Systems, methods, and catalysts for the production of sustainable aviation fuel

Abstract

Provided herein are systems and methods for converting CO2 and a reduction gas, such as H2 or a hydrocarbon, using a reduction catalyst and an aromatic catalyst into mixtures of paraffins, and aromatics for use as aviation fuel. The reduction catalyst and aromatic catalyst, and systems and methods incorporating the same, provide advantages over other methods in the art related to increased yield, catalyst stability and longevity.

Description

[0001] SYSTEMS, METHODS, AND CATALYSTS FOR THE PRODUCTION OF SUSTAINABLE AVIATION FUEL

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of 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 each of which are incorporated herein by reference in their entirety.

[0004] BACKGROUND

[0005] As the concentration of carbon dioxide in the atmosphere increases, it is advantageous to develop technologies that remove or mitigate carbon dioxide emissions. As such, development of transportation technologies that afford decreased CO2 emissions, such as electric cars, has been a priority. However, the development of electric airplanes, especially commercial electric airplanes, is problematic due to low energy density of the batteries required. Therefore, a need remains for the development of sustainable aviation fuel (SAF), and currently available technologies will not be able to meet market demand.

[0006] Currently, jet fuel (Jet- A) consists of normal paraffins, iso-paraffins, naphthenes, and aromatics refined from crude oil. In order to produce SAF that can be directly substituted for Jet- A, the SAF has to match the current composition of Jet-A derived from crude oil. Current technologies for SAF production involve making SAF from vegetable oils, animal fats, and waste oils. However, the SAF made from these processes contains mainly paraffins, and does not have enough naphthenes and aromatics to be directly substituted for Jet-A derived from crude oil. Accordingly, there is a need for technologies that produce SAF that can be directly substituted for Jet-A derived from crude oil.

[0007] Additionally, certain processes for the production of paraffins and aromatics from CO2 involve the use of metal oxide catalysts and zeolite catalysts. However, the zeolite catalysts can suffer from deactivation pathways caused by (a) coke (carbon) formation in the pores of the zeolite, and (b) metal migration from the metal oxide catalyst to the zeolite catalyst, resulting in poisoning of the zeolite active sites. As such, there exists a need for processes for the production of aromatics and paraffins from CO2 (e.g., to prepare drop-in SAF compositions) which mitigate these zeolite deactivation pathways. SUMMARY OF THE DISCLOSURE

[0008] Disclosed herein is a method for the production of aviation fuel. The method may include: (a) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C5-9 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more C10- 16 paraffins and / or olefins; and (b) contacting the medium hydrocarbon product mixture with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-14 aromatics. The step of contacting the medium hydrocarbon product mixture with an aromatic catalyst may also include providing a second reduction gas and / or a second carbon source gas, to afford a target aromatic product mixture comprising one or more C9-14 aromatics.

[0009] The method may further comprise: contacting the medium hydrocarbon product mixture with the aromatic catalyst further affords a light aromatic product mixture comprising one or more Ce-8 aromatics; and / or contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics; and / or contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins.

[0010] The method may further comprise: contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords a light oligomerized product mixture comprising one or more C1-2 hydrocarbons; and, optionally, combining the carbon source gas with the light oligomerized product mixture prior to contacting with the reduction catalyst.

[0011] A system for the production of aviation fuel is also disclosed herein. The system may include: (i) a first reduction gas feed; (ii) a first carbon source gas feed; (iii) a reduction reactor comprising a reduction catalyst; and (iv) an aromatic reactor comprising an aromatic catalyst. The system may also include a second reduction gas feed and / or a second carbon source gas feed. The reduction reactor may have a first reduction gas feed inlet, a first carbon source feed inlet, a target hydrocarbon outlet, and a medium hydrocarbon outlet. The first reduction gas feed inlet may be coupled to the first reduction gas feed, and the first carbon source gas feed inlet may be coupled to the first carbon source gas feed. The aromatic reactor may have a medium hydrocarbon inlet, optionally a second reduction as feed inlet, optionally a second carbon source gas feed inlet, and a target aromatic product outlet. The medium hydrocarbon inlet may be coupled to the medium hydrocarbon outlet on the reduction reactor. The second reduction gas feed inlet, when present, may be coupled to the second reduction gas feed, and the second carbon source gas feed inlet, when present, may be coupled to the second carbon source gas feed.

[0012] The aromatic reactor may further comprise a light aromatic product outlet, whereby optionally the system further comprises: an alkylation reactor comprising an alkylation catalyst. The alkylation reactor may comprise a light hydrocarbon inlet, a light aromatic product inlet, and an alkyl arene product outlet. The light hydrocarbon inlet may be coupled to the light hydrocarbon outlet on the reduction reactor, and the light aromatic product inlet may be coupled to the light aromatic product outlet on the aromatic reactor. The system may further comprise: an oligomerization reactor or an oligo-alkylation reactor comprising an oligomerization catalyst. The oligomerization reactor or oligo-alkylation reactor may comprise a light hydrocarbon inlet and a target oligomerized product outlet; wherein the light hydrocarbon inlet is coupled to the light hydrocarbon outlet on the reduction reactor. The oligomerization reactor, the alkylation reactor, and / or the oligo-alkylation reactor may further comprise: a medium oligomerized product inlet, wherein the medium oligomerized product inlet is coupled to the medium oligomerized product outlet on the oligomerization reactor and / or the oligo-alkylation reactor.

[0013] Also disclosed is an reduction catalyst comprising: iron; a first element selected from copper, zinc, cobalt, or a combination thereof; and one or more second elements selected from Group IA and IIA metals. The reduction catalyst may have a selectivity for CO2 conversion to methane of less than about 11 carbon mol%, or less than about 10 carbon mol%. The first element may be zinc, optionally the molar ratio of iron to zinc is about 1 : 1 to about 7: 1. The one or more second element may be magnesium, calcium, potassium, sodium, cesium, or a combination thereof. The one or more second element may be present in an amount of about 0.2% to about 1.5% of the total weight of iron plus the first element.

[0014] An aromatic catalyst comprising an optionally modified zeolite is also disclosed. The zeolite may be selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites, SAPO type zeolites, L zeolite (LTL), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA- 114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. The aromatic catalyst may have a selectivity for aromatics of over about 50 carbon mole%, over about 55 carbon mole%, or over about 60 carbon mole%; and / or a selectivity for methane of less than about 8 carbon mole%, or less than about 5 carbon mole%. The zeolite may be ZSM- 5, and / or having a silicon to aluminum ratio (SAR) of about 30 to about 400. The zeolite comprises a modifier, optionally selected from Ga, Fe, Mn, Zn, P, Pt, or a combination thereof, and / or present in an amount of 0 wt% to about 10 wt% of the total aromatic catalyst. The aromatic catalyst may have a selectivity for C9-14 aromatics of about 5 carbon mole% to about 20 carbon mole%.

[0015] Also disclosed is an oligo-alkylation catalyst for converting a light aromatic product mixture to a mixed target product mixture comprising one or more C9-14 aromatics and one or more Cio-16 paraffin, the oligo-alkylation catalyst comprising: a liquid acid, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AICI3), an amorphous heterogeneous acid catalyst, a heterogeneous acid catalyst, such as a zeolite or a molecular sieve, and a combination thereof. The oligo-alkylation catalyst may be an amorphous or crystalline aluminosilicate molecular sieve.

[0016] BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Fig- 1 is a process flow diagram for a system of the disclosure in which adsorbent beds are used to inhibit metal migration from the reduction catalyst.

[0018] Fig- 2 is a process flow diagram for a system of the disclosure in which adsorbent beds are used to inhibit metal migration from the reduction catalyst, with additional carbon source gas and reduction gas feeds to the aromatic reactor.

[0019] Fig- 3 is a process flow diagram for a system of the disclosure wherein arene alkylation and olefin oligomerization are carried out in separate reactors.

[0020] Fig. 4 is a process flow diagram for a system of the disclosure wherein arene alkylation and olefin oligomerization are carried out in separate reactors, with additional carbon source gas and reduction gas feeds to the aromatic reactor.

[0021] Fig. 5 is a process flow diagram for a system of the disclosure wherein arene alkylation and olefin oligomerization are carried out in the same reactor.

[0022] Fig. 6 is a process flow diagram for a system of the disclosure wherein arene alkylation and olefin oligomerization are carried out in the same reactor, with additional carbon source gas and reduction gas feeds to the aromatic reactor.

[0023] Fig. 7 is a process flow diagram for a system of the disclosure incorporating two downstream hydrogenation systems for conversion of olefins and aromatics.

[0024] Fig. 8 is a graph showing the stability and selectivity of an aromatic catalyst over the period of about 8 hours to about 50 hours on stream. DETAILED DESCRIPTION OF THE INVENTION

[0025] Aviation fuel generally comprises four classes of hydrocarbon compounds: normal (linear) paraffins, isoparaffins (branched), cycloparaffins, and aromatics. The most commonly used Jet A and Jet A-l fuels are blended to have a composition that enables them to meet specifications defined by ASTM International (formerly the American Society of Testing and Materials) Standard DI 655. The ASTM D1655 standard specification for aviation turbine fuels includes physical and chemical property tests that must be met for Jet A or Jet A-l to be used in aircraft. That standard also includes limits for the concentration of acidic and sulfur- containing compounds, as well as a minimum and maximum concentration for aromatic hydrocarbons, and refers to ASTM standard tests for those limits. Aromatics are required for material compatibility with O-rings in existing turbine engines but are missing in most synthetically produced blend components for aviation fuel.

[0026] Among aromatic hydrocarbons, monocyclic aromatics and bicyclic aromatic compounds (meaning compounds that contain two fused aromatic rings) do not substantially differ in their effectiveness for O-ring compatibility, and petroleum-derived jet fuels typically contain both. ASTM D1655 also does not differentiate between them. However, polycyclic aromatics (meaning compounds that contain two or more fused aromatic rings), e.g., naphthalenes, produce a considerably larger amount of hazardous particulate emissions upon combustion than their monocyclic counterparts. For example, n-butylbenzene produces around 62% of the soot of naphthalene when burned. Thus, it is advantageous for synthetic Jet A to contain monocyclic aromatics rather than polycyclic aromatics.

[0027] Among the processes that synthesize synthetic blend components for sustainable aviation fuel, Fischer-Tropsch (FT) is commonly used, as it is a proven process that has been in operation since the early 1900s for the conversion of synthesis gas (syngas), a mixture of carbon monoxide and hydrogen gas, into paraffins. The product liquid from FT, Fischer- Tropsch Hydroprocessed Synthesized Paraffinic Kerosene (FT-SPK) was the subject of Annex Al of ASTM D7566, the first approved annex for a synthetic blend component for SAF. This paraffinic kerosene is comprised primarily of ^-paraffins and isoparaffins, with little or no cycloparaffins or aromatics. For this reason, FT-SPK must be blended with a corresponding traditional Jet A to achieve the desired concentration of cyclic compounds to meet ASTM D1655 specifications. Through the ASTM D4054 process, additional annexes to ASTM D7566 have been approved for synthetic blend components that contribute to a fully formulated Jet A. In certain aspects, the present disclosure describes a fully formulated Jet A made synthetically from carbon dioxide. The fully formulated synthetic Jet A may be drop in, meaning that the chemical and physical characteristics of the synthetic Jet A are almost identical to those of conventional jet fuel and it can be safely mixed with the latter to varying degrees, use the same supply infrastructure and do not require the adaptation of aircraft or engines. As described herein, the production process assembles aromatic compounds from carbon dioxide. This bottom-up process design substantially reduces the synthetic accessibility of larger molecules. The synthetic Jet A disclosed in the present invention thus contains fewer polycyclic aromatics than Jet A made from petroleum-derived components. In certain embodiments, the synthetic Jet A of the present disclosure comprises less than about 1 wt% polycyclic aromatics.

[0028] The compositions described herein also contain substantially fewer sulfur-containing species than the comparable fossil fuel, in certain embodiments less than 1 ppm. This is accomplished by synthesizing the jet fuel thermochemically from CO2 and H2.

[0029] Both of these features of the fuels described herein (low polycyclic aromatic and sulfur content) are difficult or impossible to achieve with petroleum-derived fuels, as those fuels are prepared by conventional methods, which ultimately retain various characteristic compounds, e.g., sulfur species and polycyclic aromatics, from the petroleum source which are prohibitively expensive or impossible to remove completely from the final fuel product.

[0030] Also provided herein are systems and processes for the production of SAF, which can in certain embodiments be directly substituted for Jet-A made from petroleum-derived components, from CO2 and renewable power.

[0031] The above-described process can produce aviation fuel which can be directly substituted for Jet-A derived from crude oil, since its ratio of iso- to normal paraffins, and aromatics to naphthenes can be controlled in the isomerization / hydrogenation reactor, and the ratio of paraffin to aromatics can be adjusted by controlling the relative size of Reactor 1 and Reactor 2. Those of skill in the art will appreciate that the flexibility of this system design allows these ratios to be adapted for other uses as desired. A particular advantage of the present system and method is that the aromatics and paraffins can be combined prior to purification, resulting in a significant savings in capital expenditure. Fuel Compositions

[0032] In certain aspects, the present disclosure provides systems and methods for producing fuel compositions from a carbon source gas (e.g., CO2) and a reduction gas (e.g., H2). The fuel compositions produced by these systems and / or methods, e.g., the compositions described below, exhibit certain unique properties and compositional features. 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 processes disclosed herein for preparing the aromatic component heavily favor the creation of monocyclic aromatics, and disfavor the creation of polycyclic aromatics. These compositional features (e.g., low sulfur content and low polycyclic aromatic content), which arise a result of the systems and processes described herein, are advantageous compared with conventional (petroleum-derived) fuels.

