For example, from the term "C..." 10 The group of compounds described by "aromatics" may include naphthalene (C 10 H8), butylbenzene (C 10 H 14 )wait.

[0084] In some embodiments, contacting the intermediate hydrocarbon product mixture, optional second reducing gas, and optional second carbon source gas with the aromatic catalyst is carried out at an aromatic temperature of about 100°C to about 450°C.

[0085] The method disclosed herein may further include passing the mixture of intermediate hydrocarbon products through an adsorbent bed prior to contact with an aromatic catalyst.

[0086] In some embodiments, the mixture of intermediate hydrocarbon products is further contacted with an aromatic catalyst to obtain a product containing one or more C44 compounds. 6-8 A mixture of light aromatic hydrocarbon products.

[0087] In some embodiments, the contacting of the intermediate hydrocarbon product mixture, optional second reducing gas, and optional second carbon source gas with the aromatic catalyst is carried out at an aromatic pressure of about 50 psi to about 1000 psi.

[0088] The method disclosed herein may further comprise contacting a mixture of light hydrocarbon products and a mixture of light aromatic products with an alkylation catalyst to obtain a target alkylaromatic product mixture comprising one or more alkylated aromatics. In some such embodiments, contacting the mixture of light hydrocarbon products and the mixture of light aromatic products with the alkylation catalyst may be carried out under any suitable conditions with any suitable catalyst. In some embodiments, contacting the mixture of light hydrocarbon products and the mixture of light aromatic products with the alkylation catalyst is carried out at an alkylation temperature. The alkylation temperature may be from about 50°C to about 300°C, from about 100°C to about 350°C, from about 100°C to about 250°C, from about 50°C to about 250°C, or from about 80°C to about 230°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.

[0089] Alkylation processes are not particularly sensitive to pressure. However, in some embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst is carried out under alkylation pressure. Alkylation pressures can be from about 0 psig to about 1000 psig, from about 100 psig to about 700 psig, from about 200 psig to about 500 psig, from about 0 psig to about 200 psig, from about 10 psig to about 120 psig, or from about 20 psig to about 100 psig.

[0090] The method disclosed herein may further include contacting a mixture of light hydrocarbon products with an oligomerizing catalyst to obtain a product containing one or more C4 ... 10-16 A mixture of target oligomers of alkanes and / or olefins.

[0091] The method disclosed herein may further include contacting a mixture of light hydrocarbon products and a mixture of light aromatic products with an alkylation catalyst and an oligomerization catalyst to obtain a product containing one or more C 9-14 Aromatics and one or more C 10-16 A mixture of target products consisting of alkanes and / or olefins.

[0092] In some embodiments, it is necessary to oligomerize the olefins generated from CO2 by the methods of this disclosure in the presence of an oligomerizing catalyst to produce a mixture of higher olefins and optionally aromatics. As used herein, the modifier “higher” with respect to hydrocarbons (e.g., alkanes) or olefins refers to hydrocarbons (e.g., alkanes) or olefins having a higher carbon number than the precursor. Exemplary higher hydrocarbons (e.g., alkanes) and olefins include, but are not limited to, C8-C. 16 Hydrocarbons (e.g., alkanes) and / or olefins. The oligomerization method can be carried out in a fixed-bed flow reactor or any other suitable reactor type.

[0093] The oligomerization temperature can be in the range of about 50°C to about 1000°C, depending on the desired product length and distribution, to adjust the degree of oligomerization. The oligomerization temperature can be about 50°C to about 400°C, about 50°C to about 300°C, about 100°C to about 350°C, about 100°C to about 250°C, about 50°C to about 250°C, or about 80°C to about 230°C. The oligomerization temperature can also be about 50°C, about 150°C, about 250°C, about 350°C, or about 400°C.

[0094] The pressure at which this oligomerization can be carried out can range from about 0 psi to about 1000 psi as needed, to adjust the degree of oligomerization based on the desired product length and distribution. Oligomerization pressures can be from about 0 psi to about 500 psi, from about 0 psi to about 400 psi, from about 0 psi to about 300 psi, from about 0 psi to about 200 psi, from about 10 psi to about 120 psi, or from about 20 psi to about 100 psi. Oligomerization pressures can be from about 0 psi, about 10 psi, about 20 psi, about 40 psi, about 60 psi, about 80 psi, about 90 psi, about 100 psi, about 120 psi, or about 150 psi.

[0095] The method disclosed herein may further include contacting a mixture of light hydrocarbon products and a mixture of light aromatic products with an oligomerization-alkylation catalyst to obtain a product containing one or more C 9-14 Aromatics and one or more C 10-16 A mixture of target products consisting of alkanes and / or olefins.

[0096] In some embodiments, the contact between the light hydrocarbon product mixture and the light aromatic product mixture and the oligomerization-alkylation catalyst is carried out at the oligomerization-alkylation temperature. The oligomerization-alkylation temperature can be about 50°C to about 300°C, about 100°C to about 350°C, about 100°C to about 250°C, about 50°C to about 250°C, or about 80°C to about 230°C. The oligomerization-alkylation temperature can also be about 50°C, about 100°C, about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, or about 400°C.

[0097] The oligomerization-alkylation process is not particularly sensitive to pressure. However, in some embodiments, the contact between the light hydrocarbon product mixture and the light aromatic product mixture and the oligomerization-alkylation catalyst is carried out under oligomerization-alkylation pressure. The oligomerization-alkylation pressure can be from about 0 psig to about 200 psig, from about 10 psig to about 120 psig, or from about 20 psig to about 100 psig.

[0098] The method disclosed herein may further comprise passing a mixture of light hydrocarbon products and / or a mixture of light aromatic products through an adsorbent bed prior to contact with an alkylation and / or oligomerization catalyst.

[0099] In some embodiments, contacting the light hydrocarbon product mixture and / or the light hydrocarbon product mixture with an oligomerizing catalyst further yields a product containing one or more C4 ...544545444444 1-2 A mixture of light oligomers of hydrocarbons.

[0100] The method disclosed herein may further include combining the carbon source gas with the mixture of light oligomers prior to contact with the reduction catalyst.

[0101] In some embodiments, the light hydrocarbon product mixture is further contacted with an oligomerizing catalyst to obtain a product containing one or more C4 ...54454444454544 3-7 A mixture of medium-oligomery products of hydrocarbons.

[0102] The method may further include blending a target hydrocarbon product mixture, a target aromatic product mixture, a target oligomeric product mixture, a target alkyl aromatic product mixture, and / or a target product mixture to produce aviation fuel. Those skilled in the art will readily understand that some or all of the products and mixtures from any one or more reactors used in the methods or systems disclosed herein may be subjected to certain treatments, such as hydrogenation and / or adsorption, to remove impurities prior to blending.

[0103] The method may include hydrogenating a mixture of target aromatic products, a mixture of target oligomer products, and / or a mixture of target alkyl aromatic products. Hydrogenating olefins converts most of the olefins to alkanes. Hydrogenating aromatics converts most of the aromatics to cycloalkanes. The hydrogenation step may include providing the mixture of target aromatic products, the mixture of target oligomer products, and / or the mixture of target alkyl aromatic products to any number of hydrogenation reactors, each containing the same or different hydrogenation catalysts. The method may include one hydrogenation reactor for olefin hydrogenation (also known as olefin hydrotreating) and / or another hydrogenation reactor for aromatic hydrogenation (also known as aromatic hydrotreating). In one embodiment, a small portion of the target aromatic product mixture may be provided to the olefin hydrogenation reactor, and the majority may be provided to the aromatic hydrogenation reactor to maintain a certain degree of aromatization and some flexibility in the blending ratio.

[0104] The method disclosed herein may further include combining a mixture of light hydrocarbon products with a mixture of medium-oligomeric products prior to contact with an oligomer catalyst.

[0105] In some embodiments, the light hydrocarbon product mixture is further contacted with an oligomerizing catalyst to obtain a product containing one or more C4 ...5445444445445444445445444444545444444545444445454444545454444454545454545454545454545454545454545454545454545454545454545454545454545454545454 17-40 Mixtures of heavy oligomers of alkanes and / or olefins.

[0106] In some embodiments, contacting the first reducing gas and the carbon source gas with the reducing catalyst further yields a mixture containing one or more C atoms. 17-40 A mixture of heavy hydrocarbon products of alkanes and / or alkenes.

[0107] The method disclosed herein may further comprise contacting a third reducing gas and a mixture of heavy oligomers and / or a mixture of heavy hydrocarbon products with a hydrocracking catalyst to obtain a product containing one or more C 1-18 A mixture of hydrocracking products of alkanes and / or olefins.

[0108] 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 is carried out at a hydrocracking temperature of about 250°C to about 450°C.

[0109] In some embodiments, contacting the third reducing gas and the mixture of heavy oligomers and / or heavy hydrocarbon products with 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.

[0110] Catalysts used to convert carbon sources into olefins and alkanes

[0111] The systems and methods disclosed herein may include the use of a reduction catalyst. The conversion of carbon dioxide and carbon dioxide-containing mixtures can be achieved via catalytic carbon dioxide conversion, in which the reduction catalyst plays a key role in the process. As used herein, the reduction catalyst 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 capable of converting a carbon source gas (e.g., CO2) into hydrocarbons containing olefins and / or alkanes.

[0112] Any known reduction catalyst may be used according to this disclosure.

[0113] Transition metal catalysts, especially alkali metals, are particularly effective as reduction catalyst systems due to their high electron density, multiple oxidation states, and abundant spectrum of cermet materials. This can enhance carbon dioxide activation and flexibly modulate the conversion pathway. In addition to the metal element, the reduction catalyst may also contain one or more other materials, such as binders, lubricants, and / or support materials, which can be added to optimize the catalyst formation process, metal dispersion, and other chemical and physical properties.

[0114] Some commonly known reduction catalysts contain copper, iron, zinc, cobalt, or combinations thereof. Copper is known to be one of the most efficient reduction catalysts for producing oxygen-containing compounds as major products. These catalysts may include copper as the core metal, with various supporting elements, including but not limited to zinc, zirconium, aluminum, chromium, alkali metals, and alkaline earth metals. Supporting elements, metal alloys, and metal oxides provide electronic and structural support to better tune the reactivity and selectivity of carbon dioxide hydrogenation.

[0115] The reduction catalyst may contain iron and / or cobalt. Iron and cobalt catalysts are widely used in carbon dioxide hydrogenation, particularly in the Fischer-Tropsch process, for example, to form longer-chain hydrocarbons and oxygen-containing products. Similar to the copper group catalysts, iron and cobalt catalysts may contain additional metal promoters to improve carbon dioxide adsorption and hydrogenation selectivity. Metal promoters may be selected from zinc, manganese, molybdenum, copper, nickel, alkali metals, and alkaline earth metals.

[0116] 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, as well as those exemplified herein, some or all oxygen atoms of the metal oxide may bond to other atoms in the catalyst mixture, and / or may be partially or completely removed from the catalyst mixture during the activation step (e.g., converted to CO2 and removed). Furthermore, those skilled in the art will understand that for such catalysts, such as the reduction and / or alkane catalysts described below, the molar ratio of oxygen relative to the total composition may vary. Moreover, it will be understood that when defining a catalyst made from a metal oxide, the molar ratio of one metal to another is defined on a metal-based (rather than metal oxide) basis.

[0117] The reduction catalyst can be an alkane catalyst or an olefin catalyst. As used herein, the term "alkane catalyst" refers to a catalyst primarily used to convert a carbon source and reducing gas into alkanes, but the catalyst itself does not necessarily contain alkanes. An alkane catalyst can be selected when the desired product is an alkane. Alkane catalysts can be used to convert a carbon source and reducing gas primarily into alkanes, and small amounts of olefins and / or other hydrocarbons. As used herein, the term "olefin catalyst" refers to a catalyst primarily used to convert a carbon source and reducing gas into olefins, but the catalyst itself does not necessarily contain olefins. An olefin catalyst can be selected when the desired product is an olefin. Olefin catalysts can be used to convert a carbon source and reducing gas primarily into olefins, and small amounts of alkanes and / or other hydrocarbons.

[0118] The reduction catalyst may comprise: zinc; one or more first elements selected from iron or cobalt; and oxygen, carbon, or nitrogen. The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; and oxygen, carbon, or nitrogen. The reduction catalyst may also comprise aluminum. The reduction catalyst may also comprise one or more second elements selected from Group V, Group VI, Group VII, Group VIII, Group IX, Group X, and Group XI metals (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may also comprise one or more Group IA and Group IIA metals.

[0119] The reduction catalyst may comprise: zinc; one or more first elements selected from iron or cobalt; oxygen or carbon or nitrogen; and aluminum. The reduction catalyst disclosed herein may comprise: 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, Group VI, Group VII, Group VIII, Group IX, Group X, and Group 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 or carbon or nitrogen; aluminum; and one or more Group IA and Group IIA metals.

[0120] 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, Group VI, Group VII, Group VIII, Group IX, Group X, and Group 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 Group IIA metals.

[0121] 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.%.

[0122] The reduction catalyst may comprise a cobalt-embedded interconnect matrix of reduced copper nanoparticles and aluminum-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 in cobalt, 0.05-4 in copper, and 0.05-2 in zinc. In some embodiments, the Co:Cu:Zn ratio is in the range of 1-2 in cobalt, 1-3 in copper, and 0.5-1 in zinc. In some embodiments, the Co:Cu:Zn ratio is about 1:2.5:1. In some embodiments, zinc is preferably 0.3-1 of the molar content of copper. In some embodiments, cobalt is preferably 0.1-1 of the molar content of copper.

[0123] The reduction catalyst may comprise an iron-embedded interconnect matrix of reduced copper nanoparticles and aluminum-modified zinc oxide. 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 other embodiments, the iron oxide is magnetite (Fe3O4). In still other embodiments, the iron oxide is a combination of magnetite (Fe3O4) and hematite (Fe2O3).

[0124] 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 in iron, from about 0.05 to about 4 in copper, and from about 0.05 to about 4 in zinc. In some embodiments, the Fe:Cu:Zn ratio is from about 0.4 to about 2 in iron, from about 1 to about 3 in copper, and in the range of about 0.5 to 3 in zinc. In some embodiments, the Fe:Cu:Zn ratio is about 1:2.3:2.3. In some embodiments, zinc is preferably from about 0.3 to about 1 of the molar content of copper. In some embodiments, iron is from about 0.5 to about 5 of the molar content of copper.

[0125] The reduction catalyst may contain one or more elements selected from transition metals or metals of Group VI, VII, VIII, IX, X, or XI. In some embodiments, the reduction catalyst contains one or more second elements selected from Group VI metals. In some embodiments, the reduction catalyst contains one or more second elements selected from Group VII metals. In some embodiments, the reduction catalyst contains one or more second elements selected from Group VIII metals. In some embodiments, the reduction catalyst contains one or more second elements selected from Group IX metals. In some embodiments, the reduction catalyst contains one or more second elements selected from Group X metals. In some embodiments, the reduction catalyst contains one or more second elements selected from Group XI metals.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] The reduction catalyst may comprise one or more Group IA or Group IIA metals. In some embodiments, the one or more Group IA or Group IIA metals comprise magnesium, calcium, potassium, sodium, or cesium. In some embodiments, the one or more Group IA or Group IIA metals are composed of magnesium, calcium, potassium, sodium, or cesium. In some embodiments, the one or more Group IA or Group IIA metals comprise sodium and / or cesium or are composed of the same.

[0131] In some embodiments, the reduction catalyst comprises one or more Group IA or Group IIA metals in a molar ratio to copper of about 0.01 to about 1.0, about 0.05 to about 0.50, about 0.10 to about 0.30, about 0.20 to about 0.50, about 0.30 to about 0.50, or about 0.40 to about 0.50.

[0132] In some embodiments, the reduction catalyst comprises one or more Group IA metals. The one or more Group IA or Group IIA metals may comprise potassium, sodium, or cesium. In some embodiments, the one or more Group IA or Group IIA metals are composed of potassium, sodium, or cesium. In some embodiments, the one or more Group IA or Group IIA metals comprise potassium. In some embodiments, the one or more Group IA or Group IIA metals comprise sodium. In some embodiments, the one or more Group IA or Group IIA metals comprise cesium.

[0133] 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.

[0134] 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.

[0135] The reduction catalyst may contain one or more metal oxides selected from the group consisting of zinc oxide, copper oxide, cobalt oxide, iron oxide, nickel oxide, and any combination thereof.

[0136] The reduction catalyst may contain alumina.

[0137] In some embodiments, the reduction catalyst comprises alumina (Al₂O₃), wherein aluminum is present relative to copper in a molar ratio 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 generated in situ as a component of the reduction catalyst, for example, by co-precipitation of aluminum nitrate with the first element, copper, and zinc precursors.

[0138] 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 ratios of the above components may be as described above.

[0139] 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.

[0140] 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, or Cu(ZnO)CoMoA / Al2O3, where A is an alkali metal, and the relative amounts of other elemental components are as described above.

[0141] 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, where the relative amounts of the elemental components are as described above.

[0142] 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 / Al2O3, where the relative amounts of the elemental components are as described above.

[0143] In other respects, this paper provides reduction catalysts comprising the following:

[0144] One or more metals;

[0145] One or more second elements selected from copper and zinc;

[0146] Optional one or more Group VI, VII, VIII, IX, X or XI metal additives;

[0147] Optional Group IA or Group IIA metals that act as promoters.

[0148] One or more metals may be selected from cobalt, iron, nickel, indium, yttrium, lanthanides, and combinations thereof. In some embodiments, one or more metals are cobalt. In other embodiments, one or more metals are iron. In still other embodiments, one or more metals are a combination of iron and cobalt.

[0149] One or more metals may be present in the form of oxides, nitrides, or carbides. In some embodiments, one or more metals are present in the form of iron oxide.

[0150] In other embodiments, one or more second elements are copper. In other embodiments, one or more second elements are zinc. In still other embodiments, one or more second elements are both copper and zinc. In some embodiments, one or more second elements are present in the form of oxides, nitrides, or carbides. In yet another embodiment, one or more second elements are zinc oxide.

[0151] In some embodiments, one or more Group VI, VII, VIII, IX, X, or XI metal additives, when present, are selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. In other embodiments, Group IA or IIA metals, when present, are Group IA elements. In other embodiments, one or more Group IA or IIA metals, when present, are magnesium, calcium, lithium, sodium, potassium, or cesium. In other embodiments, Group IA or IIA metals, when present, are lithium, sodium, potassium, or cesium. In still other 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.

[0152] In some embodiments, the reduction catalyst comprises one or more Group VI or Group VII metals, such as manganese (Mn), chromium (Cr), or combinations thereof. In some embodiments, the reduction catalyst comprises one or more Group VI or Group 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.

[0153] In some respects, the reduction catalyst comprises: one or more alkane metal oxides; an optional support; and optional 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, if present, may comprise carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, or silicon carbide. The one or more metal additives, if present, may be selected from Group IA or Group IIA elements, palladium, platinum, ruthenium, or combinations thereof.

[0154] In some aspects, this disclosure provides catalytic compositions comprising one or more reduction catalysts and a reduction catalyst. The reduction catalyst support can be any suitable material capable of serving as a catalyst support.

[0155] The reduction catalyst support may comprise one or more materials selected from 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.

[0156] 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.

[0157] 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 some 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.

[0158] 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-zeolite (LTL), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In some embodiments, the reduction catalyst support is MCM-49. In other embodiments, the zeolite contains additional metals, such as Zn, Ga, Fe, or other transition metals. In still other embodiments, the additional metal is present as a zeolite-supported metal or as an isomorphous substitution in the zeolite framework.

[0159] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine and / or sulfur.

[0160] 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 those skilled in the art will appreciate, the physical properties of the mesoporous material (e.g., mesopore volume and surface area) can be measured using standard gas adsorption 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 referred to as "surface area").

[0161] In some embodiments, the mesopore volume of the reduction catalyst support is from about 0.01 to about 3.0 cc / g.

[0162] 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 the reduction catalyst support and catalyst disclosed herein is about 10 m². 2 / g to approximately 1000 m 2 / g.

[0163] The catalytic composition may be in the form of particles with an average size of about 10 nm to about 5 µm, an average size of about 20 nm to about 5 µm, an average size of about 50 nm to about 1 µm, an average size of about 100 nm to about 500 nm, or an average size of about 50 nm to about 300 nm.

[0164] The catalytic composition may comprise 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.

[0165] 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 non-agglomerated particles is from about 100 nm to about 500 nm.

[0166] The reduction catalyst may comprise: iron; optional alumina; optional first element selected from copper, zinc, cobalt, manganese, chromium, or combinations thereof; and optional one or more second elements selected from Group IA and Group IIA metals.

[0167] In some embodiments, the reduction catalyst further comprises an additive mixture containing potassium, manganese, ruthenium, and MgO. In other embodiments, the reduction catalyst comprises about 1% to about 10% by weight of the additive mixture.

[0168] 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.

[0169] The reduction catalyst may contain one or more Group IA or Group IIA metals. One or more Group IA or Group IIA metals may contain magnesium, calcium, potassium, sodium, or cesium. One or more Group IA or Group IIA metals may be composed of magnesium, calcium, potassium, sodium, or cesium. One or more Group IA or Group IIA metals may contain magnesium. One or more Group IA or Group IIA metals may contain calcium. One or more Group IA or Group IIA metals may contain potassium. One or more Group IA or Group IIA metals may contain sodium. One or more Group IA or Group IIA metals may be composed of magnesium. One or more Group IA or Group IIA metals may be composed of calcium. One or more Group IA or Group IIA metals may be composed of potassium. One or more Group IA or Group IIA metals may be composed of sodium. One or more Group IA or Group IIA metals may be composed of cesium.

[0170] The reduction catalyst may contain: 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 optional alumina.

[0171] 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.

[0172] 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.

[0173] In some embodiments, the reduction catalyst comprises:

[0174] iron;

[0175] K, Cs, Mg, Rh, Ca or combinations thereof, in a molar ratio of 0 to about 0.20 relative to iron;

[0176] Na, Cu, Cr, Mn or combinations thereof, in a molar ratio to iron of 0 to about 0.60;

[0177] Co, Ru, Ni, or combinations thereof, in a molar ratio to iron of 0 to about 0.50.

[0178] In some embodiments, the reduction catalyst comprises Co in a molar ratio of 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.

[0179] Iron can be in metallic form, in 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).

[0180] The reduction catalyst may contain: iron; a first element selected from copper, zinc, cobalt, or combinations thereof; and optionally one or more second elements selected from Group IA and Group IIA metals.

[0181] The reduction catalyst may also include one or more third elements selected from Group V, Group VI, Group VII, Group VIII, Group IX, Group X and Group XI metals (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum or nickel).

[0182] The reduction catalyst may include: iron; and the first element is zinc. One or both of iron and zinc may be present in the form of oxides or carbides. Iron oxide may be in the form of FeO, hematite (Fe2O3), magnetite (Fe3O4), 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.

[0183] 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 some 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.

[0184] 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.

[0185] 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 Group IIA metals.

[0186] One or more Group IA or Group IIA metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn may be present in a molar ratio of 0 to about 0.50 relative to iron.

[0187] 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.

[0188] The reduction catalyst may comprise 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 plus the first element. In some embodiments, the reduction catalyst comprises 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 plus the first element. In other embodiments, when the first element is zinc, the reduction catalyst may comprise 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 plus zinc.

[0189] Reduction catalysts can provide methane selectivity of less than about 11 mol% or less than about 10 mol%. Olefin catalysts can provide methane selectivity of about 4 mol% to about 11 mol% or about 5 mol% to about 10 mol%. Unless otherwise explicitly stated, the selectivity values ​​disclosed herein are in mol% carbon.

[0190] The reduction catalyst can provide product streams with an olefin to alkane ratio (O / P) greater than about 7. The reduction catalyst can provide product streams with an olefin to alkane ratio (O / P) of about 7 to about 9, about 8 to about 9, or about 8.

[0191] In some respects, 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.

[0192] In some embodiments, the reduction catalyst comprising the reduction catalyst support is in the form of particles 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.

[0193] In some embodiments, the reduction catalyst comprising the reduction catalyst support accounts for 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.

[0194] In some embodiments, the reduction catalyst support is a high surface area scaffold. In other embodiments, the reduction catalyst support comprises mesoporous silica. In still other embodiments, the reduction catalyst support comprises a carbon allotrope.

[0195] In some embodiments, the reduction catalyst is pretreated with syngas. In other embodiments, the reduction catalyst is pretreated with hydrogen. In still other embodiments, the reduction catalyst is heated with an inert gas (including but not limited to nitrogen and argon) prior to manufacturing.

[0196] The reduction catalyst disclosed herein has improved selectivity of olefins and / or alkanes relative to methane and improved means of adjusting the olefin to alkane ratio.

[0197] Carbon conversion using the reduction catalyst disclosed herein can convert a carbon source gas into a hydrocarbon mixture comprising olefins and alkanes. The hydrocarbon mixture may have an olefin to alkane ratio (O / P) greater than about 7. The reduction catalyst can provide product streams with an olefin to alkane ratio (O / P) of about 7 to about 9, about 8 to about 9, or about 8.

[0198] Methane is typically an undesirable byproduct of carbon dioxide conversion. Therefore, methane production is a factor in catalyst effectiveness, as it is undesirable. Consequently, a lower methane yield (also referred to herein as methane selectivity SC1, defined in Equation 1) indicates a better catalyst. Referring to Equation 1, Cmol.CH4 represents the mole fraction of methane in the product stream, and Cmol.CO... 2进料 The mole fraction of CO2 in the feed stream is expressed in Cmol.CO. 2产物 This indicates the mole fraction of CO2 in the product stream.

[0199] Equation 1: Methane selectivity (SC1) = [Cmol.CH4 / (Cmol.CO] 2进料 - Cmol.CO 2产物 )]

[0200] The reduction catalysts disclosed herein may have methane selectivity (SC1) of less than about 15 mol%, less than about 11 mol%, or less than about 10 mol%. The reduction catalysts may have methane selectivity of about 2 to about 15 mol%, about 4 to about 15 mol%, about 5 to about 12 mol%, about 5 to about 11 mol%, about 6 to about 11 mol%, or about 8 to about 11 mol%. The reduction catalysts described herein may have selectivity for C2 to C4 hydrocarbons (SC2-C4) of greater than about 15 mol%, greater than about 20 mol%, greater than about 25 mol%, greater than about 30 mol%, greater than about 35 mol%, or greater than about 35 mol%. The reduction catalysts described herein may have SC2-C4 selectivity of about 15 to about 50 mol%, about 20 to about 45 mol%, or about 25 to about 45 mol%. The reduction catalyst described herein may have SC2-C4 having approximately 28 mol% carbon, approximately 35 mol% carbon, approximately 38 mol% carbon, approximately 39 mol% carbon, or approximately 45 mol% carbon. 2-4 The selectivity is determined by adding (the selectivity of C2) + (the selectivity of C3) + (the selectivity of C4), where each selectivity value is calculated according to Equation 2. Refer to Equation 2: C x Represents hydrocarbons with x carbon atoms; Cmol.C x Indicates C in the product flowx mole fraction; 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.

[0201] Equation 2: Hydrocarbon C x Selectivity (SC) x ) = [Cmol.C x / (Cmol.CO 2进料 - Cmol.CO 2产物 )]

[0202] The reduction catalysts disclosed herein may have a C % (greater than about 20 mol%, greater than about 22 mol%, greater than about 25 mol%, greater than about 28 mol%, greater than about 30 mol%, greater than about 32 mol%, or greater than about 34 mol%) of C. 5+ Hydrocarbon selectivity (SC) 5+ C 5+ (Refers to any hydrocarbon with 5 or more carbon atoms). The reduction catalysts disclosed herein may have about 20 to about 45 mol% carbon atoms, about 22 to about 43 mol% carbon atoms, about 25 to about 43 mol% carbon atoms, about 28 to about 43 mol% carbon atoms, or about 30 to about 40 mol% carbon atoms. 5+ Hydrocarbon selectivity (SC) 5+ The reduction catalysts disclosed herein may have approximately 29 mol% C, approximately 31 mol% C, approximately 33 mol% C, approximately 34 mol% C, approximately 35 mol% C, or approximately 43 mol% C content. 5+ Hydrocarbon selectivity (SC) 5+ C 5+ The higher the selectivity of hydrocarbons, the better the performance of the catalyst used in the carbon dioxide conversion process disclosed in this paper.

[0203] Oxygen-containing compounds are typically undesirable byproducts of carbon dioxide conversion. The reduction catalysts disclosed herein can exhibit oxygen-containing selectivity (Soxy) of less than about 20 mol% of carbon dioxide, less than about 16 mol% of carbon dioxide, less than about 14 mol% of carbon dioxide, or less than about 15 mol% of carbon dioxide. The reduction catalysts can exhibit oxygen-containing selectivity of about 2 to about 20 mol% of carbon dioxide, about 4 to about 18 mol% of carbon dioxide, or about 4 to about 16 mol% of carbon dioxide.

[0204] 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 may 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 corrosion within the system; and iii) catalyst deactivation: metal leaching results in the loss of active material from the catalyst, as well as a loss of efficiency in terms of activity and selectivity. The higher the leaching rate, the faster the catalyst deactivates.

[0205] The reduction catalyst disclosed herein offers significant improvements over other catalysts, including unsupported metal catalysts, in metal leaching. The shaped reduction catalyst disclosed herein (i.e., a catalyst including a binder) exhibits significantly reduced metal leaching compared to the powdered form of the same catalyst (i.e., without a binder). When comparing the powdered catalyst with the shaped catalyst, the amount of metal leaching can be reduced by more than about 50%, more than about 70%, more than about 80%, or more than about 90%.

[0206] Once the reaction reaches a steady state, the total amount of metal leached in the effluent can be measured by the following steps: i) separating the aqueous portion of the effluent from the oil portion; and ii) analyzing the aqueous portion sample by ICP-MS to obtain the concentration of metal leached in the aqueous sample. The method for measuring metal leaching may further include: iii) dissolving the oil portion in an acid, such as nitrohydrochloric acid; iv) analyzing the dissolved oil portion sample by ICP-MS to obtain the concentration of metal leached in the oil sample; and v) adding the metal concentrations in the oil sample and the aqueous sample to obtain the total metal leaching. After reaching a steady state, the oil sample typically contains less than about 1 ppm of leached metal. Before reaching a steady state, loose powder from the catalyst migrates into the effluent and dissolves in the oil portion of the effluent, and 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.

[0207] After a period of operation, the reaction reaches a steady state such that the concentration (ppm) of the second element is about 10 ppm or less, about 8 ppm or less, or about 6 ppm or less. After a period of operation, the reaction reaches a steady state such that the concentration (ppm) of the second element is 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. After an 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 is reached. The steady state of the reaction can be determined by the concentration of the second element, since the second element leaches more than the active metal and is present in a lower amount in the catalyst than the active metal. (1) When the reducing 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 may 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 may 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.