[0033] In some aspects, provided herein are fuel compositions comprising: monocyclic aromatics; cyclo-paraffins; n-paraffins; and iso-paraffins. The composition may comprise less than about 1 wt% polycyclic aromatics.

[0034] The fuel composition may comprise less than about 5 wt% tetralins and indanes, or less than about 1 wt% tetralins and indanes. In some embodiments, the fuel composition comprises from 0 wt% to about 5 wt% tetralins and indanes, or from 0 wt% to about 1 wt% tetralins and indanes. In certain embodiments, the composition comprises essentially no tetralins and no indanes.

[0035] The fuel composition may comprise less than about 0.5 wt% polycyclic aromatics. The fuel composition may comprise from about 0 wt% to about 0.5 wt% polycyclic aromatics, or about 0.1 wt% to about 1 wt% polycyclic aromatics. In certain embodiments, the fuel composition comprises 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 polycyclic aromatics. In certain embodiments, the fuel composition comprises essentially no polycyclic aromatics, e.g, as determined by GC- MS.

[0036] In certain embodiments, essentially all of the aromatic compounds present in fuel composition of the present disclosure are monocyclic aromatics.

[0037] The fuel composition may comprise about 5 wt% to about 25 wt% monocyclic aromatics. The fuel composition may comprise about 8 wt% to about 15 wt% monocyclic aromatics. The fuel composition may comprise about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, or about 14 wt% monocyclic aromatics. The fuel composition may comprise about 14.5 wt% monocyclic aromatics.

[0038] The fuel composition may comprise about 15 wt% to about 65 wt% cyclo-paraffins The fuel composition may comprise from about 15 wt% to about 35 wt% cyclo-paraffins. The fuel composition may comprise about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, or about 35 wt% cyclo-paraffins. The fuel composition may comprise about 29 wt% cyclo- paraffins.

[0039] The fuel composition may comprise about 5 wt% to about 40 wt% iso-paraffins. The fuel composition may comprise from about 5 wt% to about 15 wt% iso-paraffins. The fuel composition may comprise about 5 wt%, about 7 wt%, about 9 wt%, about 11 wt%, about 13 wt%, or about 15 wt% iso-paraffins. The fuel composition may comprise about 8.8 wt% isoparaffins.

[0040] The fuel composition may be compliant with ASTM D4054 - Tier 1.

[0041] The fuel composition may have a total acidity of less than about 0.10 mg KOH / g. In certain embodiments, the composition has a total acidity of about 0.05 mg KOH / g to about 0.10 mg KOH / g. In further embodiments, the composition has a total acidity of about 0.05 mg KOH / g, about 0.06 mg KOH / g, about 0.07 mg KOH / g, about 0.08 mg KOH / g, about 0.09 mg KOH / g, or about 0.10 mg KOH / g. In certain embodiments, the composition has a total acidity of about 0.07 mg KOH / g.

[0042] In certain embodiments, the composition comprises less than about 0.3 wt% total sulfur, for example as measured by ASTM D2622. In some embodiments, the composition comprises less than about 1 ppm sulfur-containing impurities. In certain embodiments, the composition comprises essentially no sulfur-containing impurities. In certain embodiments, the composition comprises less than about 0.003 wt% sulfur mercaptan. In other embodiments, the composition comprises about 0 wt% sulfur mercaptan, for example as measured by ASTM D3227.

[0043] The fuel composition may have a flash point of at least about 38 °C. In certain embodiments, the composition has a flash point from about 38 °C to about 370 °C, or about 38 °C to about 100 °C. In further embodiments, the composition has a flash point from about 38 °C to about 50 °C. In yet further embodiments, the composition has a flash point of about 38 °C, about 39 °C, about 40 °C, about 41 °C, about 42 °C, about 43 °C, about 44 °C, about 45 °C, about 46 °C, about 47 °C, about 48 °C, about 49 °C, or about 50 °C. In certain embodiments, the composition has a flash point of about 42 °C. The fuel composition may have a density from about 775 kg / m3to about 840 kg / m3at 15 °C. In some embodiments, the composition has a density from about 775 kg / m3to about 785 kg / m3at 15 °C. In certain embodiments, the composition has a density of about 775 kg / m3, about 778 kg / m3, about 780 kg / m3, about 782 kg / m3, or about 785 kg / m3at 15 °C. In further embodiments, the composition has a density of about 780 kg / m3at 15 °C.

[0044] The fuel composition may have a freezing point of less than about -40 °C. In certain embodiments, the composition has a freezing point of from about -70 °C to about -40 °C. In further embodiments, the composition has a freezing point of about -70 °C, about -65 °C, about -60 °C, about -55 °C, about -50 °C, about -45 °C, or about -40 °C. In some embodiments, the composition has a freezing point of about -51 °C.

[0045] The fuel composition may have a viscosity of less than about 8.0 cSt at -20 °C. In some embodiments, the composition has a viscosity of less than about 12 mm2 / s at -40 °C. In certain embodiments, the composition has a viscosity of about 3.2 mm2 / s at -20 °C.

[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 from about 42.8 MJ / kg to about 51 MJ / kg. In further embodiments, the composition has a net heat of combustion of about 42.8 MJ / kg, about 43.4 MJ / kg, about 45 MJ / kg, about 47 MJ / kg, about 49 MJ / kg, or about 51 MJ / kg. In certain 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 further embodiments, the composition has a smoke point of from about 25 mm to about 45 mm. In still further embodiments, the composition has a smoke point of about 25 mm, about 30 mm, about 35 mm, about 40 mm, or about 45 mm. In certain 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 gives a filter pressure drop of from 0 mm Hg to about 25 mm Hg. In certain embodiments, the composition gives a filter pressure drop of about 0 mm Hg.

[0049] The fuel composition may have a tube deposit rating of less than about 3, with essentially no peacock or abnormal color deposits. In certain embodiments, the composition gives tube deposit rating of 1 VTR Color Code. The fuel composition may have a lubricity of less than about 0.85 mm wear scar diameter (WSD). In some embodiments, the composition has a lubricity of from 0 mm WSD to about 0.85 mm WSD. In certain embodiments, the composition has a lubricity of about 0.52 mm WSD.

[0050] The fuel composition may be compliant with ASTM DI 655.

[0051] In certain embodiments, the monocyclic aromatics are not petroleum-derived. In some embodiments, the monocyclic aromatics are derived from CO2. In some embodiments, the monocyclic aromatics, cyclo-paraffins, n-paraffins, and iso-paraffins are not petroleum- derived. In other embodiments, the monocyclic aromatics, cyclo-paraffins, n-paraffins, and isoparaffins are derived from CO2.

[0052] The fuel composition may further comprise at least one fuel additive. The fuel additive may be any such additive known for use in the art. For example, the fuel additive may be incorporated to provide certain desired characteristics or properties to the fuel.

[0053] Systems for Aviation Fuel Production

[0054] Provided herein are systems for the conversion of carbon source gases and reduction gases to aviation fuel. Certain components of these systems are described as being “coupled” to one another. As will be appreciated, the term “coupled” as used herein describes components that are operationally linked to one another, but does not preclude the presence of intervening components between those said to be coupled to one another. Additionally, as will be appreciated, various system components are described as “having” certain features. For example, in certain embodiments the reduction reactor

[0025] is described as having a first reduction gas feed inlet

[0023] , a first carbon source inlet

[0023] , and a paraffin product outlet

[0027] , Such descriptions do not preclude, and specifically contemplate, the presence of additional features, such as inlets, outlets, valves, control mechanisms, measurement devices, heating and / or cooling systems, etc. Additionally, in the systems of the present disclosure, certain components are described as having one or more outlets or inlets. Such outlets and inlets may represent separate structural elements, or may be combined into a single inlet or outlet as suitable. The person of ordinary skill in the art will recognize that, once the critical features and operating conditions of systems such as those described herein are understood, the detailed design and operation of such systems involved many choices, such as specific reagent flows, separation steps, etc. While the present disclosure provides a number of specific embodiments, any suitable combination of these design choices may be made. Further, the various systems and methods of the present disclosure sometimes reference fractions with particular carbon numbers (e.g., CX-Y). AS will be understood, these carbon numbers refer to the carbon makeup of the majority of the fraction, but said fractions may include additional components with carbon numbers that are higher or lower than indicated. Separators which are capable of creating these fractions are well known in the art, and can be adjusted as needed to afford suitable product mixtures as disclosed herein, or as otherwise desired by the operator. Certain components of said system are referred to by numbers in brackets (i.e.,

[0010] ).

[0055] Systems for the production of aviation fuel are disclosed herein. The systems may include: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst; and an aromatic reactor comprising an aromatic catalyst.

[0056] The reduction reactor may have a first reduction gas feed inlet, a first carbon source feed inlet, a target hydrocarbon outlet, and a medium hydrocarbon outlet. The first reduction gas feed inlet may be coupled to the first reduction gas feed. The first carbon source gas feed inlet may be coupled to the first carbon source gas feed. The reduction reactor may further comprise a light hydrocarbon outlet.

[0057] The aromatic reactor may include a medium hydrocarbon inlet, optionally a second reduction as feed inlet, optionally a second carbon source gas feed inlet, and a target aromatic product outlet. The medium hydrocarbon inlet may be coupled to the medium hydrocarbon outlet on the reduction reactor, the second reduction gas feed inlet, when present, may be coupled to the second reduction gas feed, and the second carbon source gas feed inlet, when present, may be coupled to the second carbon source gas feed. The aromatic reactor may further comprise a light aromatic product outlet.

[0058] The system may also include a second reduction gas feed. The system may also include a second carbon source gas feed.

[0059] The systems of the disclosure may comprise a first adsorbent bed having a medium hydrocarbon inlet and a medium hydrocarbon outlet. The medium hydrocarbon inlet may be coupled to the medium hydrocarbon outlet on the reduction reactor, and the medium hydrocarbon outlet may be coupled to the medium hydrocarbon inlet on the aromatic reactor.

[0060] The systems of the disclosure may comprise an alkylation reactor comprising an alkylation catalyst. The alkylation reactor may include a light hydrocarbon inlet, a light aromatic product inlet, and an alkyl arene product outlet. The light hydrocarbon inlet may be coupled to the light hydrocarbon outlet on the reduction reactor, and the light aromatic product inlet may be coupled to the light aromatic product outlet on the aromatic reactor.

[0061] The systems of the disclosure may comprise an oligomerization reactor comprising an oligomerization catalyst. The oligomerization reactor may have a light hydrocarbon inlet and a target oligomerized product outlet. The light hydrocarbon inlet may be coupled to the light hydrocarbon outlet on the reduction reactor.

[0062] The systems of the disclosure may comprise an oligo-alkylation reactor comprising an oligomerization catalyst and an alkylation catalyst. The oligo-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 coupled to the light hydrocarbon outlet on the reduction reactor, and the light aromatic product inlet may coupled to the light aromatic product outlet on the aromatic reactor.

[0063] The systems of the disclosure may comprise a second adsorbent bed having a light hydrocarbon inlet and / or a light aromatic product inlet, and a light hydrocarbon outlet and / or a light aromatic product outlet. The light hydrocarbon inlet, when present, may be coupled to the light hydrocarbon outlet on the reduction reactor; the light aromatic product inlet, when present, may be coupled to the light aromatic product outlet on the aromatic reactor; the light hydrocarbon outlet, when present, may be coupled to the light hydrocarbon inlet on the alkylation reactor; and / or the oligomerization reactor, or the oligo-alkylation reactor, and the light aromatic product outlet, when present, may be coupled to the light aromatic product inlet on the alkylation reactor or the oligo-alkylation reactor.

[0064] The oligomerization reactor and / or the oligo-alkylation reactor may comprise a light oligomerization product outlet. In some embodiments, the light oligomerization product outlet on the oligomerization reactor and / or the oligo-alkylation reactor is coupled to the first carbon source gas feed and / or the second carbon source gas feed.

[0065] In certain embodiments, the oligomerization reactor and / or the oligo-alkylation reactor further comprises a medium oligomerized product outlet.

[0066] In some embodiments, the oligomerization reactor, the alkylation reactor, and / or the oligo-alkylation reactor further comprise a medium oligomerized product inlet, wherein the medium oligomerized product inlet is coupled to the medium oligomerized product outlet on the oligomerization reactor and / or the oligo-alkylation reactor.

[0067] In some embodiments, the oligomerization reactor and / or the oligo-alkylation reactor further comprises a heavy oligomerized product outlet. In certain embodiments, the reduction reactor further comprises a heavy hydrocarbon outlet.