[0208] The total concentration of one or more second elements in the effluent under steady-state conditions may 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 may 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) may 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 may be from about 0 ppm to about 6 ppm, or greater than about 0 ppm to about 6 ppm.

[0209] 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, Group IIA, and / or Group X metal ions present in the effluent tested after a period of operation.

[0210] Because the catalyst may contain less of a secondary element than iron or zinc, reducing the leaching of this secondary element may be particularly important for maintaining catalyst lifetime. The leaching levels of secondary elements (e.g., Na, K) in the effluent tested after approximately 200 to approximately 400 hours of operation may be less than approximately 10 ppm, less than approximately 8 ppm, less than approximately 5 ppm, or less than approximately 2 ppm. The leaching levels of secondary elements in the effluent tested after approximately 400 hours of operation may be less than approximately 10 ppm, less than approximately 8 ppm, less than approximately 5 ppm, or less than approximately 2 ppm. The leaching levels of secondary elements in the effluent tested after approximately 400 hours of operation may 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.

[0211] The leaching amount of the second element of the formed catalyst in the effluent tested after approximately 200 hours of operation may 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 may 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.

[0212] The shaped reduction catalysts mentioned herein contain a binder and are formed by any means known in the art, such as (but not limited to) extrusion, compression, powder compression into granules, flakes, or other shaped forms. The shaped catalysts (in extrusion or granule form) may have compressive strengths 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 catalysts (in extrusion, granule, or flake form) may have compressive strengths from about 20 N / mm to about 100 N / mm, from about 20 N / mm to about 80 N / mm, from about 20 N / mm to about 65 N / mm, from about 30 N / mm to about 65 N / mm, from about 35 N / mm to about 60 N / mm, or from about 40 N / mm to about 55 N / mm.

[0213] Due to reduced metal leaching, the reduction catalysts disclosed herein exhibit a longer lifetime (i.e., before deactivation) compared to 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 one year to about five years, about two years to about five years, about three years to about five years, or about four years to about five years. The term "maintained activity" means that the catalyst retains approximately 75% of its initial activity in the conversion of CO2 to hydrocarbons.

[0214] Product stream may include C1-C 40 Hydrocarbons. C1-C of the product stream 40 Hydrocarbons may include (i) alkanes (n-alkanes, isoalkanes, cycloalkanes), alkenes (n-alkenes, isoalkenes) and (2) aromatics. The product stream may also include (3) oxygen-containing compounds (alcohols, ketones, esters, aldehydes and acids) and (4) water.

[0215] The feed stream may contain a carbon source gas (e.g., CO2) and a reducing gas (e.g., H2). In some embodiments, the feed stream may further contain one or more of the following: CO, CH4, C2H4, C2H6, C3H6, C3H8, C4H8, C4H 10 .

[0216] The reduction catalyst may comprise iron and zinc; one or more second elements selected from Group IA, Group IIA, and Group 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; optional alumina; optional first elements selected from copper, cobalt, manganese, chromium, or combinations thereof; optional one or more second elements selected from Group IA, Group IIA, and Group X metals; and a binder.

[0217] 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.

[0218] The reduction catalyst may contain one or more second elements selected from Group IA or Group IIA metals. One or more Group IA or Group IIA metals may contain magnesium, calcium, potassium, sodium, cesium, rubidium, or any combination thereof. One or more Group IA or Group IIA metals may be composed of magnesium, calcium, potassium, sodium, cesium, or rubidium. One or more Group IA or Group IIA metals may contain magnesium. One or more Group IA or Group IIA metals may contain calcium. One or more Group IA or Group IIA metals may contain potassium. One or more Group IA or Group IIA metals may contain sodium. One or more Group IA or Group IIA metals may contain cesium. One or more Group IA or Group IIA metals may contain rubidium. One or more Group IA or Group IIA metals may be composed of magnesium. One or more Group IA or Group IIA metals may be composed of calcium. One or more Group IA or Group IIA metals may be composed of potassium. One or more Group IA or Group IIA metals may be composed of sodium. One or more Group IA or Group IIA metals may be composed of cesium. One or more Group IA or Group IIA metals may be composed of rubidium.

[0219] The reduction catalyst may contain a second element, which is a Group X metal. The Group X metal may be selected from palladium, platinum, iridium, nickel, and rhodium. Platinum may be a Group X metal. Palladium may be a Group X metal. Nickel may be a Group X metal.

[0220] The reduction catalyst may also include 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). The reduction catalyst may include manganese. The reduction catalyst may include silver. The reduction catalyst may not contain any third element selected from Group V, VI, VII, VIII, IX, and XI metals.

[0221] The reduction catalyst may comprise from about 0.1 wt% to about 60 wt% of Group IA, Group IIA, or Group X metals by weight of total iron, zinc, and other Group IA, Group IIA, or Group 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, Group IIA, or Group X metals by weight of total iron, zinc, and other Group IA, Group IIA, or Group 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 other Group IA metals. The reduction catalyst may contain 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 weight of total iron, zinc and Group IA metals.

[0222] 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.

[0223] Iron can be in metallic form, in 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).

[0224] The reduction catalyst may include 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, hematite (Fe2O3), magnetite (Fe3O4), 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.

[0225] 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 some 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.

[0226] 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.

[0227] 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 Group IIA metals. The one or more Group IA and Group IIA metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn is present 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, Group IIA, and Group X metals. The one or more Group IA, Group IIA, and Group X metals may be present in a molar ratio of 0 to about 0.60 relative to iron; and Zn is present in a molar ratio of 0.2 to about 3 relative to iron.

[0228] 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.

[0229] The reduction catalyst may comprise, by weight of iron to zinc, 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 total weight of iron and zinc. In some embodiments, the reduction catalyst comprises, by weight of iron to zinc, 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 total weight of iron and zinc. In some embodiments, the reduction catalyst comprises, by weight of iron to zinc, 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 total weight of iron and zinc.

[0230] The reduction catalyst may comprise iron, zinc, and one or more Group IA or Group 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 Group IIA metals are present in an amount from about 0.5% to about 1.0% of the total weight of iron and zinc.

[0231] The reduction catalyst may comprise iron, zinc, and one or more Group IA, Group IIA, or Group 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 is present in an amount from about 0.5% to about 1.0% of the total weight of iron and zinc.

[0232] In some respects, 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.

[0233] In some embodiments, the catalyst support comprises one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, and tin. In other embodiments, the catalyst support comprises one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron, and tin. In some preferred embodiments, the catalyst support comprises 7-alumina. In some embodiments, the catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silicon carbide. In some embodiments, an additional support is selected from carbon, silica, zeolite, alumina, iron oxide, zirconium oxide, titanium oxide, and silicon carbide. In some embodiments, the catalyst support is alumina formed in situ as part of a reduction catalyst. In some embodiments, the catalyst support is selected from, but not limited to, Al₂O₃, ZrO₂, SnO₂, SiO₂, ZnO, and TiO₂. In some embodiments, the catalyst support is selected from Al2O3, ZrO2, SnO2, SiO2, ZnO, and TiO2. In some embodiments, the catalyst support is selected from Al2O3, ZrO2, SnO2, SiO2, ZnO, Fe2O3, Fe3O4, FeO, and TiO2.

[0234] 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.

[0235] 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 some 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.

[0236] 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-zeolite (LTL), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In some embodiments, the reduction catalyst support is MCM-49. In other embodiments, the zeolite contains a modifier, such as Zn, Ga, Fe, or other transition metals. In still other embodiments, the modifier is present as a zeolite-supported metal or as an isomorphous substitution in the zeolite framework.

[0237] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine and / or sulfur.

[0238] In some embodiments, the reduction catalyst support is a mesoporous material. In such embodiments, as those skilled in the art will appreciate, the physical properties of the mesoporous material (e.g., mesopore volume and surface area) can be measured using standard gas adsorption 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 referred to as "surface area"). In other embodiments, the mesopore volume of the reduction catalyst support is from about 0.01 to about 3.0 cc / g.

[0239] 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 reduction catalyst comprising the reduction catalyst support is approximately 10 m². 2 / g to approximately 1000 m 2 / g.

[0240] In some embodiments, the reduction catalyst comprises a reduction catalyst support in the form of particles having 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.

[0241] In some embodiments, the reduction catalyst comprises a reduction catalyst support in an amount of 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.%.

[0242] In some embodiments, the reduction catalyst support is a high surface area scaffold. In other embodiments, the reduction catalyst support comprises mesoporous silica. In still other embodiments, the reduction catalyst support comprises a carbon allotrope.

[0243] In some embodiments, the reduction catalyst is a nanoparticle catalyst. In other embodiments, the particle size of the reduction catalyst on the support surface may be 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 non-agglomerated particles is 100-500 nm.

[0244] In some embodiments, the reduction catalyst is pretreated with syngas. In other embodiments, the reduction catalyst is pretreated with hydrogen. In still other embodiments, the reduction catalyst is heated with an inert gas (including but not limited to nitrogen and argon) prior to manufacturing.

[0245] The reduction catalyst may include a binder. The binder may be any binder known in the art. The binder may be freely selected 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.

[0246] 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. In some embodiments, the binder is present in an amount of about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 20 wt%, about 1 wt% to about 30 wt%, about 1 wt% to about 20 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 20 wt%, about 5 wt% to about 15 wt%, or about 15 wt% to about 25 wt% of the total catalyst composition.

[0247] The binder may contain a promoter element selected from Na, K, Cs, Li, Rb, or combinations thereof. Promoters in the binder have been found to improve catalyst performance, such as activity, selectivity, and stability, by maintaining a constant promoter level on the active metal component. Specifically, the benefits of doped binders include:

[0248] • Improve methane selectivity;

[0249] • Acidity increases hydrocarbon yield;

[0250] • Creating mesopores in the shaped catalyst may improve product selectivity; and

[0251] • Reduce metal leaching.

[0252] The binder may be a heterogeneous, amorphous, or microporous material. In some embodiments, the binder may be selected from the group consisting of sodium aluminate, potassium silicate, sodium silicate, and any combination thereof. The binder may be selected from sodium aluminate, potassium aluminate, sodium silicate, potassium silicate, sodium zirconate, potassium zirconate, Na-tungsten, K-tungsten, or combinations thereof.

[0253] When accelerators are added to binders, the performance of the catalyst (e.g., regarding SC1 and SC) is affected. 5+ (For example) significantly improved. When comparing the performance of a catalyst with a binder without a accelerator to the performance of the same catalyst and binder with a accelerator, 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%, 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.

[0254] Preferably, a binder is selected that minimizes or eliminates any strong metal-support interaction with the active metal, as such interaction would inhibit the catalytic properties of the active metal. The preferred binder binds small active metal particles together to form fairly large extrusions / agglomerates (1-5 mm). These extrusions / agglomerates are suitable for applications in industrial reactors. They also offer better handling characteristics and avoid pressure drop in large-scale reactors.

[0255] The binder disclosed herein reduces metal leaching, which improves catalyst lifetime. In the case of powder, the surface area is extremely large, thus reducing thermal shock in large-scale reactors by forming extrudates with the binder.

[0256] In some embodiments, when the reduction catalyst comprises iron oxide and zinc oxide, as well as a Group IA or Group IIA metal, and when the first carbon source gas and the first reducing gas are fed into the reduction reactor, the iron oxide reaction is 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.

[0257] CO2 reduction catalyst composition

[0258] In some aspects, this disclosure provides reduction catalyst compositions comprising one or more of the reduction catalysts disclosed herein and an additional support. The additional support can be any suitable material that can serve as a catalyst support, as defined above.

[0259] In some embodiments, the catalyst composition is in the form of particles with an average size of about 10 nm to about 5 μm. In some embodiments, the catalyst composition is in the form of particles with an average size of about 20 nm to about 5 μm. In some embodiments, the catalyst composition is in the form of particles with an average size of about 50 nm to about 1 μm. In some embodiments, the catalyst composition is in the form of particles with an average size of about 100 nm to about 500 nm. In some embodiments, the catalyst composition is in the form of particles with an average size of about 50 nm to about 300 nm.

[0260] In some embodiments, the catalyst composition comprises about 5 wt.% to about 80 wt.% of catalyst. In some embodiments, the catalyst composition comprises about 5 wt.% to about 70 wt.% of catalyst. In some embodiments, the catalyst composition comprises about 20 wt.% to about 70 wt.% of catalyst. In some embodiments, the catalyst composition comprises about 30 wt.% to about 70 wt.% of catalyst.

[0261] In some embodiments, the carrier is a high surface area scaffold. In some embodiments, the carrier comprises mesoporous silica. In some embodiments, the carrier comprises a carbon allotrope.

[0262] Preparation methods of catalysts and catalyst compositions for CO2 reduction

[0263] The reduction catalysts and catalyst compositions disclosed herein can be prepared by any suitable method. In some aspects, this disclosure provides methods for preparing the catalysts or catalyst compositions disclosed herein, comprising preparing the catalyst by co-precipitation, wet impregnation, or ball milling.

[0264] In some embodiments, a method for preparing a powder catalyst includes the following steps:

[0265] (a) Provide a first solution containing a zinc source, an iron source, an alkali and water;

[0266] (b) Heating the first solution at a first temperature for a first time period, thereby producing a first reaction mixture;

[0267] (c) Heating the first reaction mixture at a second temperature for a second time period to remove water, thereby producing a solid precursor; and

[0268] (d) The solid precursor is heated to a third temperature for a third time period to obtain the catalyst.

[0269] In other embodiments, the method for preparing the powdered catalyst includes the following steps:

[0270] (a) Provide a second solution containing a zinc source, an iron source, and water;

[0271] (b) Provide a third solution containing alkali;

[0272] (c) Heating the third solution at a third temperature for a third time period;

[0273] (d) Alumina is added to the third solution, thereby producing a second reaction mixture;

[0274] (e) The second solution is added to the second reaction mixture at a fourth temperature for a fourth time period, thereby producing a third reaction mixture;

[0275] (f) The third reaction mixture is heated at a fifth temperature for a fifth time period, thereby producing a solid precursor;

[0276] (g) Separate the solid precursor;

[0277] (h) Contacting the solid precursor with a solution containing a Group IA metal, thereby producing a catalyst precursor; and

[0278] (i) The catalyst precursor is heated to a sixth temperature for a sixth time period, thereby separating the catalyst.

[0279] In some embodiments, the method includes the following steps: providing a first solution containing a zinc source and an aluminum source; combining the first solution with an alkaline precipitant (e.g., a carbonate) to increase the pH of the metal salt-containing solution, thereby precipitating solid particles; and drying and calcining the solid particles to form a solid catalyst.

[0280] In some embodiments, the base comprises a carbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium. In other embodiments, the base comprises a bicarbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium.

[0281] In some embodiments, the method includes the steps of: providing a first solution containing a cobalt source and introducing it into a pre-formed copper-zinc alumina material via initial wetting or wet impregnation, followed by drying and calcination to form a solid catalyst.

[0282] In some embodiments, the method includes the steps of: mixing a cobalt source and a carrier in a grinding jar to provide a first mixture; ball milling the first mixture for 2 hours to 2 weeks to provide a first precipitate; filtering the first precipitate and heating it to a first temperature to provide a ball-milled cobalt source; mixing the ball-milled cobalt source with copper and zinc sources and an alumina source to provide a second mixture; and separating solid material from the second mixture.

[0283] In some embodiments, the method further comprises combining a solid material with one or more Group IA metal sources. In some embodiments, the method further comprises compressing the solid material into granules. In some embodiments, the method further comprises compressing the solid material into granules and then introducing them into a flow reactor.

[0284] A method for preparing a shaped catalyst includes: providing a powdered catalyst prepared by any suitable method known in the art; combining the powdered catalyst, a binder, and a lubricant to prepare a dry mixture; and combining the dry mixture with a first solution containing a pectin, wherein the pectin activates the binder, thereby forming an extrudable dough. The extrudable dough can be processed in an extruder to provide a shaped catalyst, which can take the form of an extrudate, granules, flakes, etc. The shaped catalyst can be further processed by heating to a drying temperature for a first time period to provide a dry shaped catalyst and / or heating to a calcination temperature for a second time period to provide a calcined shaped catalyst. The calcined shaped catalyst can be a shaped catalyst, which can be selected from extrudates, granules, flakes, etc.

[0285] The first drying period can be about 1 to about 3 hours, about 1.5 to about 2.5 hours, or about 2 hours. The drying temperature can be about 80°C to about 200°C, about 100°C to about 180°C, or about 110°C to about 130°C. The second calcination period can be about 2 to about 6 hours, about 3 to about 5 hours, about 3.5 to about 4.5 hours, or about 4 hours. The calcination temperature can be about 280°C to about 420°C, about 300°C to about 400°C, or about 320°C to about 370°C.

[0286] Another method for preparing a shaped catalyst includes: providing a powdered catalyst prepared by any suitable method known in the art; and combining the powdered catalyst with a slurry comprising a peptizing agent and a binder to prepare an extrudable dough. The extrudable dough can be processed as described above. The method may include combining the powdered catalyst and a lubricant to prepare a dry mixture prior to combination with the slurry.

[0287] The lubricant can be any suitable lubricant known in the field. For example, lubricants may be selected from magnesium stearate, stearic acid, calcium stearate, sodium stearoyl fumarate, polyethylene glycol, silica (also known as colloidal silica), talc, beeswax, and hydrogenated vegetable oils (such as STEROTEX). ® LUBRITAB ® (and any combination thereof.) The lubricant may be hydrogenated vegetable oil.

[0288] The colloidal solvent can be any suitable peptide known in the art. For example, the colloidal solvent can be selected from acids, Group IA hydroxides, polymers, or combinations thereof. The colloidal solvent can be an acid selected from the group consisting of inorganic and organic acids. The colloidal solvent can be nitric acid, phosphoric acid, acetic acid, hydrochloric acid, formic acid, sulfuric acid, oxalic acid, and any combination thereof. The colloidal solvent can be nitric acid.

[0289] Catalysts used to convert carbon sources and reducing gases into aromatics

[0290] In some respects, the systems and methods of this disclosure involve the use of aromatic catalysts. As used herein, the term "aromatic catalyst" refers to a catalyst primarily used to convert a carbon source and reducing gas into aromatics, but the catalyst itself does not necessarily contain aromatics. The use of aromatic catalysts may also produce smaller amounts of other hydrocarbons.

[0291] In some embodiments, the aromatic catalyst comprises a zeolite. In some embodiments, the zeolite is selected from: 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-zeolite (LTL); mordenite; MWW-type zeolite, such as MCM-22, MCM-36, MCM-49, PSH-3, MCM-56; DA-114; microcrystalline USY zeolite; microcrystalline USY zeolite and combinations thereof. In some embodiments, the zeolite is ZSM-5, MCM-49, PSH-3, or MCM-22. The zeolite may be ZSM-5. ZSM-5 may have a silicon-to-aluminum ratio (SAR) of about 30 to about 1000, about 80 to about 400, about 30 to about 280, or about 80 to about 280.

[0292] The zeolite may contain a modifier. The modifier may be Ga, Fe, Mn, Zn, P, Pt, or a combination thereof. In some embodiments, the zeolite contains 0 wt% to about 10 wt% of a modifier. In other embodiments, the zeolite contains 0.01 wt% to about 10 wt% of a modifier, 0.01 wt% to about 5 wt% of a modifier, 0.01 wt% to about 3 wt% of a modifier, 0.1 wt% to about 1.5 wt% of a modifier, or 0.5 wt% to about 1 wt% of a modifier. In some embodiments, the zeolite is ZSM-5 modified with Ga, Fe, Mn, Zn, P, Pt, or a combination thereof. The zeolite may be ZSM-5 modified with Zn, optionally in an amount of 0 wt% to about 10 wt% of the total catalyst composition.

[0293] Optional features of the present invention associated with the catalyst described above for converting carbon source and reducing gas into aromatics may also constitute optional features associated with catalysts for converting carbon source into alkanes or catalysts for converting carbon source gas and reducing gas into straight-chain α-olefins, and vice versa.

[0294] Aromatic catalysts may include binders. The binder may be any binder known in the art. In some embodiments, the binder may be selected 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, silicon, zirconium, silica, pseudoboehmite alumina (e.g., VERSAL) ®V-250), bentonite, or any combination thereof. The binder may be present in an amount from about 0% to about 60% by weight or from about 0% to about 40% by weight of the entire catalyst composition. In some embodiments, the binder may be present in an amount from about 0.1% to about 30% by weight, about 0.1% to about 20% by weight, about 1% to about 30% by weight, about 1% to about 20% by weight, about 1% to about 15% by weight, about 5% to about 30% by weight, about 5% to about 20% by weight, about 5% to about 15% by weight, about 0.5% to about 10% by weight, or about 0.5% to about 5% by weight of the entire catalyst composition. In one embodiment, the aromatic catalyst comprises a silica binder in an amount from about 15% to about 25% by weight or about 20% by weight of the entire catalyst composition.

[0295] In some embodiments, the aromatic catalyst of this disclosure is capable of converting a carbon source gas (e.g., CO2) into aromatics. In some embodiments, the aromatic catalyst of this disclosure is capable of converting a carbon source gas (e.g., CO2) and an olefin source into aromatics. The olefin source for conversion into aromatics may be a mixture of hydrocarbon products (e.g., containing one or more C4 ...5444444444454444444454444445444444544 4-9 A mixture of hydrocarbon products (alkanes and / or alkenes), or a mixture of olefin products (e.g., containing one or more C4 ... 4-9 (Olefin feed stream).

[0296] The feed stream through the aromatic catalyst may be a carbon source gas. The carbon source gas may be a mixture of hydrocarbons, including (but not limited to) olefins. Therefore, the selectivity of the aromatic catalyst refers to the conversion of hydrocarbons (including (but not limited to) olefins) into a specified aromatic molecule. Optionally, the selectivity of the aromatic catalyst refers to the conversion of hydrocarbons (including (but not limited to) olefins) into a specified aromatic molecule in the presence of a carbon gas source. The aromatic catalysts used herein may have selectivity to aromatics of more than about 50 mol% carbon, more than about 55 mol% carbon, more than about 60 mol% carbon, or more than about 65 mol% carbon. The aromatic catalysts may have selectivity to aromatics of about 50 mol% carbon to about 90 mol% carbon, about 55 mol% carbon to about 85 mol% carbon, about 60 mol% carbon to about 85 mol% carbon, or about 65 mol% carbon to about 80 mol% carbon. The aromatic catalysts used herein may have selectivity to the target aromatic hydrocarbon of about 5 mol% carbon to about 20 mol% carbon, or about 7 mol% carbon to about 15 mol% carbon. The aromatic catalysts used in this paper exhibit selectivity for methane of less than about 8 mol%, less than about 5 mol%, or less than about 4 mol%. The aromatic catalysts used in this paper exhibit selectivity for methane of about 1 mol% to about 8 mol%, about 2 mol% to about 6 mol%, about 2 mol% to about 5 mol%, or about 3 mol% to about 4 mol%.

[0297] The aromatics reactor can yield an aromatics product mixture comprising a light aromatics product mixture and a target aromatics product mixture. The aromatics product mixture may comprise approximately 70% to approximately 93% by weight of the light aromatics product mixture and approximately 7% to approximately 15% by weight of the target aromatics product mixture from the total aromatics product mixture. Alternatively, the aromatics product mixture may comprise approximately 80% to approximately 93% by weight of the light aromatics product mixture and approximately 7% to approximately 10% by weight of the target aromatics product mixture from the total aromatics product mixture.

[0298] The light aromatic product mixture may include a mixture of benzene, toluene, and A8 (an aromatic molecule having 8 carbon atoms). The aromatic product mixture may contain about 10% to about 20% by weight of benzene and about 40% to about 50% by weight of toluene. The aromatic product mixture may contain about 12% to about 18% by weight of benzene and about 40% to about 46% by weight of toluene, and optionally about 25% to about 35% by weight of A8 aromatics. The aromatic product mixture may contain less than about 5% by weight, less than about 3% by weight, and less than about 2% by weight of naphthalene. The aromatic product mixture may contain about 10% to about 20% by weight of benzene, about 40% to about 50% by weight of toluene, and less than about 5% by weight or less than about 2% by weight of naphthalene. The aromatic product mixture may contain about 12% to about 18% benzene and about 40% to about 46% to toluene, about 25% to about 35% A8 aromatics and less than about 5% or less than about 2% naphthalene.

[0299] Catalysts for hydrogenation

[0300] In some aspects, the systems and methods of this disclosure relate to the hydrogenation of a certain percentage of produced hydrocarbons using a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst may be independently selected from the catalysts described below.

[0301] In some embodiments, the hydrogenation catalyst of this disclosure is an aluminosilicate catalyst, such as zeolite. In other embodiments, the isomerization catalyst and / or hydrogenation catalyst is AlCl3. In still other embodiments, the hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In yet another embodiment, the hydrogenation catalyst is Pt on β-zeolite. In some embodiments, the hydrogenation catalyst of this disclosure comprises an isomerization catalyst metal and a zeolite support. In other embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo.

[0302] The additional support may comprise one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the additional support comprises γ-alumina. In some embodiments, the additional support is selected from carbon, silicon dioxide, zeolite, alumina, zirconium oxide, titanium oxide, and silicon carbide. In some embodiments, the additional support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite. In some embodiments, the additional support is alumina formed in situ as part of a reduction catalyst. In some embodiments, the additional support is selected from, but not limited to, MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, and TiO2. In some embodiments, the additional support is selected from MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silicon carbide, and TiO2.

[0303] The hydrogenation catalyst support may comprise: A) one or more oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin, such as MgO, Al2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silicon carbide, and TiO2; B) carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide;

[0304] C) SiAlO x A) SO4-ZrO2, zirconium tungstate, tungstate-titanium dioxide and anatase (SiO2-Al2O3, SiO2-TiO2); D) aluminum-based materials, such as alumina (e.g. γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite and thermal shock gibbsite; or E) zeolites, such as Y-type zeolites, β-zeolites, ZSM-type zeolites (e.g. ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g. SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. Optionally, the zeolite contains a modifier, such as Zn, Ga, Fe or other transition metals; and / or the modifier is optionally present in the form of a zeolite-supported metal or in the form of isomorphous substitution in the zeolite framework.

[0305] Additional carriers may include one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0306] Additional carriers can be selected from SiAlO xSO4-ZrO2, zirconium tungstate, tungstate-titanium dioxide, and anatase (SiO2-Al2O3, SiO2-TiO2). In other embodiments, the additional carrier is an aluminum-based material, such as alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermal shock gibbsite.

[0307] The additional support may be 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), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In other embodiments, the zeolite contains an additional metal, such as Zn, Ga, Fe, or other transition metals. In still other embodiments, the additional metal exists as a zeolite-supporting metal or as an isomorphous substitution in the zeolite framework. The additional support may be modified with molybdenum, chlorine, and / or sulfur.

[0308] In other embodiments, the hydrogenation catalyst may be selected from Pt / ZrO2 / WO3, Pt / ZrWO4, or Pt / SiAlO2. x , Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlO x , Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO.

[0309] Catalysts for hydrocracking

[0310] The systems and methods disclosed herein can use any suitable hydrocracking catalyst, including those known in the art. In some embodiments, catalysts similar to those described for the hydrogenation and isomerization steps (above) are also used for hydrocracking.

[0311] Any suitable hydrocracking catalyst known in the art can be used in these processes. However, specific examples set forth below are provided to illustrate the use and identification of such catalysts, which are particularly suitable for use in conjunction with other features of the systems and methods disclosed herein.

[0312] In other embodiments, 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 serve as a catalyst support.

[0313] The hydrocracking support may comprise one or more materials selected from 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.

[0314] 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.

[0315] In some embodiments, the hydrocracking support is selected from SiAlO. x SO4-ZrO2, zirconium tungstate, tungstate-titanium dioxide, and anatase (SiO2-Al2O3, SiO2-TiO2). In other 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.

[0316] 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-zeolite (LTL), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In other embodiments, the zeolite contains a modifier, such as Zn, Ga, Fe, or other transition metals. In still other embodiments, the modifier is present as a zeolite-supported metal or as an isomorphous substitution in the zeolite framework.

[0317] In some embodiments, the hydrocracking support is modified with molybdenum, chlorine and / or sulfur.

[0318] In some embodiments, the hydrocracking metal comprises about 0.5 wt% to about 40 wt% of the hydrocracking catalyst. In other embodiments, the hydrocracking metal comprises about 0.5 wt% of the hydrocracking catalyst. In still other embodiments, the hydrocracking metal comprises about 1 wt% of the hydrocracking catalyst. In yet another embodiment, the hydrocracking metal comprises about 10 wt% of the hydrocracking catalyst. In some embodiments, the hydrocracking metal comprises about 20 wt% of the hydrocracking catalyst. In some embodiments, the hydrocracking metal comprises about 30 wt% of the hydrocracking catalyst. In yet another embodiment, the hydrocracking metal comprises about 40 wt% of the hydrocracking catalyst.

[0319] Optional features of the present invention related to the above-described catalysts for hydrocracking 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 aromatics, or catalysts for hydrogenation and isomerization, and vice versa.

[0320] Catalysts for aromatic alkylation

[0321] The alkylation step can be carried out using any suitable catalyst. In some embodiments, the alkylation catalyst is a liquid acid, such as HF; solid phosphoric acid (SPA); a Friedel-Crafts alkylation catalyst (e.g., HF / AlCl3); tungsten; platinum; or zeolite. In other embodiments, the alkylation catalyst is a zeolite, such as an acidic zeolite. In still other embodiments, the zeolite is selected from: Y-type zeolite; β-zeolite; ZSM-type zeolite (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-57); SAPO-type zeolite (e.g., SAPO-11, SAPO-5, SAPO-31, SAPO-41); L-zeolite (LTL); mordenite; MWW structure type zeolite, 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.

[0322] Weight-based space velocity (WHV) is the amount of reactant per unit time per unit mass of catalyst. The WHV range for alkylation catalysts is from about 0.1 g reactant / g catalyst / hour (0.1 h⁻¹) to about 50 h⁻¹, or from about 0.5 h⁻¹ to about 20 h⁻¹.

[0323] Catalysts for oligomerization

[0324] Oligomeric catalysts can be heterogeneous acid catalysts, such as zeolites or molecular sieves. Oligomeric catalysts can be amorphous or crystalline aluminosilicate molecular sieves. Oligomeric catalysts can be zeolites. Oligomeric catalysts can be aluminosilicate zeolites. Oligomeric catalysts 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; MWW structure type zeolites, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56; and any combination thereof. Oligomeric catalysts can be ZSM-5, β-zeolite, MCM-22, MCM-49, PSH-3, mordenite, SAPO-5, or combinations thereof. The oligomerization catalyst can be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof. The oligomerization catalyst can be ZSM-5. The oligomerization catalyst can be MCM-22, PSH-3, or MCM-49.