[0068] The systems of the disclosure may further comprise: a third reduction gas feed; and a hydrocracking reactor comprising a hydrocracking catalyst. The hydrocracking reactor may have a reduction gas inlet, a heavy oligomerized product inlet and / or a heavy hydrocarbon inlet, and a hydrocracked product outlet. The reduction gas inlet may coupled to the third reduction gas feed; the heavy oligomerized product inlet, when present, may be coupled to the heavy oligomerized product outlet on the oligomerization reactor and / or the oligo-alkylation reactor; and the heavy hydrocarbon inlet, when present, may be coupled to the heavy hydrocarbon outlet on the reduction reactor.

[0069] In certain embodiments, the reduction reactor further comprises a reduction gas outlet, wherein the reduction gas outlet is coupled to the first carbon source gas feed and / or the first reduction gas feed.

[0070] Systems of the disclosure may further comprise: a blender having a target hydrocarbon product inlet, a target aromatic product inlet, an alkyl arene product inlet, a target oligomerized product inlet, and / or a mixed target product inlet, and an aviation fuel outlet. The target hydrocarbon inlet, when present, may be coupled to the target hydrocarbon product outlet on the reduction reactor; the target aromatic product inlet, when present, may be coupled to the target aromatic product outlet on the aromatic reactor; the alkyl arene product inlet, when present, may be coupled to the alkyl arene product outlet on the alkylation reactor; the target oligomerized product inlet, when present, may be coupled to the target oligomerized product outlet on the oligomerization reactor; and the mixed target product inlet, when present, may be coupled to the mixed target product outlet on the oligo- alkylation reactor.

[0071] Methods for Aviation Fuel Production

[0072] As described below, the present disclosure provides various methods for conversion of carbon source gases to aviation fuel. The disclosure includes exemplary process conditions (e.g., temperature, pressure, space velocities, etc.) which provide certain advantages in context of the systems and methods disclosed herein. However, any suitable conditions may be used, and the person of ordinary skill in the art will appreciate how to vary the conditions of any particular process described herein to obtain results and tune product distribution as needed for particular applications, as contemplated. The present disclosure provides numerous catalysts that may be used to prepare paraffins, olefins, and mixtures thereof. The skilled artisan will recognize that any suitable catalyst or mixture of catalysts may be used in the methods and systems of the present disclosure to provide paraffins and olefins in the desirable ratios provided herein.

[0073] Provided herein are methods for the production of aviation fuel. The methods may comprise: (i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C5-9 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more C10-16 paraffins and / or olefins; and (ii) contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-14 aromatics.

[0074] In certain embodiments, contacting the first reduction gas and the first carbon source gas with the reduction catalyst occurs at a paraffin temperature which may be at least 80°C, or at least 100°C, or at least 120°C. The paraffin temperature may be 550 °C or less, or 600 °C or less, or 650 °C or less. The paraffin temperature may be from about 100 °C to about 600 °C. The paraffin temperature may be from about 200 °C to about 500 °C, or about 350 °C.

[0075] In certain embodiments, contacting the first reduction gas and the first carbon source gas with the reduction catalyst occurs at a paraffin pressure from about 50 psi to about 4000 psi. The paraffin pressure may be about 75 psi to about 225 psi. The paraffin pressure may be about 75 psi, about 100 psi, about 125 psi, about 150 psi, about 175 psi, about 200 psi, or about 225 psi.

[0076] In certain embodiments, each of the light hydrocarbon product mixture, the medium product mixture, and / or the target hydrocarbon product mixture comprise olefins and paraffins. In further embodiments, the ratio of olefins to paraffins in each of the light hydrocarbon product mixture, the medium product mixture, and / or the target hydrocarbon product mixture is at least about 1 : 1, with the amount of olefins being about equal to or more than the amount of paraffins present therein. The ratio of olefins to paraffins in each of the light hydrocarbon product mixture, the medium 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 ratio of olefins to paraffins in each of the light hydrocarbon product mixture, the medium 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.

[0077] In certain embodiments, contacting the first reduction gas and the carbon source gas with a reduction catalyst further affords a light hydrocarbon product mixture comprising one or more C2-4 paraffins and / or olefins. In some embodiments, the ratio of C2-4 olefins to C2-4 paraffins in the light hydrocarbon product mixture is at least about 5 : 1. In further embodiments, the ratio of C2-4 olefins to C2-4 paraffins in the light hydrocarbon product mixture is preferably at least about 8: 1. In certain embodiments, the ratio of C2-4 olefins to C2-4 paraffins in the light hydrocarbon product mixture is about 5: 1 to about 15: 1, or about 8: 1 to about 10: 1. In certain embodiments, the ratio of C2-4 olefins to C2-4 paraffins in the light hydrocarbon product mixture is about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1, or about 10: 1.

[0078] In some embodiments, the medium hydrocarbon product mixture comprises one or more C5-9 paraffins and olefins. In certain embodiments, the ratio of C5-9 olefins to C5-9 paraffins in the medium hydrocarbon product mixture is at least about 3 : 1 , or at least about 5: 1. In certain embodiments, the ratio of C5-9 olefins to C5-9 paraffins in the medium hydrocarbon product mixture is about 3: 1 to about 12: 1. In certain embodiments, the ratio of C5-9 olefins to C5-9 paraffins in the medium hydrocarbon product mixture is about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, or about 8: 1.

[0079] In certain embodiments, methods of the disclosure involve mixtures comprising aromatics. These aromatics may be described in terms of a carbon number e.g, “CX-Y aromatics.” As will be appreciated by one of skill in the art, this carbon number refers to the total number of carbon atoms in the molecule, and not necessarily to the number of ring atoms. For example, the group of compounds described by the term “C10 aromatics” may include naphthalene (CioHs), butylbenzene (C10H14), etc.

[0080] In some embodiments, contacting the medium hydrocarbon product mixture, optionally the second reduction gas, and optionally the second carbon source gas, with an aromatic catalyst occurs at an aromatic temperature from about 100 °C to about 450 °C.

[0081] Methods of the disclosure may further comprise passing the medium hydrocarbon product mixture through an adsorbent bed prior to contacting with the aromatic catalyst.

[0082] In certain embodiments, contacting the medium hydrocarbon product mixture with the aromatic catalyst further affords a light aromatic product mixture comprising one or more Ce-8 aromatics. In certain embodiments, contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas, with an aromatic catalyst occurs at an aromatic pressure from about 50 psi to about 1000 psi.

[0083] Methods of the disclosure may further comprise contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics. In certain such embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst may be performed with any suitable catalyst under any suitable conditions. In certain embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst occurs at an alkylation temperature. The alkylation temperature may be 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 alkylation temperature may 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.

[0084] The alkylation process is not particularly sensitive to pressure. However, in certain embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst occurs at an alkylation pressure. The alkylation pressure may be about 0 psig to about 1000 psig, about 100 psig to about 700 psig, about 200 psig to about 500 psig, about 0 psig to about 200 psig, about 10 psig to about 120 psig, or about 20 psig to about 100 psig.

[0085] Methods of the disclosure may further comprise contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins.

[0086] Methods of the disclosure may further comprise contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst and an oligomerization catalyst to afford a mixed target product mixture comprising one or more C9- 14 aromatics and one or more Cio-16 paraffins and / or olefins.

[0087] In some embodiments, it is desirable to oligomerize the olefins produced from CO2 by methods of the disclosure in the presence of an oligomerization catalyst to produce a mixture of higher olefins and optionally aromatics. As used herein, the modifier “higher” with respect to hydrocarbons (e.g., paraffins) or olefins will refer to hydrocarbons (e.g., paraffins) or olefins with a higher number of carbons than a precursor. Exemplary higher hydrocarbons (e.g., paraffins) and olefins include, but are not limited to Cs-Ci6 hydrocarbons (e.g., paraffins) and / or olefins. Said oligomerization process can be carried out in a fixed bed flow reactor, or any other suitable reactor type.

[0088] The temperature at which this oligomerization may be carried out can range from about 50 °C to about 1000 °C as needed to tailor the degree of oligomerization based on the desired product length and distribution. The oligomerization temperature may 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 may be about 50 °C, about 150 °C, about 250 °C, about 350 °C, or about 400 °C.

[0089] The pressure at which this oligomerization may be carried out can range from about 0 psi to about 1000 psi as needed to tailor the degree of oligomerization based on the desired product length and distribution. The oligomerization pressure may be about 0 psi to about 500 psi, about 0 psi to about 400 psi, about 0 psi to about 300 psi, about 0 psi to about 200 psi, about 10 psi to about 120 psi, or about 20 psi to about 100 psi. The oligomerization pressure may be 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.

[0090] Methods of the disclosure may further comprise contacting the light hydrocarbon product mixture and the light aromatic product mixture with an oligo-alkylation catalyst to afford a mixed target product mixture comprising one or more C9-14 aromatics and one or more C10-16 paraffins and / or olefins.

[0091] In certain embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with the oligo-alkylation catalyst occurs at an oligo-alkylation temperature. The oligo-alkylation temperature may 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 oligo-alkylation temperature may 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.

[0092] The oligo-alkylation process is not particularly sensitive to pressure. However, in certain embodiments, contacting the light hydrocarbon product mixture and the light aromatic product mixture with an oligo-alkylation catalyst occurs at an oligo-alkylation pressure. The oligo-alkylation pressure may be about 0 psig to about 200 psig, about 10 psig to about 120 psig, or about 20 psig to about 100 psig.

[0093] Methods of the disclosure may further comprise passing the light hydrocarbon product mixture and / or the light aromatic product mixture through an adsorbent bed prior to contacting with the alkylation and / or oligomerization catalysts. In certain embodiments, contacting the light hydrocarbon product mixture and / or the light hydrocarbon product mixture with the oligomerization catalyst further affords a light oligomerized product mixture comprising one or more C1-2 hydrocarbons.

[0094] Methods of the disclosure may further comprise combining the carbon source gas with the light oligomerized product mixture prior to contacting with the reduction catalyst.

[0095] In certain embodiments, contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords a medium oligomerized product mixture comprising one or more C3-7 hydrocarbons.

[0096] Methods may further include blending the target hydrocarbon product mixture, the target aromatic product mixture, the target oligomerized product mixture, the target alkyl arene product mixture, and / or the target product mixture to produce aviation fuel. One of ordinary skill in the art will readily understand that some or all of the products and mixtures from any one or more of the reactors used in the method or systems disclosed herein may be subjected to certain treatments such as hydrogenation and / or absorption for removing impurities before blending.

[0097] The method may include hydrogenating the target aromatic product mixture, the target oligomerized product mixture, and / or the target alkyl arene product mixture. Hydrogenating olefins may convert a majority of olefins to paraffins. Hydrogenating aromatics may convert a majority of aromatics to cycloparaffins. The step of hydrogenating may comprise providing the target aromatic product mixture, the target oligomerized product mixture, and / or the target alkyl arene product mixture to any number of hydrogenation reactors comprising the same or different hydrogenation catalyst in each of the reactors. The method may include one hydrogenation reactor for olefin hydrogenation (also referred to as olefin hydrotreating), and / or another hydrogenation reactor for aromatic hydrogenation (also referred to as aromatic hydrotreating). In an embodiment, a minority portion of the target aromatic product mixture may be provided to the olefin hydrogenation reactor and a majority portion may be provided to the aromatic hydrogenation reactor to maintain some aromatization and maintain some flexibility of blend ratios.

[0098] Methods of the disclosure may further comprise combining the light hydrocarbon product mixture with the medium oligomerized product mixture prior to contacting with the oligomerization catalyst. In certain embodiments, contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords a heavy oligomerized product mixture comprising one or more C17-40 paraffins and / or olefins.

[0099] In some embodiments, contacting the first reduction gas and the carbon source gas with a reduction catalyst further affords a heavy hydrocarbon product mixture comprising one or more C17-40 paraffins and / or olefins.

[0100] Methods of the disclosure may further comprise contacting a third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with a hydrocracking catalyst to afford a hydrocracked product mixture comprising one or more Ci-is paraffins and / or olefins.

[0101] In certain embodiments, contacting the third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with the hydrocracking catalyst occurs at a hydrocracking temperature from about 250 °C to about 450 °C.

[0102] In some embodiments, contacting the third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with the hydrocracking catalyst occurs at a hydrocracking pressure of less than about 1000 psig. In certain embodiments, the hydrocracking pressure is from 0 psig to about 1000 psig.

[0103] Catalysts for Conversion of Carbon Sources to Olefins and Paraffins

[0104] The systems and methods of the present disclosure may include the use of a reduction catalyst. The conversion of carbon dioxide and carbon dioxide containing mixtures can be achieved through catalytic carbon dioxide transformations, where the reduction catalyst plays the key role in the process. Reduction catalysts, as used herein may also be understood to be carbon dioxide hydrogenation catalysts, which are catalysts that enhance carbon dioxide activation and conversion, and may also control the selectivity of the hydrogenation products. The reduction catalysts are active in the conversion of a carbon source gas, such as CO2, to hydrocarbons comprising olefins and / or paraffins.

[0105] Any known reduction catalyst may be used in accordance with this disclosure.