[0325] Weight-based space velocity (WHV) is the amount of reactant per unit time per unit mass of catalyst. The WHV range for oligomeric catalysts is from about 0.1 g reactant / g catalyst / hour (0.1 h⁻¹) to about 50 h⁻¹, from about 0.5 h⁻¹ to about 20 h⁻¹, or from about 0.5 h⁻¹ to about 5 h⁻¹.

[0326] When using an oligo-alkylation reactor, combinations of one or more alkylation catalysts and one or more oligomeric catalysts can be combined within the reactor. The one or more alkylation catalysts and one or more oligomeric catalysts can be mixed, stratified, and optionally subjected to intermediate quenching within the reactor. In other embodiments, oligo-alkylation catalysts can be used. Oligo-alkylation catalysts can be liquid acids, such as HF; solid phosphoric acid (SPA); Fourier-Krawst alkylation catalysts (e.g., HF / AlCl3); amorphous heterogeneous acid catalysts (e.g., tungsten / Zr oxide); heterogeneous acid catalysts, such as zeolites or molecular sieves; and combinations thereof. In some embodiments, the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve. In other embodiments, the oligomerization-alkylation 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; zeolites of the MWW structure type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56; and any combination thereof. In other embodiments, the oligomerization-alkylation catalyst is ZSM-5, β-zeolite, MCM-22, PSH-3, MCM-49, mordenite, SAPO-5, or any combination thereof.

[0327] Reducing gas, carbon source gas and their ratio

[0328] 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 and reducing gas may be provided separately to the necessary reaction vessel, or in some embodiments they may be premixed (e.g., a first reducing gas feed and a first carbon source gas feed may refer to the same physical characteristics as a second reducing gas feed and a second carbon source gas feed in some embodiments) to provide a single feed stream comprising both the carbon source gas and the reducing gas, coupled to a suitable reactor.

[0329] Alternatively, 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 carbon source gas and reducing gas, which can be connected to both the aromatics reactor and the reduction reactor.

[0330] In some embodiments, the single gas feed may include CO2, H2, CO, C2, C3, CH4, and any combination thereof. The feed stream may contain about 10% to about 95% H2 / CO2, and each of CO, C2, C3, and CH4 in the range of about 0% to about 65%. The sources of CO, C2, C3, and / or CH4 may be from the recirculated stream or may be introduced into the fresh feed stream.

[0331] 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, syngas (CO / H2), or independently selected from flare gas, exhaust gas, or natural gas, or gases derived from flare gas, exhaust gas, or natural gas.

[0332] In some embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is H2. In other embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is syngas. In still other 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 other embodiments, the first reducing gas, the second reducing gas, the third reducing gas, and / or the fourth reducing gas is flare gas, exhaust gas, or natural gas, or a gas 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.

[0333] In some embodiments, the first carbon source gas and / or the second carbon source gas is CO2. In other embodiments, the first carbon source gas and / or the second carbon source gas contains CO2. In still other embodiments, the first carbon source gas and / or the second carbon source gas is CO. In still other embodiments, the first carbon source gas and / or the second carbon source gas contains CO.

[0334] 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 elsewhere in the disclosed systems and methods) can be adjusted as needed to provide the desired product output characteristics.

[0335] Furthermore, as those skilled in the art will understand, the carbon source gas and reducing gas can provide any suitable ratio to achieve the desired product output characteristics. In some embodiments, the molar ratio of the first reducing gas to the first carbon source gas is from about 10:1 to about 1:10. In other embodiments, the molar ratio of the first reducing gas to the first carbon source gas is from about 5:1 to about 0.5:1. In still other embodiments, the molar ratio of the second reducing gas to the second carbon source gas is from about 10:1 to about 1:10. In still other embodiments, the molar ratio of the second reducing gas to the second carbon source gas is from about 5:1 to about 0.5:1.

[0336] definition

[0337] 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 described herein in conjunction with 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 well-known and commonly used in the respective fields.

[0338] Unless otherwise indicated, the methods and techniques disclosed herein are generally performed according to conventional methods well known in the art and as described in the various general and more specific references cited and discussed throughout this invention. 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 ed., WH Freeman & Co., New York (2000); Griffiths et al., Introduction to Genetic Analysis, 7th ed., WH Freeman & Co., NY (1999); and Gilbert et al., Developmental Biology, 6th ed., Sinauer Associates, Inc., Sunderland, MA (2000).

[0339] Unless otherwise defined herein, chemical terms used herein are used in accordance with their usual usage in the field, as illustrated in The McGraw-Hill Dictionary of Chemical Terms, edited by Parker, S., McGraw-Hill, San Francisco, CA (1985).

[0340] All the foregoing references and any other publications, patents, and published patent applications mentioned herein are specifically incorporated herein by reference. In case of conflict, this specification (including its specific definitions) shall prevail.

[0341] As used herein, the terms “Log of solubility,” “LogS,” or “logS” are used in the field to quantify the water solubility of compounds. The water solubility of a compound significantly affects its adsorption and distribution characteristics. Low solubility is generally associated with poor adsorption. The LogS value is the unit logarithm (base 10) of solubility measured in moles per liter.

[0342] As used herein, the term "monocyclic aromatic hydrocarbon" refers to a compound containing only a single 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 indene).

[0343] As used herein, the term "polycyclic aromatic hydrocarbon" 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 hydrocarbon" may be used to refer to a group of compounds comprising naphthalene and / or naphthalene derivatives.

[0344] As used herein, the term "petroleum-derived" refers to compounds and compositions derived from petroleum feedstocks by physical and chemical methods, but excludes compounds and compositions 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).

[0345] When the amount of impurities is specified at the level of “approximately 0”, those skilled in the art should understand that, based on the relevant detection methods used, such measurement is accurate to a certain effective number.

[0346] As used herein, certain components, fractions, and feeds are defined according to the number of carbons (e.g., C) in the components, fractions, feeds, etc. X-Y The descriptions are provided. These descriptions indicate the possible (non-limiting) number of carbons in the hydrocarbons present in the component, but do not require the presence of every carbon number 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.

[0347] 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 selectivity value observed in a reaction carried out under conditions chosen by a person skilled in the art with suitable reagents to maximize or minimize the production 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. As will be understood by a person skilled in the art, selectivity may be a function of the catalyst used in the process, and / or a function of process design or parameters (e.g., temperature, pressure, reagent concentration, GHSV, etc.). Those skilled in the art are familiar with how to calculate the selectivity of a given product. However, where an explicit method for calculating selectivity is provided herein, that method shall prevail.

[0348] As used herein, the term "oligomery" and its grammatical variations will be understood by those skilled in the art to refer to methods that may involve dimers, trimers, tetramers, pentamers, hexamers, heptomers, octamers, nonamers, decanters, higher oligomers, and combinations thereof. The degree of oligomerization in a particular reaction will determine the composition of the product stream and depends on aspects of the reactant stream and the reaction conditions.

[0349] Example

[0350] The invention has now been generally described. The invention will be more readily understood with reference 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.

[0351] Example 1: CO2 to Alkane Catalyst Composition

[0352] Some reduction catalysts disclosed herein comprise mixed metal oxides. Examples of mixed oxide compositions are given below:

[0353] The mixed oxide composition is represented as A a B b Fe 100 Zn x O y The catalyst is a mixed oxide composed of iron, zinc oxide, and additional promoter metals. The catalyst is designated as A. a B b Fe 100 Zn x O y , where a, b, and x represent the atomic composition of each metal, and y is the number of oxygen atoms in the supplementary metal. A is at least one of K, Li, Zr, Cs, Mg, and Ca, and B is at least one of Au, Cu, Na, Cr, Al, Ga, and Mn. The ranges of a, b, and x are shown below:

[0354] a.0 ≤ a < 20

[0355] b.0 ≤ b < 60

[0356] c. 0 ≤ x < 50

[0357] The mixed oxide composition is represented as A a B b Fe 100 X c The mixed oxide component of the catalyst consists of additional metal-modified iron and zinc oxide, denoted as A. a B b Fe 100 X c Where a, b, and c represent the atomic composition of each metal. A is at least one of K, Cs, Rh, Mg, and Ca; B is at least one of Na, Cu, Cr, and Mn; and X is at least one of Co, Ru, and Ni. The ranges of a, b, and c are shown below:

[0358] a.0 ≤ a < 20

[0359] b.0 ≤ b < 60

[0360] c.0 ≤ c < 50

[0361] The mixed oxide composition is represented as A a B b X c The mixed oxide component of the catalyst includes additional metal-modified cobalt or iron, denoted as A. a B b X 100 Where a, b, and c represent the atomic composition of each metal. A is at least one of K, Cs, Rh, Mg, Na, and Ca; B is at least one of Zn, Cu, Cr, and Mn; and X is at least one of Co, Fe, and Ni. The ranges of a, b, and c are shown below:

[0362] a.0 ≤ a < 20

[0363] b.0 ≤ b < 90

[0364] c.0 ≤ c < 50

[0365] Example 2: Synthesis of certain CO2-to-alkane catalyst compositions

[0366] I. Preparation of Mixed Oxide Catalyst: First, an iron oxide-zinc oxide complex was prepared by co-precipitation using a 0.5 M metal nitrate precursor solution. This complex was then reacted with 1.2 molar equivalents of sodium carbonate, and mixed at 338 K using a parallel addition method for 1 hour.

[0367] The resulting slurry was then aged while continuously stirred at 353 K for 1 hour. A precipitate was then obtained using vacuum filtration and a 0.25-micron filter. Excess sodium was removed by three washing steps with distilled water, using 300 mL of distilled water in each step. The resulting solid contained less than 0.1% residual sodium. The precipitate was dried at 393 K for 4 hours and then ground into a fine powder.

[0368] Potassium was impregnated using an initial wetting impregnation method. In this method, a 2 M potassium carbonate solution was prepared and then sprayed onto a solid iron and zinc complex, simultaneously incorporating it via a shaking table. It was then calcined at 623 K for 6 hours. The resulting catalyst was Na. 0.6 K4Fe 100 Zn 16 O y .

[0369] II. A a B b Fe 100 X c Catalyst preparation: Mined magnetite was ground to a particle size of 0.25 and impregnated with potassium at 5 wt% relative to iron using an initial wetting impregnation method. Impregnation was carried out with potassium carbonate solution using sufficient distilled water to achieve a water-to-magnetite ratio of 0.2 g / g. The impregnation step was performed dropwise in an ultrasonic bath. After the solution was completely added to the magnetite, the slurry was left in the ultrasonic bath for 10 minutes. It was then dried in an oven at 393 K for 4 hours, followed by calcination at 623 K for 6 hours. The resulting catalyst was Fe. 100 K5.

[0370] III. A a B b Fe 100 X c Catalyst preparation: Fe and Co metal solutions were prepared using metal nitrates as precursors, and a sodium carbonate alkaline solution with a concentration of 2.4 molar equivalents relative to the metal nitrates was prepared at 0.5 M.

[0371] Add enough water to submerge the stirrer into a 2 L round-bottom flask and heat to 343 K while continuously stirring. Transfer the metal and alkali solution to the round-bottom flask via a peristaltic pump for parallel addition, with a target flow rate ensuring that half of the alkali solution is completely added to the molten metal in approximately 1 hour. The temperature is then raised to 353 K for aging for 1 hour. After 1 hour, the mixture is cooled to room temperature and then reheated to 343 K. The remaining alkali solution is added over 1 hour, and the resulting slurry is aged at 353 K for another hour.

[0372] The precipitate was vacuum filtered using a 0.25-micron filter. The product was then washed three times and mixed with approximately 300 mL of water, filtered at each step to remove excess sodium until less than 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 Fe. 100 Co 14 K1.

[0373] IV. A a B b X 100 Catalyst preparation: Solutions of Fe and Co metals were prepared using metal nitrates as precursors. Iron and cobalt were added to a solid material containing certain metals and support oxides using an initial wetting impregnation method. After the solution was completely added to the solid material, the slurry was left in an ultrasonic bath for 10 minutes. It was then dried in an oven at 393 K for 4 hours, followed by calcination at 623 K for 6 hours.

[0374] Example 3: A general procedure for converting CO2 into alkanes and alkenes

[0375] The formation of alkanes from CO2 and hydrogenation were carried out in a fixed-bed flow reactor. A 1 kg CoRu / In / alumina catalyst was charged into the flow reactor. The catalyst was reduced in situ at 250 °C for 2 hours in a hydrogen atmosphere. After pretreatment, the reactor was heated to 250 °C. A feed mixture of 80% hydrogen and 20% CO2 was introduced at 500 psi and 9,000 h. -1 The gas hourly space velocity (GHSV) is introduced into the reactor. CO2 is converted into carbon chains with a selective range of carbon chain numbers (C6-C6). 40 A mixture of alkanes and alkenes.

[0376] Example 4: Exemplary Procedure I for the Conversion of CO2 into Alkanes and Alkenes

[0377] The catalyst (e.g., Na) prepared by the method of Example 1 0.6 K4Fe 100 Zn 16 O yThe granules were granulated to a size of 40-60 mesh and pretreated with H2 for 5 hours at 623 K, 150 PSIG, and GHSV 1200. Subsequently, the granules were conditioned with syngas (H2 / CO=2) at 623 K and GHSV 600. The CO2 hydrogenation of the catalyst was then tested to produce CO with C2 content. 10 -C 16 The alkane fraction of the SAF within the hydrocarbon range. The CO2 conversion to the SAF was measured in a fixed-bed reactor under conditions of 623 K, GHSV 1500, and 450 PSIG using feed gas H2 = 72 mol%, CO2 = 24 mol%, and N2 = 4 mol% as internal standards.

[0378] Table 1: Product distribution obtained by exemplary procedure I for converting CO2 into alkanes.

[0379]

[0380] Analysis of higher molecular weight products (C) in the SAF product range 10 -C 16 The carbon type distribution of ) is shown in Table 2 below. The distribution of each carbon number is summarized in Table 2 below, where others include isoalkanes and cycloalkanes.

[0381] Table 2: C obtained through exemplary procedure I for converting CO2 into alkanes 10 -C 16 Hydrocarbon distribution.

[0382]

[0383] Example 5: Procedure II for the conversion of CO2 into alkanes and alkenes

[0384] The catalyst (e.g., Fe) prepared by the method in Example 1 100 K5 particles were granulated to a size of 40-60 mesh and pretreated with H2 for 10 hours at 150 PSIG, 623 K, and GHSV 400. After hydrogen treatment, CO2 to SAF conversion was carried out in a fixed-bed reactor at 623 K, GHSV 1500, and 450 PSIG using feed gas H2 = 63 mol%, CO2 = 23 mol%, and N2 = 4 mol% as internal standards.

[0385] Table 3: By using CO2 is converted into alkanes and alkenes. The product distribution obtained by procedure II.

[0386]

[0387] Analysis of higher molecular weight products (C) in the SAF product range 10 -C16 The distribution of carbon types is shown in Table 4 below. The distribution of each carbon number is summarized in Table 4 below, where others include isoalkanes and cycloalkanes.

[0388] Table 4: By using CO2 is converted into alkanes and alkenes. The C obtained by program II 10 -C 16 Hydrocarbon distribution.

[0389]

[0390] Example 6: Procedure III for the conversion of CO2 into alkanes and alkenes

[0391] The catalyst (e.g., Fe) prepared by the method in Example 1 100 Co 14 K1) was granulated to a size of 40-60 mesh and pretreated with H2 for 5 hours at 150 PSIG, 623 K, and GHSV 200. After hydrogen treatment, the catalyst was conditioned with syngas (H2 / CO=2) at 145 PSIG, 623 K, and GHSV 600 for 1 hour. The CO2 to SAF conversion was measured in a fixed-bed reactor at 623 K, GHSV 1500, and 450 PSIG using feed gas of H2 = 63 mol%, CO2 = 23 mol%, and N2 = 4 mol% as internal standards.

[0392] Table 5: By using CO2 is converted into alkanes and alkenes. The product distribution obtained by procedure III.

[0393]

[0394] Analysis of higher molecular weight products (C) in the SAF product range 10 -C 16 The distribution of carbon types is shown in Table 6 below. The distribution of each carbon number is summarized in Table 6, where others include isoalkanes and cycloalkanes.

[0395] Table 6: By using CO2 is converted into alkanes and alkenes. The C obtained by program III 10 -C 16 Hydrocarbon distribution.

[0396]

[0397] Example 7: Procedure IV for the conversion of CO2 into alkanes and alkenes

[0398] The catalyst prepared by the method of Example 1 (e.g., A) a B b X 100The particles were granulated to a size of 40-60 mesh and pretreated with nitrogen containing diluted H2 for 15 hours at 150 PSIG, 623 K, and GHSV 200. The CO2 to SAF conversion was measured in a fixed-bed reactor at 623 K, GHSV 1500, and 450 PSIG using feed gas of H2 = 63 mol%, CO2 = 23 mol%, and N2 = 4 mol% as internal standards.

[0399] Table 7: By using CO2 is converted into alkanes and alkenes. The product distribution obtained by procedure IV.

[0400]

[0401] Analysis of higher molecular weight products (C) in the SAF product range 10 -C 16 The distribution of carbon types is shown in Table 8 below. The distribution of each carbon number is summarized in Table 8, where others include isoalkanes and cycloalkanes.

[0402] Table 8: By using CO2 is converted into alkanes and alkenes. The C obtained by the IV program 10 -C 16 Hydrocarbon distribution.

[0403]

[0404] Example 8: A general procedure for separating hydrocarbons within a target range

[0405] A feed mixture of 50% CO2 to alkane products and 50% CO2 to aromatic products is introduced into the distillation system under ambient pressure (N2). The fraction from 150°C to 300°C is collected.

[0406] Example 9: General Procedure for Hydrocracking

[0407] The collected fraction from the separation step (e.g., from Example 4) was fed into a hydrocracking reactor loaded with 1 kg Pt (0.5 wt% Pt) / Y zeolite catalyst. The reaction was carried out at 750 psi, with a hydrogen to hydrocarbon molar ratio set at 20 and a liquid weight hourly space velocity (WHSV) of 1.0 h⁻¹. -1 The fraction is converted to carbon chain numbers in the range of C8 and C6. 15 A mixture of saturated n-alkanes, isoalkanes, and alkenes.

[0408] Example 10: Fe / Zn-Na reduction catalyst Preparation of .

[0409] Solutions of Fe and Zn metals were prepared using metal nitrates as precursors. A sodium carbonate alkali solution containing 2.4 molar equivalents relative to the metal nitrate was prepared at a concentration of 0.5 M. Sufficient water was added to a 2 L round-bottom flask to submerge the stirrer, and the mixture was heated to 343 K while continuously stirring. The metal and alkali solutions were transferred to the round-bottom flask via a peristaltic pump for parallel addition, with a target flow rate ensuring that half of the alkali solution was completely added to the metal solution within approximately 1 hour. The temperature was then raised to 353 K for aging for 1 hour. After 1 hour, the mixture was cooled to room temperature and then reheated to 343 K. The remaining alkali solution was added within 1 hour, and the resulting slurry was aged again at 353 K for 1 hour.

[0410] The precipitate was vacuum filtered using a 0.25-micron filter. The product was then washed three times and mixed with approximately 300 mL of water, filtered at each step to remove excess sodium until less than 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 with 0.5% Na. As will be readily understood by those skilled in the art, the ratio of iron to zinc components can be adjusted. For example, catalysts with the following Fe:Zn ratios of 0.5% Na by weight have been synthesized according to the above method: 1:1, 2:1, 3:1, 4:1, and 6:1.

[0411] Example 11: Catalyst evaluation for CO2 hydrogenation.

[0412] The FeZn catalyst was prepared using the methods of Examples 1 and 10, wherein the molar ratio of iron to zinc was approximately 6:1, but different metal promoters, namely Na, Rh, or Cs, were used. The catalyst was granulated to a size of 40-60 mesh and pretreated with H2 for 5 hours at 623 K, 150 PSIG, and GHSV 1200. It was then conditioned with syngas (H2 / CO = 2) at 623 K and GHSV 600. The catalyst was subsequently tested for CO2 hydrogenation 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, 450 PSIG, CO2 to C2 values ​​were measured for each of the different catalysts using feed gas H2 = 72 mol%, CO2 = 24 mol%, and N2 = 4 mol% as internal standards. 10 -C 16 Conversion rate of alkanes and / or alkenes.

[0413] Table 7: Product distribution of FeZn catalysts containing Group IA or Group IIA metals

[0414]

[0415] Methane production is a factor in catalyst effectiveness because it is undesirable. Therefore, the lower the methane production (SC1), the better the catalyst. O / P is the ratio of olefins to alkanes produced through the reaction between the feed and 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 alkane ratio, and a greater amount of C5+ products.

[0416] Although this example 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.

[0417] 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 its effect on methane yield and O / P selectivity.

[0418] Table 8: Product distribution when H2 partial pressure decreases

[0419]

[0420] It was found that decreasing the H2 / CO2 ratio from 3 to 2 improved both the methane selectivity (SC1) and the O / P ratio. Furthermore, the test showed no significant difference in product selectivity between 6Fe:1Zn and 2.25Fe:1Zn.

[0421] Example 12: Evaluation of catalysts for CO2 hydrogenation using olefin- and CH4-rich feedstocks

[0422] The catalyst (e.g., FeZnNa) prepared by the method in Example 10 was granulated to a size of 40-60 mesh and pretreated with H2 for 5 hours at 623 K, 150 PSIG, and GHSV 1200. It was then conditioned with syngas (H2 / CO=2) at 623 K and GHSV 600. The catalyst was subsequently tested for CO2 hydrogenation 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, CO2 to C2H4 was measured using feed gas H2 = 47 mol%, CO2 = 23.8 mol%, CO = 3 mol%, CH4 = 15 mol%, C2H6 = 2.2 mol%, C3H6 = 2.3 mol%, C3H8 = 0.3%, and N2 = 4 mol% as internal standards. 10 -C 16 Conversion rates of alkanes and / or alkenes. Expected C 5+ The production of alkanes and / or olefins will increase while the production of methane will decrease.

[0423] Table 9: Expected Product Distribution of Mixed Hydrocarbon Feed

[0424]

[0425] Example 13: Extrudate Synthesis Method - Sodium Aluminate Binder

[0426] The nutri-bullet was used to blend 80 g of powdered catalyst (FeZnNa) from Example 10, 20 g of sodium aluminate, and 1 g of STEROTEX. ® To form a well-mixed dry powder, nitric acid was added dropwise to 15.7951 g of deionized water to form solution A. Solution A was then added dropwise to the powder under constant stirring. An additional 10.2 g of deionized water was added to the slurry to obtain an extrudable dough. The prepared dough was extruded at 45 Hz to form extrudates with a diameter of 1.6 mm. The first extrudate was discarded. Successful extrudates were collected separately. The extrudates were dried at 120 °C for 2 hours, followed by calcination at 350 °C for 4 hours to prepare the shaped catalyst.

[0427] Example 14: Extrusion Synthesis Method - Sodium Silicate Binder

[0428] The nutri-bullet was used to blend 80 g of powdered catalyst (FeZnNa) from Example 10, 20 g of sodium silicate, and 1 g of STEROTEX. ® To form a well-mixed dry powder, nitric acid was added dropwise to 16.0213 g of deionized water to form solution A. Solution A was then added dropwise to the powder under constant stirring. An additional 9.3138 g of deionized water was added to the slurry to obtain an extrudable dough. The prepared dough was extruded at 45 Hz to form extrudates with a diameter of 1.6 mm. The first extrudate was discarded. Successful extrudates were collected separately. The extrudates were dried at 120 °C for 2 hours and calcined at 350 °C for 4 hours to prepare the shaped catalyst.

[0429] Example 15: Detailed Method for Extrusion Synthesis - Potassium Silicate Binder

[0430] The nutri-bullet was used to blend 80 g of powdered catalyst (FeZnNa) from Example 10, 20 g of potassium silicate, and 1 g of STEROTEX. ® To form a well-mixed dry powder, nitric acid was added dropwise to 30.3788 g of deionized water to form solution A. Solution A was then added dropwise to the powder under constant stirring. An additional 10.2 g of deionized water was added to the slurry to obtain an extrudable dough. The prepared dough was extruded at 45 Hz to form extrudates with a diameter of 1.6 mm. The first extrudate was discarded. Successful extrudates were collected separately. The extrudates were dried at 120 °C for 2 hours and calcined at 350 °C for 4 hours to prepare the shaped catalyst.

[0431] Example 16: Catalyst Evaluation for CO2 Hydrogenation

[0432] Powdered catalyst samples were prepared according to the procedure described in Example 10, with a final composition of Fe:Zn molar ratio of 2:1 and 0.61 wt% Na. The powdered catalyst was segmented and processed according to the procedure in Example 11, the difference being the incorporation of different binders to prepare 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 5 was prepared. Sample 6 was prepared using undoped silica binder (Hi-Sil). Sample 7 was prepared using Na-doped silica binder. Sample 8 was prepared using K-doped silica binder.

[0433] After reaching a steady state, the effluent or liquid product from the conversion reaction is collected. The steady state can be measured over time-to-run (TOS) or determined by collecting samples approximately every 24 hours and testing the metal concentrations in the samples. In typical experiments, liquid products (hydrocarbon and aqueous phases) 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 subsequently analyzed using ICP-MS. Separately, the aqueous product of the sample is injected into the instrument, where plasma ionizes the sample to provide mass spectrometry readings. The MS data are analyzed to obtain metal concentrations, and the total concentration is calculated by adding the phase concentrations calculated for each sample. The total metal concentrations in both the aqueous and oil phases are summed and reported as total metal leaching in Table 10.

[0434] Table 10: Examples of the influence of binders on the performance of active metal catalysts

[0435]

[0436]

[0437] The results were compared between samples of shaped catalysts with different binder compositions. The performance of sample 2, with an undoped binder, was compared with that of sample 3, which had a sodium aluminate binder. The results were evaluated using doped binders, methane selectivity, and C... 5+ Hydrocarbon selectivity was significantly improved. Specifically, between sample 2 and sample 3, SC1 decreased by 37.5%, and SC... 5+ An increase of 61%.

[0438] The performance of samples 4 and 5 with undoped binders was compared with that of samples 6 and 7 with sodium silicate and potassium silicate binders. The use of doped binders significantly improved methane selectivity and C2O3O4O5O3O4O5O3O4O5O6O7 ... 5+ Hydrocarbon selectivity. Specifically, between the undoped sample 4 and the doped samples 6 and 7, SC1 decreased by 49%, and SC... 5+ The increases were 36% and 38% respectively. That is, between the undoped sample 5 and the doped samples 6 and 7, SC1 decreased by 53% and 52% respectively, and SC... 5+ They increased by 70% and 72% respectively.

[0439] Example 17: Leaching rates of different metals during runtime

[0440] Leaching rates were tested for the powdered catalyst from Example 1 (with a final composition of Fe:Zn = 2:1 molar ratio and 0.61 wt% Na) and the shaped catalyst extrudate from Sample 3 after different run times. Metal leaching of the catalysts was analyzed using ICP-MS. Liquid products (hydrocarbon / oil and aqueous phases) 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 in the water fraction because the reaction had reached a steady state and the metal content in the oil fraction was less than 1 ppm. Table 11 shows the metal leaching rates for the powdered catalyst, and Table 12 shows the metal leaching rates for the shaped catalyst. When comparing similar run times, the introduction of a binder showed a reduced metal leaching rate.

[0441] Table 11: FeZn=2 molar ratio, 1% wt Na powder catalyst

[0442]

[0443]

[0444] Table 12: FeZn = 2 molar ratio, 1% wt Na, extruded with sodium aluminate binder

[0445]

[0446] Example 18: Toluene alkylation on β-zeolite alkylation catalyst

[0447] In this example, the alkylation catalyst comprises β-zeolite. The β-zeolite in H form was granulated, pulverized, and sieved to a particle size of 0.25–0.4 mm. 2.6 g of this granulated sample was diluted with silicon carbide (0.4 mm–0.25 mm) to obtain a 10 cm⁻¹ particle size. 3 The bed volume was determined. The mixture was loaded into a downflow stainless steel fixed-bed reactor and fed at a molar ratio of 4 for toluene and 1-hexene at 200 °C, 35 bar, and a WHSV of 1.6 h⁻¹ based on the total feed. The composition of the liquid product taken from the tank after 18 hours was determined by GC-FID analysis. A 96% hexene conversion was achieved. Of this, 99% was obtained through alkylation and 1% through oligomerization. The selectivity for monoalkylation products was 96%, and the selectivity for dialkylation products was 4%.

[0448] Example 19: Oligopolymerization of 1-hexene on PSH-3 catalyst

[0449] In this example, the oligomeric catalyst comprises PSH-3. The H-form PSH-3 is granulated, pulverized, and sieved to a particle size of 0.25–0.4 mm. 1.25 g of this granulated sample is diluted with silicon carbide (0.4 mm–0.25 mm) to obtain a 10 cm⁻¹ particle size. 3 The bed volume was determined. The mixture was loaded into a downflow stainless steel fixed-bed reactor and treated with the 1-hexene feedstock at a temperature of 190 °C, a pressure of 35 bar, and a WHSV of 1 h⁻¹ based on 1-hexene. The composition of the liquid product taken from the tank after 20 hours was determined by GC-FID analysis. It was found that 81 wt% of the 1-hexene feedstock was converted into hexene dimers and trimers, of which 85 wt% of the oligomerization product was a hexene dimer.

[0450] Example 20: Oligopolymerization / alkylation of 1-hexene and toluene on PSH-3 and β catalysts

[0451] In this example, the alkylation catalyst comprises β-zeolite, and the oligomerization catalyst comprises PSH-3. The PSH-3 or β-zeolite in H form, or combinations of these catalysts using a stacked bed catalyst concept, are granulated, pulverized, and sieved to a particle size of 0.25–0.4 mm. 1.25 g of this granulated sample is diluted with silicon carbide (0.4 mm–0.25 mm) to obtain a 10 cm⁻¹ particle size. 3The mixture was loaded into a downflow stainless steel fixed-bed oligomerization-alkylation reactor and treated with different feed ratios of 1-hexene and aromatic sources at 190 °C, 35 bar, and a WHSV of 1 h⁻¹ based on the mixture. The composition of the liquid product removed from the tank after 20 hours was determined by GC-FID analysis. GC analysis data indicated high conversions of hexene and toluene, and that both products were obtained through aromatic alkylation and hexene oligomerization.

[0452] Example 21: Selectivity Evaluation of Aromatic Catalysts

[0453] Zn-modified ZSM-5 was synthesized using an ion exchange method, and its selectivity for converting olefins to aromatics was evaluated. The reaction conditions were set as follows:

[0454] 2 g catalyst, 500°C, 50 psi

[0455] 140 sccm of a mixture of N2 and propylene (N2:propylene = 3.4:1).