[0106] Transition metal catalysts, especially base metals, are particularly effective as reduction catalysts due to their high electron density, various oxidation states and rich spectrum of metal-ceramic materials, which provides enhanced carbon dioxide activations and flexible tuning of transformation pathways. In addition to the metal elements, the reduction catalyst may contain one or more additional materials, such as a binder, lubricant and / or supporting material, which can be added to optimize the forming catalyst process, metal dispersity and other chemical and physical properties.

[0107] Certain commonly known reduction catalysts contain copper, iron, zinc, cobalt, or some combination thereof. The reduction catalyst may comprise copper. Copper catalysts are known to be one of the most efficient reduction catalysts producing oxygenates as the 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 metal and alkali earth metals. The supporting element, metal alloy and metal oxide provide electronic and structure support to better tune the reactivity and selectivity of carbon dioxide hydrogenation.

[0108] The reduction catalyst may comprise iron and / or cobalt. Iron and cobalt catalysts are widely used in carbon dioxide hydrogenation, and specifically used in the Fischer-Tropsch process, for example, to form longer chain hydrocarbon and oxygenate products. Similar to the copper family, iron and cobalt catalyst may contain additional metal promoters to improve both carbon dioxide adsorption and selectivity of the hydrogenation. The metal promoter may be selected from zinc, manganese, molybdenum, copper, nickel, alkali and alkali earth metals.

[0109] Reduction catalysts of the disclosure may comprise and / or be derived from a particular metal oxide, or a combination of multiple metal oxides. One of ordinary skill in the art will appreciate that during the various catalyst preparation and activation methods known in the art, and in those exemplified herein, some or all of the oxygen atoms of the metal oxide may become bonded to other atoms in the catalyst mixture, and / or may be removed from the catalyst mixture partially or entirely during an activation step (e.g., converted to CO2 and removed). Additionally, one of ordinary skill in the art would appreciate that for such catalysts, e.g., the reduction and / or paraffin catalysts described below, the molar ratio of oxygen relative to the total composition may vary. Further, as will be understood, when defining catalysts made from metal oxides, the molar ratios of one metal to another are defined on a metal (rather than metal oxide) basis.

[0110] The reduction catalyst may be a paraffin catalyst or an olefin catalyst. As used herein, the term “paraffin catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to paraffins, predominantly, but which catalyst does not necessarily itself comprise paraffins. A paraffin catalyst may be selected when the desired product is paraffins. The paraffin catalyst may be used for the conversion of carbon sources and reduction gases to paraffins predominantly, as well as olefins and / or other hydrocarbons in a minority amount. As used herein, the term “olefin catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to olefins, predominantly, but which catalyst does not necessarily itself comprise olefins. An olefin catalyst may be selected when the desired product is olefins. The olefin catalyst may be used for the conversion of carbon sources and reduction gases to olefin predominantly, as well as paraffins and / or other hydrocarbons in a minority amount.

[0111] The reduction catalyst may comprise: zinc; one or more first elements selected from iron or cobalt; and oxygen or carbon or nitrogen. The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; and oxygen or carbon or nitrogen. The reduction catalyst may also include aluminum. The reduction catalyst may also include one or more second elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may also include one or more Group IA and IIA metals.

[0112] 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 of the disclosure 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 a Group V,

[0113] VI, VII, VIII, IX, X, and XI metal (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 IIA metals.

[0114] 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 a Group V, VI,

[0115] VII, VIII, IX, X, and XI metal (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may comprise: copper; zinc; one or more first elements selected from iron or cobalt; oxygen or carbon or nitrogen; aluminum; and one or more Group IA and IIA metals.

[0116] The one or more first elements may be present in an amount 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.%, of the total amount of the copper, zinc, cobalt, iron, the optional second element, and the optional Group IA and IIA metal.

[0117] The reduction catalyst may comprise a cobalt-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide. In some embodiments, the cobalt is present as cobalt oxide. In some embodiments, the copper is present as 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 approximately 1 :2.5: 1. In some embodiments, the zinc is preferably 0.3 - 1 the molar content of the copper. In some embodiments, the cobalt is preferably 0.1 - 1 the molar content of the copper.

[0118] The reduction catalyst may comprise an iron-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide. In some embodiments, the iron is present as iron oxide. In certain embodiments, the iron oxide is magnetite (FesCU), hematite (Fe20s), or a combination thereof. In further embodiments, the iron oxide is magnetite (FesCU). In yet further embodiments, the iron oxide is a combination of magnetite (FesC ) and hematite (Fe20s).

[0119] In some embodiments, the copper is present as copper oxide. In some embodiments, the molar ratio of iron to copper to zinc (Fe:Cu:Zn) is about 0.1 to about 100 in iron, about 0.05 to about 4 in copper, and about 0.05 to about 4 in zinc. In some embodiments, the Fe:Cu:Zn ratio is in the range of about 0.4 to about 2 in iron, about 1 to about 3 in copper, and about 0.5- 3 in zinc. In some embodiments, the Fe:Cu:Zn ratio is approximately 1 :2.3:2.3. In some embodiments, the zinc is preferably about 0.3 to about 1 the molar content of the copper. In some embodiments, the iron is about 0.5 to about 5 the molar content of the copper.

[0120] The reduction catalyst may comprise one or more elements selected from a transition, or Group VI, VII, VIII, IX, X, or XI metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group VI metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group VII metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group VIII metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group IX metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group X metal. In some embodiments, the reduction catalyst comprises one or more second elements selected from a Group XI metal.

[0121] The one or more second elements may comprise manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. The one or more second elements may comprise nickel. The one or more second elements comprise silver. The one or more second elements may comprise palladium. The one or more second elements may comprise niobium. The one or more second elements may comprise manganese. The one or more second elements may comprise zirconium. The one or more second elements may comprise molybdenum.

[0122] In some embodiments, the reduction catalyst comprises the one or more second elements at a molar ratio 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 relative to the one or more first elements.

[0123] In some embodiments, the reduction catalyst comprises copper at a molar ratio 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 relative to the one or more first elements.

[0124] In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.3 to about 3, about 1 to about 2.5, or about 0.4 to about 1, relative to copper.

[0125] The reduction catalyst may comprise the one or more Group IA or IIA metals. In some embodiments, the one or more Group IA or IIA metals comprise magnesium, calcium, potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals consist of magnesium, calcium, potassium, sodium, or cesium. In certain embodiments, the one or more Group IA or IIA metals comprise or consist of sodium and / or cesium.

[0126] In some embodiments, the reduction catalyst comprises the one or more Group IA or IIA metals at a molar ratio of about 0.01 to about 1.0 relative to copper, about 0.05 to about 0.50 relative to copper, about 0.10 to about 0.30 relative to copper, about 0.20 to about 0.50 relative to copper, about 0.30 to about 0.50 relative to copper, about 0.40 to about 0.50 relative to copper

[0127] In some embodiments, the reduction catalyst comprises one or more Group IA metals. The one or more Group I A or IIA metals may comprise potassium, sodium or cesium. In some embodiments, the one or more Group IA or IIA metals consist of potassium, sodium or cesium. In some embodiments, the one or more Group IA or IIA metals comprise potassium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In some embodiments, the one or more Group IA or IIA metals comprise cesium.

[0128] In some embodiments, the reduction catalyst comprises potassium at a molar ratio 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 l.Orelative to copper.

[0129] In some embodiments, the reduction catalyst comprises aluminum at a molar ratio of about 0.1 to about 10, about 0.1 to about 1, about 0.1 to about 0.2, about 0.5 to about 1 relative to copper.

[0130] The reduction catalyst may comprise 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

[0131] The reduction catalyst may comprise alumina.

[0132] In some embodiments, the reduction catalyst comprises aluminum oxide (AI2O3) wherein the aluminum is present 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 relative to copper.. In some embodiments, the alumina can be added as a support to increase the surface area of the copper and zinc, or produced in-situ as a component of the reduction catalyst, e.g. from aluminum nitrate co-precipitation with first element, copper, and zinc precursors.

[0133] In some embodiments, the reduction catalyst comprises copper, zinc oxide, cobalt, and alumina. In some embodiments, the reduction catalyst comprises copper, zinc oxide, nickel, and alumina. In some embodiments, the reduction catalyst comprises copper, zinc oxide, iron, and alumina. In some embodiments, the reduction catalyst comprises copper, zinc oxide, cobalt, alumina, and a Group IA metal. In some embodiments, the reduction catalyst comprises copper, zinc oxide, nickel, alumina, and a Group IA metal. In some embodiments, the reduction catalyst comprises copper, zinc oxide, iron, alumina, and a Group IA metal. The molar ratios of the foregoing components may be as described above.

[0134] The reduction catalyst may comprise Cu, Zn, Al, and O. The reduction catalyst may comprise Cu, Zn, Al, O, and an alkali metal, and optionally also comprise Ni, Fe, Co, Nb, Mo, In, Se, or any combination thereof.

[0135] The elemental composition of the reduction catalyst material may be Cu(ZnO)CoA / Al2O3, Cu(ZnO)CoFeA / Al2O3, Cu(ZnO)CoNbA / Al2O3, Cu(ZnO)CoNiA / A12O3, Cu(ZnO)CoMoA / A12O3 wherein A is an alkali metal and further wherein the relative amounts of the elemental components are as described above.

[0136] The elemental composition of the reduction catalyst material may be Cu(ZnO)Co / Al2O3, Cu(ZnO)CoFe / Al2O3, Cu(ZnO)CoNb / Al2O3, Cu(ZnO)CoNi / Al2O3, Cu(ZnO)CoMo / A12O3, wherein the relative amounts of the elemental components are as described above.

[0137] The elemental composition of the reduction catalyst material may be CuO(ZnO), Cu(ZnO)Co, Cu(ZnO)CoK, Cu(ZnO)CoFe, Cu(ZnO)CoFeK, Cu(ZnO)CoNi, Cu(ZnO)CoNiK, Cu(ZnO)CoNb, Cu(ZnO)CoNbK, Cu(ZnO)CoMo, Cu(ZnO)CoMoK on AI2O3, wherein the relative amounts of the elemental components are as described above.

[0138] In further aspects, provided herein are reduction catalysts comprising: one or more metals; optionally one or more second elements selected from copper and zinc; optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives; optionally a Group IA or IIA metal, which acts as a promoter.

[0139] The one or more metals may be selected from cobalt, iron, nickel, indium, yttrium, a lanthanide, and combinations thereof. In certain embodiments, the one or more metals is cobalt. In other embodiments, the one or more metals is iron. In still further embodiments, the one or more metals is a combination of iron and cobalt.

[0140] The one or more metals may be present in the form of an oxide, nitride, or carbide. In certain embodiments, the one or more metals is present in the form of an iron oxide.

[0141] In further embodiments, the one or more second elements is copper. In yet further embodiments, the one or more second elements is zinc. In still further embodiments, the one or more second elements are copper and zinc. In certain embodiments, the one or more second elements is present in the form of an oxide, nitride, or carbide. In yet further embodiments, the one or more second elements is zinc oxide.

[0142] In certain embodiments, the one or more Group VI, VII, VIII, IX, X, or XI metal additives, when present, is selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. In further embodiments, the Group IA or IIA metal, when present, are Group IA elements. In yet further embodiments, the one or more Group IA or IIA metals, when present, are magnesium, calcium, lithium, sodium, potassium, or cesium. In yet further embodiments, the Group IA or IIA metal, when present, is lithium, sodium, potassium, or cesium. In still further embodiments, the one or more second elements is present in an amount of about 0.5 to about 40 wt.% of the total amount of the one or more metals, the second element, the optional one or more Group VI, VII, VIII, IX, X, or XI metal additives, and the optional Group IA or IIA metal.

[0143] In some embodiments, the reduction catalyst comprises one or more Group VI or VII metals, such as manganese (Mn), Chromium (Cr), or a combination thereof. In some embodiments, the reduction catalyst comprises the one or more Group VI or VII metals at a molar ratio from 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, about 0.40 to about 0.50 relative to copper or cobalt.

[0144] In certain aspects, the reduction catalyst comprises: one or more paraffin metal oxides; optionally a support, and optionally one or more metal additives. The one or more paraffin metal oxides may be selected from cobalt oxide, iron oxide, nickel oxide, indium oxide, yttrium oxide, a lanthanide oxide, and combinations thereof. The support, when present, may comprise carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, or silica carbide. The one or more metal additives, when present, may be selected from a Group IA or IIA element, palladium, platinum, ruthenium, or combinations thereof.

[0145] In certain aspects, the present disclosure provides catalytic compositions, comprising one or more of reduction catalyst and a reduction catalyst support. The reduction catalyst support may be any suitable material that can serve as a catalyst support.

[0146] The reduction catalyst support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some embodiments, the reduction catalyst support comprises y-alumina. In certain embodiments, the reduction catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the reduction catalyst support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the reduction catalyst support is an aluminum oxide that is formed in-situ as part of the reduction catalyst. In some embodiments, the reduction catalyst support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the reduction catalyst support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2. In some embodiments, the reduction catalyst support comprises one or more carbonbased materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0147] In some embodiments, the reduction catalyst support is selected from SiA10x, SO4- ZrCh, zirconium tungstate, tungstated-titania, and anatases (SiCh-AhCh, SiCh-TiCh). In further embodiments, the reduction catalyst support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0148] In some embodiments, the reduction catalyst support is a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM- 49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the reduction catalyst support is MCM-49. In further embodiments, the zeolites comprise additional metals such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the additional metals are present as zeolite supported metals or as isomorphous substitution in the zeolite framework.

[0149] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine, and / or sulfur.

[0150] In some embodiments, the support is a high surface area scaffold. In some embodiments, the support comprises carbon allotropes. In some embodiments, the support comprises mesoporous material, such as mesoporous silica. In such embodiments, as will be appreciated by one of ordinary skill in the art, the physical characteristics of the mesoporous material, e.g., mesopore volume and surface area may be measured using standard gas absorption measurement techniques known in the art including, for example, the Barrett- Joy ner-Halenda (BJH) method for determining pore size distributions and pore volumes, and the Brunauer, Emmett and Teller (BET) method for obtaining the specific surface area (hereinafter “surface area”).

[0151] In some embodiments, the reduction catalyst support has a mesopore volume from about 0.01 to about 3.0 cc / g.

[0152] In some embodiments, the reduction catalyst support has surface area from about 10 m2 / g to about 1000 m2 / g. In some embodiments, the catalytic composition comprising the reduction catalyst support and a catalyst disclosed herein has a surface area from about 10 m2 / g to about 1000 m2 / g. The catalytic composition may be in a form of particles having an average size from about 10 nm to about 5 pm, an average size from about 20 nm to about 5 pm, an average size from about 50 nm to about 1 pm, an average size from about 100 nm to about 500 nm, or an average size from about 50 nm to about 300 nm.

[0153] 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 the reduction catalyst.

[0154] In some embodiments, the reduction catalyst is a nanoparticle catalyst. The particle sizes of the reduction catalyst on the surface of the scaffold may be about 1 nm to about 5 nm, about 5 nm to about 100 nm, or about 100 to about 500 nm. In some embodiments, the particles not subjected to agglomeration are about 100 nm to about 500 nm in particle size.

[0155] The reduction catalyst may comprise: iron; optionally alumina; optionally a first element selected from copper, zinc, cobalt, manganese, chromium, or combinations thereof; and optionally one or more second elements selected from Group IA and IIA metals.

[0156] In certain embodiments, the reduction catalyst further comprises an additive mixture comprising potassium, manganese, ruthenium, and MgO. In further embodiments, the reduction catalyst comprises from about 1% to about 10% by weight of the additive mixture.

[0157] The reduction catalyst may comprise 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.

[0158] The reduction catalyst may comprise one or more Group IA or IIA metals. The one or more Group IA or IIA metals may comprise magnesium, calcium, potassium, sodium, or cesium. The one or more Group IA or IIA metals may consist of magnesium, calcium, potassium, sodium or cesium. The one or more Group I A or IIA metals may comprise magnesium. The one or more Group IA or IIA metals may comprise calcium. The one or more Group I A or IIA metals may comprise potassium. The one or more Group I A or IIA metals may comprise sodium. The one or more Group IA or IIA metals may comprise cesium. The one or more Group IA or IIA metals may consist of magnesium. The one or more Group IA or IIA metals may consist of calcium. The one or more Group IA or IIA metals may consist of potassium. The one or more Group IA or IIA metals may consist of sodium. The one or more Group IA or IIA metals may consist of cesium. The reduction catalyst may comprise: iron; a first element selected from K, Li, Zr, Cs, Mg, Rh, Ca, or a combination thereof; one or more second elements selected from Au, Cu, Na, Cr, Al, Ga, Mn Co, Ru, Ni, or a combination thereof; and optionally alumina.

[0159] The reduction catalyst may comprise: iron; K, Li, Zr, Cs, Mg, Rh, Ca, or a combination thereof, at a molar ratio of from 0 to about 0.20 relative to iron; Au, Cu, Na, Cr, Al, Ga, Mn, or a combination thereof, at a molar ratio from 0 to about 0.60 relative to iron; and Zn at a molar ratio from 0 to about 0.50 relative to iron.

[0160] In certain embodiments, the catalyst comprises K at a molar ratio of from 0 to about 0.20 relative to iron, and / or Na at a molar ratio from 0 to about 0.60 relative to iron.

[0161] In certain embodiments, the reduction catalyst comprises: iron;

[0162] K, Cs, Mg, Rh, Ca, or a combination thereof, at a molar ratio of from 0 to about 0.20 relative to iron;

[0163] Na, Cu, Cr, Mn, or a combination thereof, at a molar ratio of from 0 to about 0.60 relative to iron;

[0164] Co, Ru, Ni, or a combination thereof, at a molar ratio of from 0 to about 0.50 relative to iron.

[0165] In some embodiments, the reduction catalyst comprises Co at a molar ratio of from 0 to about 0.50, or about 0.1 to about 0.2 relative to iron. In certain embodiments, the reduction catalyst comprises Co at a molar ratio of about 0.14 relative to iron, and K at a molar ratio of about 0.01 relative to iron.

[0166] The iron may be in metal form, in the form of an iron oxide, or a combination thereof. In certain embodiments, the iron is in the iron oxide form. The iron oxide may be FeO, magnetite (Fes CL), hematite (Fe2CL), or a combination thereof. In some embodiments, the iron oxide is magnetite (FesC ). In other embodiments, the iron oxide is a combination of magnetite (FesC ) and hematite (Fe2CL). In other embodiments, the iron oxide is a combination of FeO, magnetite (FesO-t) and hematite (Fe20s).

[0167] The reduction catalyst may comprise: iron; a first element selected from copper, zinc, cobalt, or combinations thereof; and optionally one or more second elements selected from Group IA and IIA metals.

[0168] The reduction catalyst may also include one or more third elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, chromium, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel). The reduction catalyst may include: iron; and the first element being zinc. One or both of the iron and zinc may be present in oxide or carbide forms. The iron oxide may be in the form of FeO, Fe20s (hematite), Fe^Cf (magnetite) or a combination thereof. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of Fe20s. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of FesC

[0169] The reduction catalyst may comprise zinc at a molar ratio of about 0.2 to about 3 relative to iron, or about 0.3 to about 3 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.2 to about 1 relative to iron, or about 0.4 to about 1 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.5 relative to iron. In other embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.0 relative to iron. In certain embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.75 relative to iron, about 0.6 relative to iron, about 0.5 relative to iron, about 0.4 relative to iron, about 0.3 relative to iron, or about 0.25 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.5 relative to iron.

[0170] The reduction catalyst may comprise a molar ratio of iron to zinc 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: l to about 3: l. The reduction catalyst may comprise a molar ratio of iron to zinc 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 comprise a molar ratio of iron to zinc of about 2: 1.

[0171] In some embodiments, the reduction catalyst comprises: iron; zinc at a molar ratio of about 0.2 to about 3 relative to iron; and one or more Group IA or IIA metals.

[0172] The one or more Group IA or IIA metals may be present at a molar ratio from 0 to about 0.60 relative to iron; and Zn at a molar ratio from 0 to about 0.50 relative to iron.

[0173] The reduction catalyst may comprise K, Na, Cs, Rh, or a combination thereof at a molar ratio 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 relative to iron. In other embodiments, the reduction catalyst comprises Na at a molar ratio 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 relative to iron.

[0174] The reduction catalyst may comprise K, Na, Cs, Rh, or a combination 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 certain 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.

[0175] The reduction catalyst may afford a product stream having a methane selectivity of less than about 11 carbon mole%, or less than about 10 carbon mole%. The olefin catalyst may afford a product stream having a methane selectivity of about 4 carbon mole% to about 11 carbon mole%, or about 5 carbon mole% to about 10 carbon mole%. Unless specifically identified otherwise, selectivity values disclosed herein are in carbon mole%.

[0176] The reduction catalyst may afford a product stream having an olefin to paraffin ratio (O / P) of greater than about 7. The reduction catalyst may afford a product stream having an olefin to paraffin ratio (O / P) of about 7 to about 9, about 8 to about 9, or about 8.

[0177] In certain aspects, the reduction catalyst further comprise a reduction catalyst support. The reduction catalyst support may be any suitable material that can serve as a catalyst support, or any reduction catalyst support disclosed above.

[0178] In certain embodiments, the reduction catalyst comprising the reduction catalyst support is in a form of particles having an average size from about 10 nm to about 5 pm, about 20 nm to about 5 pm, about 50 nm to about 1 pm, about 100 nm to about 500 nm, or about 50 nm to about 300 nm.

[0179] In certain embodiments, the reduction catalyst comprising the reduction catalyst support comprises from 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.

[0180] In certain embodiments, the reduction catalyst support is a high surface area scaffold. In further embodiments, the reduction catalyst support comprises mesoporous silica. In yet further embodiments, the reduction catalyst support comprises carbon allotropes.

[0181] In certain embodiments, the reduction catalyst is pretreated with syngas. In yet further embodiments, the reduction catalyst is pretreated with hydrogen. In still further embodiments, the reduction catalyst is heated with inert gas (including but not limited to nitrogen gas, argon) before the production.

[0182] Reduction catalysts disclosed herein have improved selectivity for olefins and / or paraffins over methane and improved means for adjusting the olefin to paraffin ratio.

[0183] By using a reduction catalyst disclosed herein with carbon conversion, a carbon source gas may be converted into a hydrocarbon mixture comprising olefins and paraffins. The hydrocarbon mixture may have an olefin to paraffin ratio (O / P) of greater than about 7. The reduction catalyst may afford a product stream having an olefin to paraffin ratio (O / P) of about 7 to about 9, about 8 to about 9, or about 8.

[0184] Methane is generally an undesirable byproduct of carbon dioxide conversion. Methane production is therefore a factor of the effectiveness of the catalyst, as methane production is undesirable. Accordingly, the lower the methane production (also referred to herein as methane selectivity, SCi, defined in Equation 1), the better the catalyst. Referring to Equation 1, Cmol.CEU represents mole fraction of methane in the product stream, Cmol.CChfeed represents mole fraction of CCh in the feed stream, and Cmol.CChproduct represents the mole fraction of CO2 in the product stream.

[0185] Eq. 1: Selectivity for methane (SCi) = [Cmol.CEU / (Cmol.CChfeed -

[0186] Cmol . CCUproduct)]

[0187] The reduction catalyst disclosed herein may have a methane selectivity (SCi) of less than about 15 carbon mole%, less than about 11 carbon mole%, or less than about 10 carbon mole%. The reduction catalyst may have a methane selectivity of about 2 to about 15, about 4 to about 15, about 5 to about 12, about 5 to about 11, about 6 to about 11, or about 8 to about 11 carbon mole%. The reduction catalysts described herein may have a selectivity for C2to C4 hydrocarbons (SC2-C4) of greater than about 15, greater than about 20, greater than about 25, greater than about 30, greater than about 35, or greater than about 35 carbon mole%. The reduction catalysts described herein may have a SC2-C4 from about 15 to about 50, about 20 to about 45, or about 25 to about 45 carbon mole%. The reduction catalysts described herein may have a SC2-C4 of about 28, about 35, about 38, about 39, or about 45 carbon mole%. The selectivity for C2-4 is determined by adding (selectivity for C2) + (selectivity for C3) + (selectivity for C4), with each selectivity value calculated according to Equation 2. Referring to Equation 2: Cxrepresents a hydrocarbon having a carbon number of x; Cmol.Cx represents mole fraction of Cxin the product stream; Cmol.CChfeed represents mole fraction of CO2 in the feed stream; and Cmol.CChproduct represents the mole fraction of CO2 in the product stream.

[0188] Eq. 2: Selectivity for hydrocarbon Cx(SCX) = [Cmol.Cx / (Cmol.CChfeed -

[0189] Cmol . CCEproduct)] The reduction catalysts disclosed herein may have a selectivity for C5+ hydrocarbons (SC5+, wherein C5+ refers to any hydrocarbons with a carbon number of 5 or higher) of greater than about 20, greater than about 22, greater than about 25, greater than about 28, greater than about 30, greater than about 32, or greater than about 34 carbon mole%. The reduction catalysts disclosed herein may have a selectivity for C5+ hydrocarbons (SC5+) from about 20 to about 45, about 22 to about 43, about 25 to about 43, about 28 to about 43, or about 30 to about 40 carbon mole%. The reduction catalysts disclosed herein may have a selectivity for C5+ hydrocarbons (SC5+) of about 29, about 31, about 33, about 34, about 35, or about 43 carbon mole%. The higher the selectivity for C5+ hydrocarbons, the better the catalyst performance for the processes of carbon dioxode conversion disclosed herein.

[0190] Oxygenates are generally an undesirable byproduct of carbon dioxide conversion. The reduction catalyst disclosed herein may have an oxygenate selectivity (Soxy) of less than about 20, less than about 16, less than about 14, or less than about 15 carbon mole%. The reduction catalyst may have an oxygenate selectivity of about 2 to about 20, about 4 to about 18, or about 4 to about 16 carbon mole%.

[0191] Metal leaching can be a problem associated with the use of metal-containing catalysts. Metal leaching of the catalysts can cause a number of problems, including: i) Product contamination: metal ions from the catalyst can dissolve into liquids, which can contaminate the product stream, and may require significant downstream processing to remove the metals; ii) System corrosion: metal leaching can cause corrosion in the system; and iii) Catalyst deactivation: metal leaching can cause the loss of active species from the catalyst and loss of efficacy, in terms of activity and selectivity. The higher the rate of leaching, the faster the deactivation of the catalyst.