[0456] The reaction products were analyzed, and the results are presented in Tables 9 and 10. All propylene conversions were greater than 95%.

[0457] Table 13: Selectivity of Zn-modified catalysts (mol%)

[0458]

[0459] Table 14: Aromatic hydrocarbon distribution (wt%) of Zn-modified catalysts

[0460]

[0461] In addition, all propylene conversion rates were greater than 95%.

[0462] Example 22: Stability Assessment of Aromatic Hydrocarbon Catalysts

[0463] Zn-modified ZSM-5 was synthesized using an ion exchange method, and its stability in the conversion of olefins to aromatics was evaluated. The reaction conditions were set as follows:

[0464] 2 g catalyst, 500°C, 50 psi

[0465] A mixture of CO2, N2 and propylene at 140 sccm (CO2:N2:propylene = 1.4:1:1).

[0466] The reaction products were analyzed over time. The results are shown in... Figure 7 In the middle. As the graph shows, the selectivity of aromatics remained essentially constant from approximately 10 hours of operation to approximately 50 hours. Furthermore, the percentage of each listed hydrocarbon remained below 10% and essentially constant.

[0467] Example 23: Examples of fuel compositions

[0468] Renewable fuels are produced by contacting carbon dioxide and hydrogen with a catalyst to generate a mixture of n-alkanes, isoalkanes, cycloalkanes, and aromatics. The product is analyzed by gas chromatography-mass spectrometry (GC-MS) and further characterized according to each standard method specified in Table 15 below.

[0469] Table 15. Analytical results of exemplary fuel compositions

[0470]

[0471] Example 24: Comparison of aviation fuel produced by the disclosed method with conventional aviation fuel

[0472] A comparison was made between synthetic Jet A prepared according to the above method and conventional (petroleum-based) Jet A on a small turbojet engine. Both fuels were tested sequentially in the same facility using the same engine and instrumentation. The test engine was initially run with conventional Jet A, with a 5% oil mixture added to provide necessary lubrication. The test fuel was fed from a temporary nitrogen-pressurized 2-gallon liquid distribution tank. After completing the conventional Jet A operation, the fuel tank and fuel lines were purged and replaced with synthetic jet fuel containing the 5% oil mixture, and the test was repeated. The engine was operated at multiple speeds and held for 1.5 minutes under each different operating condition to stabilize the operating temperature. Engine speed and exhaust temperature were recorded during the last 20 seconds of each operating condition. The measured data were averaged and reported as data points.

[0473] Engine start-up times for the two fuels were also compared. After completing the above performance tests, the engine was turned off and allowed to cool for 15 minutes, and the starter battery was recharged. The engine was then started, and the engine acceleration for each fuel was recorded over time until a stable idle speed was reached.

[0474] Test results showed no difference between the two fuels in terms of recorded engine speed, exhaust temperature, and start-up time.

[0475] Merging by reference

[0476] All publications and patents mentioned herein are incorporated herein by reference in their entirety, as if each individual publication or patent were specifically and separately indicated to be incorporated herein by reference. In case of conflict, this application (including any definitions herein) shall prevail.

[0477] equivalent

[0478] While specific embodiments of the invention have been discussed, the above description is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this description and the appended claims. The full scope of the invention, as well as the full scope of its equivalents, the description, and such variations, should be determined with reference to the claims.

Claims

1. A method for producing aviation fuel, comprising: The first reducing gas and the first carbon source gas are brought into contact with the reduction catalyst to obtain: Contains one or more C 4-9 A mixture of intermediate hydrocarbon products from alkanes and / or alkenes; and Contains one or more C 10-16 A mixture of target hydrocarbon products, including alkanes and / or olefins; and The mixture of intermediate hydrocarbon products, an optional second reducing gas, and an optional second carbon source gas are contacted with an aromatic catalyst to obtain a product containing one or more C atoms. 9-16 A mixture of target aromatic products.

2. The method according to claim 1, wherein the reduction catalyst comprises: One or more of the first element selected from iron or cobalt; One or more of the second element selected from copper and zinc; and One or more Group VI, Group VII, Group VIII, Group IX, Group X or Group XI metal additives may be selected.

3. The method according to claim 1, wherein the reduction catalyst comprises: copper; Zinc; One or more of the first element selected from iron or cobalt; oxygen; Optional aluminum; and One or more Group IA or Group IIA metals may be selected; The one or more first elements are present in an amount of about 1 wt.% to about 40 wt.% of the total amount of the copper, zinc, the first element and the optional Group IA or Group IIA metals.

4. The method according to any one of claims 1 to 3, wherein the reduction catalyst comprises one or more Group IA or Group IIA metals.

5. The method according to claim 1, wherein the reduction catalyst comprises: iron; The first element selected from copper, zinc, cobalt, or combinations thereof; and One or more of the second elements selected from Group IA and Group IIA metals.

6. The method of claim 5, wherein the reduction catalyst comprises the first element, and wherein the first element is copper, zinc, or a combination thereof.

7. The method according to claim 5, wherein the first element is zinc; and wherein the catalyst does not contain copper or cobalt.

8. The method according to any one of claims 5 to 7, wherein the molar ratio of iron to the first element is about 1:1 to about 7:

1.

9. The method according to any one of claims 5 to 8, wherein the molar ratio of iron to the first element is about 2:1 to about 6:

1.

10. The method according to any one of claims 5 to 9, wherein the reduction catalyst comprises one or more Group IA or Group IIA metals; and the one or more Group IA or Group IIA metals are selected from magnesium, calcium, potassium, sodium, cesium, or combinations thereof.

11. The method of claim 10, wherein the one or more Group IA or Group 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.

12. The method of claim 10, 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.

13. The method according to any one of claims 5 to 12, wherein the iron is in the form of iron oxide, and the iron oxide comprises magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof.

14. The method according to any one of claims 5 to 13, wherein the reduction catalyst has a methane selectivity of less than about 11 mol% of carbon.

15. The method of claim 14, wherein the reduction catalyst has a methane selectivity of less than about 10 mol% of carbon.

16. The method of claim 1, wherein the reduction catalyst comprises: iron; Zinc; One or more second elements selected from Group IA, Group IIA, and Group X metals; and The binder is selected from boehmite, silica-alumina hydrate, aluminates, silica, silicates, boehmite alumina, bentonite, montmorillonite clay, zirconates, tungsten, or any combination thereof.

17. The method of claim 16, wherein the adhesive comprises an accelerator element selected from Na, K, Cs, Li, Rb, or combinations thereof.

18. The method of claim 17, wherein the adhesive is selected from sodium aluminate, potassium aluminate, sodium silicate, potassium silicate, sodium zirconate, potassium zirconate, Na-tungsten, K-tungsten, or combinations thereof.

19. The method according to any one of claims 1 to 18, wherein contacting the first reducing gas and the first carbon source gas with the reducing catalyst is carried out at an alkane temperature of about 100°C to about 600°C.

20. The method according to any one of claims 1 to 19, wherein contacting the first reducing gas and the first carbon source gas with the reducing catalyst is carried out at an alkane pressure of about 50 psi to about 4000 psi.

21. The method according to any one of claims 1 to 20, wherein the aromatic catalyst comprises zeolite.

22. The method according to claim 21, wherein the zeolite is selected from 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-zeolite (LTL), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof.

23. The method according to claim 21 or 22, wherein the zeolite is ZSM-5.

24. The method according to any one of claims 21 to 23, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 1000.

25. The method according to any one of claims 21 to 24, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 400.

26. The method according to any one of claims 21 to 25, wherein the zeolite comprises a modifier.

27. The method of claim 26, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt or combinations thereof.

28. The method according to any one of claims 26 or 27, wherein the modifier is present in an amount of about 0 wt% to about 10 wt% of the total aromatic catalyst.

29. The method according to any one of claims 24 to 26, wherein the zeolite is ZSM-5 modified with Ga, Fe, Mn, Zn in an amount of about 0.1 wt% to about 5 wt% of the total aromatic catalyst.

30. The method according to any one of claims 1 to 29, wherein contacting the intermediate hydrocarbon product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the aromatic catalyst is carried out at an aromatic temperature of about 100°C to about 450°C.

31. The method according to any one of claims 1 to 30, wherein contacting the intermediate hydrocarbon product mixture, optionally the second reducing gas, and optionally the second carbon source gas with the aromatic catalyst is carried out at an aromatic pressure of about 50 psi to about 1000 psi.

32. The method according to any one of claims 1 to 31, wherein the aromatic catalyst has a selectivity of about 5 mol% to about 20 mol% for the target aromatic product mixture.

33. The method according to any one of claims 1 to 32, wherein the aromatic catalyst has a selectivity of about 7 mol% to about 15 mol% for the target aromatic product mixture.

34. The method according to any one of claims 1 to 33, wherein the ratio of olefins to alkanes in the mixture of hydrocarbon products is at least about 3.

35. The method according to any one of claims 1 to 34, wherein the ratio of olefins to alkanes in the hydrocarbon product mixture is greater than about 5.

36. The method according to any one of claims 1 to 35, wherein contacting the first reducing gas and the carbon source gas with the reducing catalyst further yields: Contains one or more C 2-4 A mixture of light hydrocarbon products of alkanes and / or alkenes.

37. The method of claim 36, wherein the ratio of olefins to alkanes in the light hydrocarbon product mixture is at least about 5.

38. The method according to claim 36 or 37, wherein the ratio of olefins to alkanes in the light hydrocarbon product mixture is greater than about 8.

39. The method according to any one of claims 36 to 38, wherein the ratio of olefins to alkanes in the light hydrocarbon product mixture is greater than about 10.

40. The method according to any one of claims 1 to 39, wherein contacting the middle hydrocarbon product mixture with the aromatic catalyst further yields: Contains one or more C 6-8 A mixture of light aromatic hydrocarbon products.

41. The method of claim 40, further comprising: The light hydrocarbon product mixture and the light aromatic hydrocarbon product mixture are contacted with an alkylation catalyst to obtain a target alkyl aromatic hydrocarbon product mixture containing one or more alkylated aromatic hydrocarbons.

42. The method according to any one of claims 40 to 41, further comprising: The mixture of light hydrocarbon products is contacted with an oligomerizing catalyst to obtain: Contains one or more C 10-16 A mixture of target oligomers of alkanes and / or olefins.

43. The method of claim 40, further comprising: The light hydrocarbon product mixture and the light aromatic product mixture are contacted with an alkylation catalyst and an oligomerization catalyst to obtain a product containing one or more C4 ...5444454544454545465444454545465465444545454654654654665454654654665454654665454654665465466545465466546546654654665465466546546654654665465466 9-16 Aromatics and one or more C 10-16 A mixture of target products consisting of alkanes and / or olefins.

44. The method according to any one of claims 41 to 43, wherein the alkylation catalyst is an acid, such as HF, solid phosphoric acid (SPA); a Friedel-Crafts alkylation catalyst (e.g., HF / AlCl3); tungsten; platinum; or zeolite.

45. The method according to any one of claims 41 to 44, wherein the alkylation catalyst is a zeolite.

46. ​​The method according to claim 43 or 45, wherein the zeolite is selected from: Y-type zeolite; β-zeolite; ZSM-type zeolite (e.g., ZSM-5, ZSM-11, HZSM-5, ZSM-12, ZSM-22, ZSM-57); SAPO-type zeolite (e.g., SAPO-5, SAPO-11, SAPO-31, SAPO-41); L-zeolite (LTL); mordenite; DA-114; microcrystalline USY zeolite; MWW structure type zeolite, such as MCM-22, MCM-36, MCM-49, PSH-3 and MCM-56; and combinations thereof.

47. The method according to any one of claims 44 to 46, wherein the zeolite is MCM-22, MCM-49, PSH-3, mordenite, Y-type zeolite, or β-zeolite.

48. The method according to any one of claims 41 to 47, wherein the contact between the light hydrocarbon product mixture and the light aromatic product mixture and the alkylation catalyst is carried out at an alkylation temperature of about 50°C to about 300°C.

49. The method according to any one of claims 41 to 47, wherein the contact of the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst is carried out at an alkylation pressure of about 0 psig to about 1000 psig.

50. The method according to any one of claims 42 to 49, wherein the oligomeric catalyst is a zeolite or a molecular sieve.

51. The method according to any one of claims 42 to 50, wherein the oligomeric catalyst is an amorphous or crystalline aluminosilicate molecular sieve.

52. The method according to any one of claims 42 to 50, wherein the oligomeric catalyst comprises a zeolite selected from the group consisting of: 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; zeolites of the MWW structure type, such as MCM-22, MCM-36, MCM-49, PSH-3 and MCM-56; or combinations thereof.

53. The method according to any one of claims 42 to 50, wherein the oligomeric catalyst comprises a zeolite selected from ZSM-5, β-zeolite, MCM-22, MCM-49, PSH-3, mordenite, or SAPO-5.

54. The method according to any one of claims 42 to 53, wherein contacting the light hydrocarbon product mixture with the oligomerization catalyst is carried out at an oligomerization temperature of about 50°C to about 400°C.

55. The method according to any one of claims 42 to 54, wherein contacting the light hydrocarbon product mixture with the oligomerization catalyst is carried out at an oligomerization temperature of about 50°C to about 250°C.

56. The method according to any one of claims 42 to 55, wherein contacting the light hydrocarbon product mixture with the oligomerizing catalyst is carried out at an oligomerization pressure of about 0 psi to about 500 psi.

57. The method according to any one of claims 42 to 56, wherein contacting the light hydrocarbon product mixture with the oligomerizing catalyst is carried out at an oligomerization pressure of about 0 psi to about 200 psi.

58. The method according to any one of claims 35 to 57, comprising passing the light hydrocarbon product mixture and / or the light aromatic product mixture through an adsorbent bed before contacting the alkylation and / or oligomerization catalyst.

59. The method according to any one of claims 42 to 58, wherein contacting the light hydrocarbon product mixture with the oligomerizing catalyst further yields: Contains one or more C 1-2 A mixture of light oligomers of hydrocarbons.

60. The method of claim 59, further comprising: The carbon source gas is combined with the mixture of light oligomers before contacting the reduction catalyst.

61. The method according to any one of claims 42 to 60, wherein contacting the light hydrocarbon product mixture with the oligomerizing catalyst further yields: Contains one or more C 3-7 A mixture of medium-oligomery products of hydrocarbons.

62. The method of claim 61, further comprising: The light hydrocarbon product mixture is combined with the medium oligomer product mixture before contacting the oligomer catalyst.

63. The method according to any one of claims 41 to 62, wherein contacting the light hydrocarbon product mixture and / or the light hydrocarbon product mixture with the oligomerizing catalyst further yields: Contains one or more C 17-25 Mixtures of heavy oligomers of alkanes and / or olefins.

64. The method according to any one of claims 1 to 63, wherein contacting the first reducing gas and the carbon source gas with the reducing catalyst further yields: Contains one or more C 17-25 A mixture of heavy hydrocarbon products of alkanes and / or alkenes.

65. The method according to claim 63 or 64, further comprising: The third reducing gas and the mixture of heavy oligomers and / or the mixture of heavy hydrocarbon products are contacted with a hydrocracking catalyst to obtain a product containing one or more C244 compounds. 1-18 A mixture of hydrocracking products of alkanes and / or olefins.