[0192] Reduction catalysts of the disclosure provide significant improvements in metal leaching over other catalysts, including unsupported metal catalysts. The formed reduction catalysts (that is, the catalyst including the binder) disclosed herein have a significant reduction in metal leaching over the powder form of the same catalyst (i.e., without the binder). The amount of metal leaching when comparing the powder catalyst to a formed catalyst may be decreased by over about 50%, over about 70%, over about 80%, or over about 90%.

[0193] The amount of total metal leaching in the effluent may be measured once the reaction has reached a steady state by: i) separating the aqueous portion from the oil portion of the effluent; and ii) analyzing a sample of the aqueous portion by ICP-MS to obtain a concentration of metal leached in the aqueous sample. The method of measuring metal leaching may further include: iii) dissolving the oil portion in an acid, such as nitrohydrochloric acid; iv) analyzing a sample of the dissolved oil portion by ICP-MS to obtain a concentration of metal in the oil sample; and v) adding the concentration of metal in the oil sample and the concentration of metal in the aqueous sample to obtain the total metal leaching. After steady state has been reached the oil sample generally includes less than about 1 ppm of leached metal. Before steady state has been reached, the loose powder in the catalyst migrates into the effluent and dissolves in the oil portion of the effluent and may be tested if warranted. As the time on stream continues, the loose powder in the catalyst is eliminated and thus the concentration of metal in the oil portion of the effluent reduces to zero.

[0194] Steady state of the reaction may be reached after a time on stream that results in the concentration (ppm) of the second element being about 10 ppm or less, about 8 or less, or about 6 ppm or less. Steady state of the reaction may be reached after a time on stream that results in the concentration (ppm) of the second element being 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. Steady state may be reached after about 100 hours to about 1000 hours, about 200 hours to about 800 hours, about 200 hours to about 600 hours time on stream. Steady state of the reaction may be determined by the concentration of the second element because the second element leaches more than the active metals and is in the lower amount in the catalyst than the active metals. (1) When the reduction catalyst is contacted with a continuous flow of fluid, the total concentration of iron, zinc, and one or more second elements in the effluent at steady state may 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 second elements in the effluent at steady state 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 second elements in the effluent tested at steady state may be 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 second elements may also be understood as the metal leaching in the reactor effluent stream tested after an amount of time on stream, or at steady state.

[0195] The total concentration of the one or more second elements in the effluent at steady state 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 the one or more second elements in the effluent tested at steady state may be 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. When the second element is sodium, the total concentration of sodium, also understood as the concentration of sodium leached from the formed catalyst, in the effluent at steady state 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 at steady state may be about 0 ppm to about 6 ppm, or greater than about 0 ppm to about 6 ppm.

[0196] The total concentration of iron, zinc, and one or more second elements in the effluent tested after about 200 hrs to about 400 hrs of time on stream may 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 second elements in the effluent tested after about 400 hrs of time on stream 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 second elements in the effluent tested after about 400 hrs of time on stream may be 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 second elements in the effluent tested after about 200 hrs of time on stream may 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 second elements in the effluent tested after about 200 hrs of time on stream may be about 0 ppm to about 50 ppm, about 1 ppm to about 40 ppm, about 1 ppm to about 20 ppm, or about 1 ppm to about 15 ppm. Metal leaching refers to the total amount (i.e., concentration) of iron, zinc and the second element selected from Group IA, IIA, and / or X metal ions present in the effluent tested after an amount of time on stream.

[0197] Because there may be less of the second element present in the catalyst than iron or zinc, reducing the leaching of the second element may be especially important in maintaining the life of the catalyst. The amount of leaching of the second element (e.g., Na, K) of the formed catalyst in the effluent tested after about 200 hrs to about 400 hrs of time on stream may be less than about 10 ppm, less than about 8 ppm, less than about 5 ppm, or less than about 2 ppm. The amount of leaching of the second element of the formed catalyst in the effluent tested after about 400 hrs of time on stream may be less than about 10 ppm, less than about 8 ppm, less than about 5 ppm, or less than about 2 ppm. The amount of leaching of the second element of the formed catalyst in the effluent tested after about 400 hrs of time on stream may be about 0 ppm to about 10 ppm, about 0 ppm to about 8 ppm, about 0 ppm to about 6 ppm, about 0.1 ppm to about 5 ppm, or about 1 ppm to about 4 ppm.

[0198] The amount of leaching of the second element of the formed catalyst in the effluent tested after about 200 hrs of time on stream may be less than about 10 ppm, less than about 8 ppm, less than about 5 ppm, or less than about 4 ppm. The amount of leaching of the second element of the formed catalyst in the effluent tested after about 200 hrs of time on stream may be about 1 ppm to about 10 ppm, about 1 ppm to about 8 ppm, about 1 ppm to about 5 ppm, or about 1 ppm to about 4 ppm.

[0199] The formed reduction catalyst referred to herein contains a binder and shape formed by any known means in the art, for example but not limited to, extrusion, press, powder pressed to pellets, tablets or other shaped forms. The formed catalyst (as extrudate or pellet) may have a crush strength greater than about 20 N / mm, greater than about 25 N / mm, greater than about 30 N / mm or greater than about 40 N / mm. The formed catalyst (as extrudate, pellet, or tablet) may have a crush strength of about 20 N / mm to about 100 N / mm, about 20 N / mm to about 80 N / mm, about 20 N / mm to about 65 N / mm, about 30 N / mm to about 65 N / mm, about 35 N / mm to about 60 N / mm, or about 40 N / mm to about 55 N / mm.

[0200] Due to the reduced metal leaching, the reduction catalyst disclosed herein have a longer life (i.e., before deactivation) than other catalysts. The reduction catalyst disclosed herein may maintain activity for over about one year, over about 18 months, over about 20 months, over about 36 months, or over about 48 months. The reduction catalyst disclosed herein may maintain activity for about one year to about 5 years, about two years to about 5 years, about 3 years to about 5 years, or about 4 years to about 5 years. The term “maintain activity” means that the activity of the catalyst in conversion of CO2 to hydrocarbons remains above about 75% of its initial activity.

[0201] The product stream may comprise C1-C40 hydrocarbons. The C1-C40 hydrocarbons of the product stream may comprise (i) paraffins (n-paraffms, iso-paraffins, cyclo-paraffins), olefins (n-olefins, iso-olefins), and (2) aromatics. The product stream may also comprise: (3) oxygenates (alcohols, ketones, esters, aldehydes and acids), and (4) water.

[0202] The feed stream may comprise a carbon source gas, e.g., CO2, and a reduction gas, e.g., H2, IN certain embodiments, the feed stream may further comprise one or more of the following: CO, CH4, C2H4,C2H6, C3H6, C3H8, C4H8, C4H10.

[0203] The reduction catalyst may comprise iron and zinc, one or more second elements selected from Group IA, IIA, and X metals, and a binder. When the reduction catalyst includes a binder, it may also be referred to as a formed reduction catalyst. The reduction catalyst may comprise iron and zinc; optionally alumina; optionally a first element selected from copper, cobalt, manganese, chromium, or combinations thereof; optionally one or more second elements selected from Group IA, IIA, and X metals; and a binder

[0204] The reduction catalyst may comprise 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 be free of a first element selected from copper, cobalt, or combinations thereof.

[0205] The reduction catalyst may comprise the second element selected from one or more Group IA or IIA metals. The one or more Group IA or IIA metals may comprise magnesium, calcium, potassium, sodium, cesium, rubidium, or any combination thereof. The one or more Group I A or IIA metals may consist of magnesium, calcium, potassium, sodium, cesium, or rubidium. The one or more Group IA or IIA metals may comprise magnesium. The one or more Group IA or IIA metals may comprise calcium. The one or more Group IA or IIA metals may comprise potassium. The one or more Group I A or IIA metals may comprise sodium. The one or more Group I A or IIA metals may comprise cesium. The one or more Group I A or IIA metals may comprise rubidium. The one or more Group IA or IIA metals may consist of magnesium. The one or more Group IA or IIA metals may consist of calcium. The one or more Group I A or IIA metals may consist of potassium. The one or more Group I A or IIA metals may consist of sodium. The one or more Group IA or IIA metals may consist of cesium. The one or more Group IA or IIA metals may consist of rubidium.

[0206] The reduction catalyst may comprise the second element being a Group X metal. The Group X metal may be selected from palladium, platinum, iridium, nickel, and rhodium. The Group X metal may be platinum. The Group X metal may be palladium. The Group X metal may be nickel.

[0207] The reduction catalyst may also include one or more third elements selected from a Group V, VI, VII, VIII, IX, and XI metal (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 be free of a third element selected from a Group V, VI, VII, VIII, IX, and XI metal

[0208] The reduction catalyst may comprise the Group IA, IIA, or X metal at about 0.1 wt% to about 60 wt% of the total weight of iron, zinc, and Group IA, IIA, or X metal. The reduction catalyst may comprise the Group IA, IIA, or X metal at 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 the total weight of iron, zinc, and Group IA, IIA, or X metal. The reduction catalyst may comprise a Group IA metal at about 0.1 wt% to about 60 wt% of the total weight of iron, zinc, and Group IA metal. The reduction catalyst may comprise the Group IA metal at 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 the total weight of iron, zinc, and Group I A metal.

[0209] The reduction catalyst may comprise Na, Mn, K, Cs, Li, Rb at a molar ratio from 0 to about 0.60 relative to iron. In certain embodiments, the reduction catalyst comprises: iron; K, Cs, Mg, Rh, Ca, or a combination thereof, at a molar ratio of from 0 to about 0.20 relative to iron; Na, Cu, Cr, Mn, or a combination thereof, at a molar ratio of from 0 to about 0.60 relative to iron; and / or Co, Ru, Ni, or a combination thereof, at a molar ratio of from 0 to about 0.50 relative to iron.

[0210] The iron may be in metal form, in the form of an iron oxide, or a combination thereof. In certain embodiments, the iron is in the iron oxide form. The iron oxide may be FeO, magnetite (FesCU), hematite (Fe20s), or a combination thereof. In some embodiments, the iron oxide is magnetite (FesCU). In other embodiments, the iron oxide is a combination of magnetite (FesCU) and hematite (Fe2O3). In other embodiments, the iron oxide is a combination of FeO, magnetite (FesO^ and hematite (Fe20s).

[0211] The reduction catalyst may include: iron and zinc, with one or both of the iron and zinc being present in oxide or carbide forms. The iron oxide may be in the form of FeO, Fe20s (hematite), FesO4 (magnetite) or a combination thereof. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of Fe20s. The iron oxide may be substantially (e.g., over about 80%, or over about 90%) in the form of FesO4.

[0212] The reduction catalyst may comprise zinc at a molar ratio of about 0.2 to about 3 relative to iron, or about 0.3 to about 3 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.2 to about 1 relative to iron, or about 0.4 to about 1 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.5 relative to iron. In other embodiments, the reduction catalyst comprises zinc at a molar ratio of about 1.0 relative to iron. In certain embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.75 relative to iron, about 0.6 relative to iron, about 0.5 relative to iron, about 0.4 relative to iron, about 0.3 relative to iron, or about 0.25 relative to iron. In some embodiments, the reduction catalyst comprises zinc at a molar ratio of about 0.5 relative to iron.

[0213] The reduction catalyst may comprise a molar ratio of iron to zinc 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: l to about 3: l. The reduction catalyst may comprise a molar ratio of iron to zinc 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 comprise a molar ratio of iron to zinc of about 2: 1.

[0214] In some embodiments, the reduction catalyst comprises: iron; zinc at a molar ratio of about 0.2 to about 6 relative to iron; and one or more Group IA and IIA metals. The one or more Group IA and IIA metals may be present at a molar ratio from 0 to about 0.60 relative to iron; and Zn at a molar ratio from 0 to about 0.50 relative to iron. In some embodiments, the reduction catalyst comprises: iron; zinc at a molar ratio of about 0.2 to about 6 relative to iron; and one or more Group IA, IIA, and X metals. The one or more Group IA, IIA, and X metals may be present at a molar ratio from 0 to about 0.60 relative to iron; and Zn at a molar ratio from 0.2 to about 3 relative to iron.

[0215] The reduction catalyst may comprise K, Na, Cs, Rh, Rb, Mn, Li, Pt, Pd, Ru, Cu, Mo, Ce, or a combination thereof at a molar ratio 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 relative to iron. In other embodiments, the reduction catalyst comprises Na or K at a molar ratio 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 relative to iron.

[0216] The reduction catalyst may comprise K, Na, Cs, Rh, Rb, Mn, Li, Pt, Pd, Ru, Cu, Mo, Ce, or a combination thereof in an amount of about 0.1 wt% to about 10 wt%, about 0.2% to about 10%, about 0.1% to about 2%, about 0.5% to about 5%, about 0.2% to about 1.5%, or about 0.5% to about 1.0% of the total weight of iron plus zinc. In certain embodiments, the reduction catalyst comprises Na or K in an amount of about 0.2% to about 10%, about 0.5% to about 5%, about 0.5% to about 3%, about 0.5% to about 1%, or about 1% to about 5% of the total weight of iron plus zinc. In other embodiments the reduction catalyst may comprise Na in an amount of about 0.2% to about 10%, about 0.5% to about 5%, about 0.5% to about 3%, about 0.5% to about 1%, or about 1% to about 5%of the total weight of iron plus zinc.