66. The method of claim 65, wherein contacting the third reducing gas and the mixture of heavy oligomers and / or the mixture of heavy hydrocarbon products with the hydrocracking catalyst is carried out at a hydrocracking temperature of about 250°C to about 450°C.

67. The method according to claim 65 or 66, wherein contacting the third reducing gas and the mixture of heavy oligomers and / or the mixture of heavy hydrocarbon products with the hydrocracking catalyst is carried out at a hydrocracking pressure of about 0 psig to about 1000 psig.

68. The method according to any one of claims 1 to 65, wherein contacting the first reducing gas and the carbon source gas with the reducing catalyst further yields: Contains one or more C 1-2 A cyclic mixture of hydrocarbons, CO2, CO and / or H2.

69. The method of claim 67, further comprising: The circulating mixture is combined with the first reducing gas and / or the carbon source gas before contacting the reducing catalyst.

70. The method according to any one of claims 1 to 69, further comprising: The target hydrocarbon product mixture, the target aromatic product mixture, the target oligomeric product mixture, the target alkyl aromatic product mixture, and / or the target product mixture are blended to produce aviation fuel.

71. The method according to any one of claims 1 to 70, further comprising capturing carbon source gas from the gas feed stream.

72. The method according to any one of claims 1 to 71, wherein the first reducing gas, the second reducing gas and the third reducing gas are independently selected from H2, hydrocarbons, synthesis gas (CO / H2), or independently selected from flare gas, waste gas or natural gas or gases derived from flare gas, waste gas or natural gas.

73. The method according to any one of claims 1 to 71, wherein the first reducing gas, the second reducing gas and the third reducing gas are H2.

74. The method according to any one of claims 1 to 71, wherein the first reducing gas, the second reducing gas and the third reducing gas are hydrocarbons, such as CH4, ethane, propane or butane.

75. The method according to any one of claims 1 to 71, wherein the first reducing gas, the second reducing gas and the third reducing gas are flare gas, exhaust gas or natural gas or derived from flare gas, exhaust gas or natural gas.

76. The method according to any one of claims 1 to 75, wherein the first carbon source gas and / or the second carbon source gas is CO2.

77. The method according to any one of claims 1 to 76, wherein the molar ratio of the first reducing gas to the first carbon source gas is about 10:1 to about 1:

10.

78. A system for producing aviation fuel, comprising: First reducing gas feed; First carbon source gas feed; A reduction reactor containing a reduction catalyst, the reduction reactor having a first reducing gas inlet, a first carbon source inlet, a target hydrocarbon outlet and a middle 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; Optional second carbon source gas feed; and An aromatic reactor comprising an aromatic catalyst, the aromatic reactor having a middle hydrocarbon inlet, an optional second reducing gas feed inlet, an optional second carbon source gas feed inlet, and a target aromatic product outlet; wherein the middle hydrocarbon inlet is connected to the middle hydrocarbon outlet on the reduction reactor, the second reducing gas feed inlet is connected to the second reducing gas feed when present, and the second carbon source gas feed inlet is connected to the second carbon source gas feed when present.

79. The system of claim 78, wherein the reduction catalyst comprises: iron; The first element selected from copper, zinc, cobalt, or combinations thereof; and One or more second elements selected from Group IA and Group IIA metals.

80. The system of claim 79, wherein the first element is copper, zinc, or a combination thereof.

81. The system of claim 80, wherein the first element is zinc; and wherein the catalyst does not contain copper or cobalt.

82. The system according to claim 80 or 81, wherein the molar ratio of iron to the first element is from about 1:1 to about 7:

1.

83. The system according to any one of claims 80 to 82, wherein the molar ratio of iron to the first element is about 2:1 to about 6:

1.

84. The system according to any one of claims 80 to 83, wherein the one or more Group IA or Group IIA metals are selected from magnesium, calcium, potassium, sodium, cesium, or combinations thereof.

85. The system of claim 84, wherein the one or more Group IA or Group 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.

86. The system according to any one of claims 80 to 85, wherein the iron is in the form of iron oxide, and the iron oxide comprises magnetite (Fe3O4), hematite (Fe2O3), or a combination thereof.

87. The system according to any one of claims 78 to 86, wherein the aromatic catalyst comprises zeolite.

88. The system of claim 87, wherein the zeolite is selected from 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-zeolite (LTL), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof.

89. The system according to claim 87 or 88, wherein the zeolite is ZSM-5.

90. The system according to any one of claims 87 to 89, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 1000.

91. The system according to any one of claims 87 to 90, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 400.

92. The system according to any one of claims 87 to 91, wherein the zeolite comprises a modifier.

93. The system of claim 92, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt or combinations thereof.

94. The system according to any one of claims 92 or 93, wherein the modifier is present in an amount of 0 wt% to about 2 wt% of the total aromatic catalyst.

95. The system according to any one of claims 87 to 94, wherein the zeolite is ZSM-5 modified with Zn in an amount of about 0.1 wt% to about 5 wt% of the total aromatic catalyst.

96. The system according to any one of claims 78 to 95, further comprising: A first adsorbent bed having a middle hydrocarbon inlet and a middle hydrocarbon outlet; wherein the middle hydrocarbon inlet is connected to the middle hydrocarbon outlet on the reduction reactor, and the middle hydrocarbon outlet is connected to the middle hydrocarbon inlet on the aromatic hydrocarbon reactor.

97. The system according to claim 78 or 96, wherein the reduction reactor further comprises a light hydrocarbon outlet.

98. The system according to any one of claims 78 to 97, wherein the aromatics reactor further comprises a light aromatics product outlet.

99. The system of claim 98, further comprising: An alkylation reactor comprising an alkylation catalyst, the alkylation reactor comprising a light hydrocarbon inlet, a light aromatic hydrocarbon product inlet, and an alkyl aromatic hydrocarbon product outlet; wherein the light hydrocarbon inlet is connected to the light hydrocarbon outlet on the reduction reactor, and the light aromatic hydrocarbon product inlet is connected to the light aromatic hydrocarbon product outlet on the aromatic hydrocarbon reactor.

100. The system according to any one of claims 98 to 99, further comprising: An oligomerization reactor containing an oligomerization catalyst, the oligomerization reactor having a light hydrocarbon inlet and a target oligomer product outlet; wherein the light hydrocarbon inlet is connected to the light hydrocarbon outlet on the reduction reactor.

101. The system of claim 98, further comprising: An oligo-alkylation reactor comprising an oligomerization catalyst and an alkylation catalyst, the oligo-alkylation reactor having a light hydrocarbon inlet, a light aromatic product inlet, and a mixed target product outlet; wherein the light hydrocarbon inlet is connected to the light hydrocarbon outlet on the reduction reactor, and the light aromatic product inlet is connected to the light aromatic product outlet on the aromatics reactor.

102. The system according to any one of claims 99 to 101, wherein the alkylation catalyst is an acid, such as HF, solid phosphoric acid (SPA); a Friedrich-Krawst alkylation catalyst (e.g., HF / AlCl3); tungsten; platinum; or zeolite.

103. The system according to any one of claims 99 to 102, wherein the alkylation catalyst is a zeolite.

104. The system according to claim 100 or 101, wherein the oligomerizing catalyst is a zeolite or a molecular sieve.

105. The system according to any one of claims 99 to 104, further comprising: A second adsorbent bed having a light hydrocarbon inlet and / or a light aromatic hydrocarbon product inlet and a light hydrocarbon outlet and / or a light aromatic hydrocarbon product outlet; wherein the light hydrocarbon inlet, if present, is connected to the light hydrocarbon outlet on the reduction reactor, the light aromatic hydrocarbon product inlet, if present, is connected to the light aromatic hydrocarbon product outlet on the aromatic hydrocarbon reactor, the light hydrocarbon outlet, if present, is connected to the light hydrocarbon inlet on the alkylation reactor, the oligomerization reactor, or the oligomerization-alkylation reactor, and the light aromatic hydrocarbon product outlet, if present, is connected to the light aromatic hydrocarbon product inlet on the alkylation reactor or the oligomerization-alkylation reactor.

106. The system according to any one of claims 100 to 105, wherein the oligomerization reactor and / or the oligo-alkylation reactor further comprises a light oligomer product outlet.

107. The system of claim 106, wherein the light oligomer product outlet on the oligomerization reactor and / or the oligo-alkylation reactor is connected to the first carbon source gas feed and / or the second carbon source gas feed.

108. The system according to any one of claims 100 to 107, wherein the oligomerization reactor and / or the oligomer-alkylation reactor further comprises an oligomer product outlet.

109. The system of claim 108, wherein the oligomerization reactor, the alkylation reactor, and / or the oligomer-alkylation reactor further comprises: A medium oligomer inlet, wherein the medium oligomer inlet is connected to the medium oligomer outlet on the oligomerization reactor and / or the oligomerization-alkylation reactor.

110. The system according to any one of claims 100 to 109, wherein the oligomerization reactor and / or the oligo-alkylation reactor further comprises a heavy oligomer product outlet.

111. The system according to any one of claims 78 to 110, wherein the reduction reactor further comprises a heavy hydrocarbon outlet.

112. The system of claim 111, further comprising: Third reducing gas feed; A hydrocracking reactor comprising a hydrocracking catalyst, the hydrocracking reactor having a reducing gas inlet, a heavy oligomer inlet and / or a heavy hydrocarbon inlet, and a hydrocracking product outlet; wherein the reducing gas inlet is connected to the third reducing gas feed, the heavy oligomer inlet, if present, is connected to the heavy oligomer outlet on the oligomerizing reactor and / or the oligomer-alkylation reactor, and the heavy hydrocarbon inlet, if present, is connected to the heavy hydrocarbon outlet on the reducing reactor.

113. The system according to any one of claims 78 to 112, wherein the reduction reactor further comprises a reducing gas outlet, wherein the reducing gas outlet is connected to the first carbon source gas feed and / or the first reducing gas feed.

114. The system according to any one of claims 78 to 113, further comprising: A blender having a target hydrocarbon product inlet, a target aromatic product inlet, an alkyl aromatic product inlet, a target oligomer product inlet and / or a mixed target product inlet, and an aviation fuel outlet; wherein the target hydrocarbon inlet, when present, is connected to the target hydrocarbon product outlet on the reduction reactor, the target aromatic product inlet, when present, is connected to the target aromatic product outlet on the aromatic reactor, the alkyl aromatic product inlet, when present, is connected to the alkyl aromatic product outlet on the alkylation reactor, the target oligomer product inlet, when present, is connected to the target oligomer product outlet on the oligomerization reactor, and the mixed target product inlet, when present, is connected to the mixed target product outlet on the oligomerization-alkylation reactor.

115. A reduction catalyst composition comprising: iron; Zinc; One or more second elements selected from Group IA, Group IIA, and Group X metals; and The binder is selected from boehmite, silica-alumina hydrate, aluminates, silica, silicates, boehmite alumina, bentonite, montmorillonite clay, zirconates, tungsten, or any combination thereof.

116. The reduction catalyst composition of claim 115, wherein the binder comprises a promoter element selected from Na, K, Cs, Li, Rb or combinations thereof.

117. The reduction catalyst composition according to claim 115 or 116, wherein the reduction catalyst has a selectivity of less than about 11 mol% for the conversion of carbon dioxide to methane.

118. The reduction catalyst composition according to any one of claims 115 to 117, wherein the reduction catalyst retains activity of more than about 75% for more than about one year.

119. The reduction catalyst composition according to any one of claims 115 to 118, wherein the molar ratio of iron to zinc is from about 1:1 to about 7:

1.

120. The reduction catalyst composition according to any one of claims 115 to 119, wherein the molar ratio of iron to zinc is from about 1:1 to about 4:

1.

121. The reduction catalyst composition according to any one of claims 115 to 120, wherein the binder is selected from sodium aluminate, potassium aluminate, sodium silicate, potassium silicate, sodium zirconate, potassium zirconate, Na-tungsten, K-tungsten, or combinations thereof.

122. The reduction catalyst composition according to any one of claims 115 to 121, wherein the amount of the binder is from about 0.1% by weight to about 60% by weight of the total catalyst.

123. The reduction catalyst composition according to any one of claims 115 to 122, wherein one or more second elements are group IA or group IIA metals selected from magnesium, calcium, potassium, sodium, cesium, or combinations thereof.

124. The reduction catalyst composition according to claim 123, comprising a Group IA metal selected from potassium, sodium, or combinations thereof.

125. The reduction catalyst composition according to claim 123 or 124, wherein the one or more Group IA or Group IIA metals are present in an amount of about 0.2% to about 10% of the total weight of iron and zinc.

126. The reduction catalyst composition according to any one of claims 115 to 122, wherein the one or more second elements are group X metals selected from the group consisting of palladium, platinum, iridium, nickel, rhodium, and any combination thereof.

127. The reduction catalyst composition according to any one of claims 115 to 126, wherein when the catalyst is contacted with a continuous fluid flow for about 100 hours to about 1000 hours, the total concentration of iron, zinc and one or more second elements in the effluent is less than about 50 ppm.

128. The reduction catalyst according to any one of claims 115 to 127, wherein the reduction catalyst is effective against C 5+ Hydrocarbons exhibit selectivity greater than approximately 28 mol% of carbon.

129. An aromatic catalyst comprising optionally modified zeolite, The zeolite mentioned is selected from 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-zeolite (LTL), mordenite, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. The aromatic catalyst described herein exhibits selectivity for aromatics exceeding approximately 50 mol% carbon; and The aromatic catalyst described therein has a selectivity for methane of less than about 8 mol% carbon.

130. The aromatic catalyst according to claim 129, wherein the zeolite is ZSM-5.

131. The aromatic catalyst according to any one of claims 129 or 130, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 400.

132. The aromatic catalyst according to any one of claims 129 to 131, wherein the zeolite has a silica-alumina ratio (SAR) of about 30 to about 280.

133. The aromatic catalyst according to any one of claims 129 to 132, wherein the zeolite comprises a modifier.

134. The aromatic catalyst according to claim 133, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt or combinations thereof.

135. The aromatic catalyst according to any one of claims 133 or 134, wherein the modifier is present in an amount of 0 wt% to about 10 wt% of the total aromatic catalyst.

136. The aromatic catalyst according to claim 133, wherein the zeolite is ZSM-5 modified with Zn in an amount of 0.1 wt% to about 5 wt% of the total aromatic catalyst.

137. The aromatic catalyst according to any one of claims 129 to 136, wherein the selectivity for aromatics exceeds about 55 carbon moles.

138. The aromatic catalyst according to any one of claims 129 to 137, wherein the selectivity for aromatics exceeds about 60 carbon moles.

139. The aromatic catalyst according to any one of claims 129 to 138, wherein the aromatic catalyst is effective against C 9-14 Aromatic hydrocarbons exhibit selectivity of approximately 5 mol% to approximately 20 mol%.

140. An oligomerization-alkylation catalyst for converting a mixture of light aromatic products into compounds containing one or more C atoms. 9-14 Aromatics and one or more C 10-16 A mixture of target products of alkanes, wherein the oligomerization-alkylation catalyst comprises: a liquid acid; a Friedel-Crafts alkylation catalyst (e.g., HF / AlCl3); an amorphous heterogeneous acid catalyst; a heterogeneous acid catalyst, such as zeolite or molecular sieve; and combinations thereof.

141. An oligo-alkylation catalyst according to claim 140, wherein the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve.

142. An oligomeric-alkylation catalyst according to claim 140, wherein the oligomeric-alkylation 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; zeolites of the MWW structure type, such as MCM-22, MCM-36, MCM-49, PSH-3 and MCM-56; and any combination thereof.

Images