[0217] The reduction catalyst may comprise iron, zinc and one or more Group IA or IIA metals, having a molar ratio of iron to zinc 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; and the one or more Group IA or IIA metals present at about 0.5% to about 1.0% of the total weight of iron plus zinc.

[0218] The reduction catalyst may comprise iron, zinc, and the one or more Group IA, IIA or X metals being sodium, lithium, platinum, cesium, rubidium, manganese, or potassium, having a molar ratio of iron to zinc of about 1.5: 1 to about 2.5: 1; and the Na, Li, Rb, Mn, Cs, Pt, or K present at about 0.5% to about 1.0% of the total weight of iron plus zinc. The reduction catalyst may comprise iron, zinc, and the one or more Group IA or IIA metals being sodium or potassium, having a molar ratio of iron to zinc of about 1.5: 1 to about 2.5: 1; and the Na or K present at about 0.5% to about 1.0% of the total weight of iron plus zinc.

[0219] In certain aspects, the reduction catalysts further comprise a reduction catalyst support. The reduction catalyst support may be any suitable material that can serve as a catalyst support.

[0220] In some embodiments, the catalyst support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, and tin. In further embodiments, the catalyst support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron, and tin. In some preferred embodiments, the catalyst support comprises 7-alumina. In certain embodiments, the catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In certain embodiments, the additional support is selected from carbon, silica, zeolite, alumina, iron oxide, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the catalyst support is an aluminum oxide that is formed in-situ as part of the catalyst. In some embodiments, the catalyst support is selected from, but not limited to, AI2O3, ZrCh, SnCh, SiCh, ZnO, and TiCh. In some embodiments, the catalyst support is selected from AI2O3, ZrCh, SnCL, SiCh, ZnO, and TiO2. In some embodiments, the catalyst support is selected from AI2O3, ZrO2, SnO2, SiO2, ZnO, Fe2O3, Fe3O4, FeO, and TiO2.

[0221] In some embodiments, the reduction catalyst support comprises one or more carbonbased materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0222] In some embodiments, the reduction catalyst support is selected from SiAlOx, SO4- ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2). In further embodiments, the reduction catalyst support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0223] In some embodiments, the reduction catalyst support is a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM- 49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the reduction catalyst support is MCM-49. In further embodiments, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the modifier is present as zeolite supported metals or as isomorphous substitution in the zeolite framework.

[0224] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine, and / or sulfur.

[0225] In certain embodiments, the reduction catalyst support is a mesoporous material. In such embodiments, as will be appreciated by one of ordinary skill in the art, the physical characteristics of the mesoporous material, e.g., mesopore volume and surface area may be measured using standard gas absorption measurement techniques known in the art including, for example, the Barrett- Joy ner-Halenda (BJH) method for determining pore size distributions and pore volumes, and the Brunauer, Emmett and Teller (BET) method for obtaining the specific surface area (hereinafter “surface area”). In further embodiments, the reduction catalyst support has a mesopore volume from about 0.01 to about 3.0 cc / g.

[0226] In certain embodiments, the reduction catalyst support has surface area from about 10 m2 / g to about 1000 m2 / g. In certain embodiments, the reduction catalyst comprising the reduction catalyst support has a surface area from about 10 m2 / g to about 1000 m2 / g.

[0227] In certain embodiments, the reduction catalyst comprises the reduction catalyst support in a form of particles having an average size from about 10 nm to about 5 pm, about 20 nm to about 5 pm, about 50 nm to about 1 pm, about 100 nm to about 500 nm, or about 50 nm to about 300 nm.

[0228] In certain embodiments, the reduction catalyst comprises the reduction catalyst support in an amount from 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.

[0229] In certain embodiments, the reduction catalyst support is a high surface area scaffold. In further embodiments, the reduction catalyst support comprises mesoporous silica. In yet further embodiments, the reduction catalyst support comprises carbon allotropes. In certain embodiments, the reduction catalyst is a nanoparticle catalyst. In further embodiments, the particle sizes of the reduction catalyst on the surface of the scaffold are about 1 nm to about 5 nm, about 5 nm to about 100 nm, or about 100 to about 500 nm. In certain embodiments, the particles not subjected to agglomeration are 100-500 nm in particle size.

[0230] In certain embodiments, the reduction catalyst is pretreated with syngas. In yet further embodiments, the reduction catalyst is pretreated with hydrogen. In still further embodiments, the reduction catalyst is heated with inert gas (including but not limited to nitrogen gas, argon) before the production.

[0231] The reduction catalyst may include a binder. The binder may be any binder known for use in the art. 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), aluminate (e.g., sodiumaluminate), silica (e.g., silicates, such as potassium-silicate and sodium-silicate, LUDOX®) pseudoboehmite alumina (e.g., VERSAL® V-250), bentonite clay, montmorillinite clay, tungsten, zirconate, or any combination thereof.

[0232] The binder may be present in an amount of about 0.1% to about 60% by weight, about 5% to about 40%, or about 10% to about 30% by weight of the total catalyst composition. In certain embodiments, the binder is present in about 0.1% to about 30%, about 0.1% to about 20%, about 1% to about 30%, about 1% to about 20%, about 5% to about 25%, about 5% to about 20%, about 10% to about 20%, about 5% to about 15%, or about 15% to about 25% by weight of the total catalyst composition.

[0233] The binder may contain a promoter element selected from Na, K, Cs, Li, Rb, or a combination thereof. It was found that a promoter in the binder improves catalyst performance, e.g., activity, selectivity and stability; by maintaining the promoter level constant on the active metal components. In particular, the benefits of doping the binder include:

[0234] • improves methane selectivity;

[0235] • the acidity improves hydrocarbon yield;

[0236] • creates meso-porosity to the formed catalyst which may improve product selectivity; and

[0237] • reduces metal leaching.

[0238] The binder may be heterogeneous, amorphous or micro-porous materials. In certain 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 Na- aluminate, K-aluminate, Na-silicate, K-silicate, Na - zirconate, K- zirconate, Na- tungsten, K-tungsten or a combination thereof.

[0239] When a promoter is added to the binder, performance (e.g., in terms of SCi and SC5+) of the catalyst improves significantly. When comparing performance of a catalyst having a binder without a promoter to the same catalyst and binder with a promoter, SCi may improve (that is, decrease) by about 20% to about 65%, about 30% to about 55%., about 30% to about 40%, or about 45% to about 55%. When comparing performance of a catalyst having a binder without a promoter to the same catalyst and binder with a promoter, SC5+ may improve (that is, increase) 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 comparisons may be between a non-doped silicate binder and a doped (with promoter) silicate binder, or between a non-doped alumina binder and a doped (with promoter) silicate binder.

[0240] A binder may be preferably selected that minimizes or does not form any strong metal support interactions with the active metal(s) because forming such interactions would inhibit the catalytic properties of the active metal. A preferred binder may bond the small active metal particles together and form a sizeable extrudate / pellets (l-5mm). These extrudates / pellets are suited for application in industrial reactors. They also have better handling properties and avoid pressure drops in large scale reactors.

[0241] The binder disclosed herein reduces metal leaching which improves the catalyst life span. With a powder, the surface area is very large and so by forming an extrudate with a binder, thermal shock in large scale reactors may be reduced.

[0242] In certain embodiments, when the reduction catalyst comprises iron oxide and zinc oxide, and a Group IA or IIA metal, and when the first carbon source gas and first reduction gas are fed into the reduction reactor, the iron oxide reacts to be in an active form selected from the group consisting of: FexOy, FexCy, and any combination thereof, where x is 1-3 and y is 0- 4. The active form acts to convert CO2 to hydrocarbons selected from the group consisting of: olefins, paraffins, oxygenates, and any combination thereof.

[0243] CO 2 Reduction Catalyst Compositions

[0244] In certain aspects, the present disclosure provides reduction catalyst compositions, comprising one or more of the reduction catalysts disclosed herein and an additional support. The additional support may be any suitable material that can serve as a catalyst support, as defined above

[0245] In some embodiments, the catalyst composition is in a form of particles having an average size from about 10 nm to about 5 pm. In some embodiments, the catalyst composition is in a form of particles having an average size from about 20 nm to about 5 pm. In some embodiments, the catalyst composition is in a form of particles having an average size from about 50 nm to about 1 pm. In some embodiments, the catalyst composition is in a form of particles having an average size from about 100 nm to about 500 nm. In some embodiments, the catalyst composition is in a form of particles having an average size from about 50 nm to about 300 nm.

[0246] In some embodiments, the catalyst composition comprises from about 5 wt. % to about 80 wt. % of the catalyst. In some embodiments, the catalyst composition comprises from about 5 wt. % to about 70 wt. % of the catalyst. In some embodiments, the catalyst composition comprises from about 20 wt. % to about 70 wt. % of the catalyst. In some embodiments, the catalyst composition comprises from about 30 wt. % to about 70 wt. % of the catalyst.

[0247] In some embodiments, the support is a high surface area scaffold. In some embodiments, the support comprises mesoporous silica. In some embodiments, the support comprises carbon allotropes.

[0248] Methods of Preparation of Catalysts and Catalyst Compositions for CO 2 Reduction

[0249] The reduction catalysts and catalyst compositions of the present disclosure may be prepared by any suitable method. In certain aspects, the present disclosure provides methods for preparing the catalysts or the catalyst compositions disclosed herein, comprising preparing the catalyst by coprecipitation, wet impregnation, or ball milling.

[0250] In some embodiments, a method of making a powder catalyst comprises the following steps:

[0251] (a) providing a first solution comprising a source of zinc, iron, a base, and water;

[0252] (b) heating the first solution at a first temperature for a first period of time, thereby producing the first reaction mixture;

[0253] (c) heating the first reaction mixture at a second temperature for a second period of time to remove the water, thereby producing a solid precursor; and

[0254] (d) heating the solid precursor to a third temperature for a third period of time to afford the catalyst. In other embodiments, a method of making a powder catalyst comprises the following steps:

[0255] (a) providing a second solution comprising a source of zinc, iron, and water;

[0256] (b) providing a third solution comprising a base;

[0257] (c) heating the third solution at a third temperature for a third period of time;

[0258] (d) adding alumina to the third solution, thereby producing a second reaction mixture;

[0259] (e) adding the second solution to the second reaction mixture at a fourth temperature for a fourth period of time, thereby producing a third reaction mixture;

[0260] (f) heating the third reaction mixture at a fifth temperature for a fifth period of time, thereby producing a solid precursor;

[0261] (g) isolating the solid precursor;

[0262] (h) contacting the solid precursor with a solution comprising a Group IA metal, thereby producing a catalyst precursor; and

[0263] (i) heating the catalyst precursor to a sixth temperature for a sixth period of time, thereby isolating the catalyst.

[0264] In some embodiments, the method comprises the following steps: providing a first solution comprising a source of zinc, and a source of aluminum. Combining the first solution with a basic precipitant, such as a carbonate, to increase the pH of the metal salt containing solution thereby precipitating solid particles. The solid particles are dried and calcined to form a solid catalyst.

[0265] In certain embodiments, the base comprises carbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium. In other embodiments, the base comprises bicarbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium.

[0266] In some embodiments, the method comprises the following steps: providing a first solution comprising a cobalt source and introducing it to a pre-made copper-zinc alumina material via incipient wetness or wet impregnation, followed by drying and calcining to form a solid catalyst.

[0267] In some embodiments, the method comprises the following steps: mixing a cobalt source and a support in a mill jar to provide a first mixture; ball milling the first mixture for between 2 hours to 2 weeks to thereby provide a first precipitate; filtering the first precipitate and heating to a first temperature to provide a ball milled cobalt source; mixing the ball milled cobalt source with a source of copper and zinc and a source of the alumina to provide a second mixture; and isolating a solid material from the second mixture.

[0268] In some embodiments, the method further comprises combining the solid material with a source of the one or more Group IA metals. In some embodiments, the method further comprises pressing the solid material into pellets. In some embodiments, the method further comprises pressing the solid material into pellets prior to introduction into a flow reactor.

[0269] A method of making a formed catalyst comprising: providing a powder catalyst made by any suitable method known in the art; combining the powder catalyst, a binder and a lubricant to make a dry mixture; combining the dry mixture with a first solution comprising a peptizing agent, wherein the peptizing agent activates the binder thereby forming an extrudable dough. The extrudable dough may be processed in an extruder to afford a formed catalyst, which may take the form of extrudates, pellets, tablets, or the like. The formed catalyst may be further processed by heating to a drying temperature for a first period of time to afford a dried, formed catalysts, and / or heating to a calcining temperature for a second period of time to afford a calcined, formed catalysts. The calcined, formed catalyst may be the formed catalyst, which may be selected from extrudates, pellets, tablets, or the like.

[0270] The first period of time for drying may be about 1 to about 3 hours, about 1.5 to about 2.5 hours, or about 2 hours. The drying temperature may be at about 80 °C to about 200 °C, about 100 °C to about 180 °C, or about 110 °C to about 130 °C. The second period of time for calcining may 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 calcining temperature may be at about 280 °C to about 420 °C, about 300 °C to about 400 °C, or about 320 °C to about 370 °C.

[0271] Another method of making a formed catalyst comprises: providing a powder catalyst made by any suitable method known in the art; combining the powder catalyst with a slurry comprising a peptizing agent and a binder to make an extrudable dough. The extrudable dough may be processed as described above. The method may comprise combining the powder catalyst and a lubricant to make a dry mixture before combining with the slurry.

[0272] The lubricant may be any suitable lubricant known for use in the art. For example, the lubricant may be selected from magnesium stearate, stearic acid, calcium stearate, sodium stearyl fumarate, polyethylene glycols, silicone dioxide (also known as colloidal silicon dioxide), talc, beeswax, a hydrogenated vegetable oil (e.g., STEROTEX®, LUBRITAB®), and any combination thereof. The lubricant may be a hydrogenated vegetable oil. The peptizing agent may be any suitable peptizing agent known for use in the art. For example, the peptizing agent may be selected from an acid, a Group IA hydroxide, a polymer, or a combination thereof. The peptizing agent may be an acid selected from the group consisting of inorganic and organic acids. The peptizing agent may be nitric acid, phosphoric acid, acetic acid, hydrochloric acid, formic acid, sulfuric acid, oxalic acid, and any combination thereof. The peptizing agent may be nitric acid.

[0273] Catalysts for Conversion of Carbon Sources and Reduction Gas to Aromatics

[0274] In certain aspects, the systems and methods of the present disclosure involve the use of aromatic catalysts. As used herein, the term “aromatic catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to aromatics, but which does not necessarily itself comprise aromatics. Use of an aromatic catalyst may also produce other hydrocarbons in a lesser amount.

[0275] In certain embodiments, the aromatic catalyst comprises a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the zeolite is ZSM-5, MCM-49, PSH-3, or MCM-22. The zeolite may be ZSM-5. The 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.

[0276] The zeolite may comprise a modifier. The modifier may be Ga, Fe, Mn, Zn, P, Pt or a combination thereof. In certain embodiments, the zeolite comprises from 0 wt% to about 10 wt% of the modifier. In further embodiments, the zeolite comprises from 0.01 wt% to about 10 wt% of the modifier, from 0.01 wt% to about 5 wt% of the modifier, from 0.01 wt% to about 3 wt% of the modifier, from 0.1 wt% to about 1.5 wt% of the modifier, or from 0.5 wt% to about 1 wt% of the modifier. In certain 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.

[0277] Optional features of the invention relating to catalysts for conversion of carbon sources and reduction gas to aromatics described above may also constitute optional features in relation to catalysts for conversion of carbon sources to paraffins or catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, and vice versa.

[0278] The aromatic catalyst may include a binder. The binder may be any binder known for use in the art. In certain 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), aluminate, silicon, zirconium, silica, pseudoboehmite alumina (e.g., VERSAL® V-250), bentonite, or any combination thereof. The binder may be present in an amount of about 0% to about 60% by weight, or about 0% to about 40% by weight of the total catalyst composition. In certain embodiments, the binder is present in about 0.1% to about 30%, about 0.1% to about 20%, about 1% to about 30%, about 1% to about 20%, about 1% to about 15%, about 5% to about 30%, about 5% to about 20%, about 5% to about 15%, about 0.5% to about 10%, about 0.5% to about 5% by weight of the total catalyst composition. In an embodiment, the aromatic catalyst includes a silica binder in amount of about 15% to about 25%, or about 20% by weight of the total catalyst composition.

[0279] In certain embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, to aromatics. In other embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, and an olefin source to aromatics. The olefin source may be a hydrocarbon product mixture, such as a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins, or an olefin product mixture, such as a stream comprising one or more C4-9 olefins, to aromatics.

[0280] 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. Accordingly, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, to the specified aromatic molecule(s). Optionally, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, in the presence of a carbon gas source to the specified aromatic molecule(s). The aromatic catalyst used herein may have a selectivity for aromatics of over about 50 carbon mole%, over about 55 carbon mole%, over about 60 carbon mole%, or over about 65 carbon mole%. The aromatic catalyst may have a selectivity for aromatics of about 50 carbon mole% to about 90 carbon mole%, about 55 carbon mole% to about 85 carbon mole%, about 60 carbon mole% to about 85 carbon mole%, or about 65 carbon mole% to about 80 carbon mole%. The aromatic catalyst used herein may have a selectivity for target aromatic of about 5 carbon mole% to about 20 carbon mole%, or about 7 carbon mole% to about 15 carbon mole%. The aromatic catalyst used herein may have a selectivity for methane of less than about 8 carbon mole%, less than about 5 carbon mole%, or less than about 4 carbon mole%. The aromatic catalyst used herein may have a selectivity for methane of about 1 carbon mole% to about 8 carbon mole%, about 2 carbon mole% to about 6 carbon mole%, about 2 carbon mole% to about 5 carbon mole%, or about 3 carbon mole% to about 4 carbon mole%.

[0281] The aromatic reactor may afford an aromatic product mixture comprising a light aromatic product mixture and a target aromatic product mixture. The aromatic product mixture may comprise the light aromatic product mixture in about 70% to about 93% by weight of the total aromatic product mixture and the target aromatic product mixture in about 7% to about 15% by weight of the total aromatic product mixture. The aromatic product mixture may comprise the light aromatic product mixture in about 80% to about 93% by weight of the total aromatic product mixture and the target aromatic product mixture in about 7% to about 10% by weight of the total aromatic product mixture.

[0282] The light aromatic product mixture may include a mixture of benzene, toluene, A8 (aromatic molecules having 8 carbons). The aromatic product mixture may comprise about 10% to about 20% by weight of benzene and about 40% to about 50% by weight of toluene. The aromatic product mixture may comprise 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 comprise less than about 5% by weight, less than about 3% by weight, less than about 2% by weight of naphthalene. The aromatic product mixture may comprise about 10% to about 20% by weight of benzene, about 40% to about 50% by weight of toluene, and less than about 5%, or less than about 2% by weight of napthalene. The aromatic product mixture may comprise about 12% to about 18% by weight of benzene and about 40% to about 46% by weight of toluene, about 25% to about 35% by weight of A8 aromatics, and less than about 5%, or less than about 2% by weight of naphthalene.

[0283] Catalysts for Hydrogenation

[0284] In certain aspects, the systems and methods of the present disclosure involve the use of hydrogenation catalysts for hydrogenating percentages of the hydrocarbons produced. In certain embodiments, the hydrogenation catalyst may be independently selected from the catalysts described below. In certain embodiments, the hydrogenation catalyst of the present disclosure is a aluminosilicate catalyst, such as a zeolite. In further embodiments, the isomerization catalyst and / or the hydrogenation catalyst is AICI3. In yet further embodiments, the hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In still further embodiments, the hydrogenation catalyst is Pt on beta-zeolite. In certain embodiments, the hydrogenation catalyst of the disclosure comprises an isomerization catalyst metal, and a zeolite support. In further embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni- Mo.

[0285] The additional support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the additional support comprises y-alumina. In certain embodiments, the additional support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the additional support is an aluminum oxide that is formed in-situ as part of the reduction catalyst. In some embodiments, the additional support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the additional support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0286] The hydrogenation catalyst support may comprise: A) one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin, such as MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2; B) a carbon-based material such as activated carbon, carbon nanotubes, graphene, and graphene oxide;

[0287] C) SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2- TiO2); D) an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites; or E) a zeolite such as Y-type zeolites, beta-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 zeolites, MCM- 49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. Optionally, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals; and / or optionally the modifier is present as a zeolite-supported metal or as isomorphous substitution in the zeolite framework.

[0288] The additional support 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.

[0289] The additional support may be selected from SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiCh-AhCh, SiO2-TiO2). In further embodiments, the additional support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0290] The additional support may be a zeolite such as Y-type zeolites, beta-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 zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In further embodiments, the zeolites comprise additional metals such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the additional metals are present as zeolite supported metals or as isomorphous substitution in the zeolite framework. The additional support may be modified with molybdenum, chlorine, and / or sulfur.

[0291] In still further embodiments, the hydrogenation catalyst may be selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiA10x, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni- W / SiA10x, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, and Ni-W / SAPO.

[0292] Catalysts for Hydrocracking

[0293] The systems and methods of the present disclosure can use any suitable hydrocracking catalyst, including those known in the art. In some embodiments, similar catalysts to those described for the hydrogenation and isomerization step (above) are also used for hydrocracking.

[0294] Any suitable hydrocracking catalysts known in the art may be used in these processes. However, the particular embodiments set forth below are provided both to exemplify the use of such catalysts and to identify catalysts particularly well-suited for use in conjunction with the other features of the systems and methods disclosed herein.

[0295] In further 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 may be any suitable material that can serve as a catalyst support. The hydrocracking support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some embodiments, the hydrocracking support comprises y-alumina. In certain embodiments, the hydrocracking support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the hydrocracking support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the hydrocracking support is an aluminum oxide that is formed in-situ as part of the reduction catalyst. In some embodiments, the hydrocracking support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the hydrocracking support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0296] 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.

[0297] In some embodiments, the hydrocracking support is selected from SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2). In further embodiments, the hydrocracking support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0298] In some embodiments, the hydrocracking support is a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM- 49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In further embodiments, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the modifier is present as a zeolite supported metal or as isomorphous substitution in the zeolite framework.

[0299] In some embodiments, the hydrocracking support is modified with molybdenum, chlorine, and / or sulfur.

[0300] In certain embodiments, the hydrocracking metal comprises from about 0.5 wt% to about 40 wt% of the hydrocracking catalyst. In further embodiments, the hydrocracking metal comprises about 0.5 wt% of the hydrocracking catalyst. In yet further embodiments, the hydrocracking metal comprises about 1 wt% of the hydrocracking catalyst. In still further embodiments, the hydrocracking metal comprises about 10 wt% of the hydrocracking catalyst. In certain embodiments, the hydrocracking metal comprises about 20 wt% of the hydrocracking catalyst. In further embodiments, the hydrocracking metal comprises about 30 wt% of the hydrocracking catalyst. In yet further embodiments, the hydrocracking metal comprises about 40 wt% of the hydrocracking catalyst.

[0301] Optional features of the invention relating to catalysts for hydrocracking described above may also constitute optional features in relation to catalysts for conversion of carbon sources to paraffins, catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, catalysts for conversion of carbon sources and reduction gas to aromatics or catalysts for hydrogenation and isomerization, and vice versa.

[0302] Catalysts for Alkylation of Aromatics

[0303] The alkylation step may be performed with any suitable catalyst. In certain embodiments, the alkylation catalyst is a liquid acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), tungsten, platinum, or a zeolite. In further embodiments, the alkylation catalyst is a zeolite, such as an acidic zeolite. In yet further embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO-11, S APO-5, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolite, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, USY zeolite, and combinations thereof. In certain embodiments, the zeolite is MCM-22, MCM-49, PSH-3, mordenite zeolite, Y-type zeolite, or beta-zeolite.

[0304] The weight-based space velocity is measured as the amount of reactant mass per unit catalyst mass per unit time. The range for the weight-based space velocity for the alkylation catalyst is between about 0.1 g of reactant per g of catalyst per hour (0.1 h-1) and about 50 h- 1, or between about 0.5 h-1 to about 20 h-1.

[0305] Catalysts for Oligomerization

[0306] The oligomerization catalyst may be a heterogeneous acid catalyst, such as a zeolite or a molecular sieve. The oligomerization catalyst may be an amorphous or crystalline aluminosilicate molecular sieve. The oligomerization catalyst may be a zeolite. The oligomerization catalyst may be an aluminosilicate zeolite. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, beta-zeolite, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. The oligomerization catalyst may be ZSM-5, beta-zeolite, MCM-22, MCM-49, PSH- 3, mordenite, SAPO-5, or a combination thereof. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof. The oligomerization catalyst may be ZSM-5. The oligomerization catalyst may MCM-22, PSH-3, or MCM-49.

[0307] The weight-based space velocity is measured as the amount of reactant mass per unit catalyst mass per unit time. The range for the weight-based space velocity for the oligomerization catalyst is between about 0.1 g of reactant per g of catalyst per hour (0.1 h-1) and about 50 h-1, between about 0.5 h-1 about 20 h-1, or between about 0.5 h-1 and about 5 h- 1.

[0308] When the oligo-alkylation reactor is used, a combination of one or more alkylation catalyst and one or more oligomerization catalysts may be combined within the oligo- alkylation reactor. The one or more alkylation catalyst and the one or more oligomerization catalysts may be mixed, layered within the reactor optionally with an intermediate quench. In other embodiments, an oligo-alkylation catalyst may be used. The oligo-alkylation catalyst may be a liquid acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), an amorphous heterogeneous acid catalyst, such as tungsten / Zr oxide, a heterogeneous acid catalyst, such as a zeolite or a molecular sieve, and a combination thereof. In some embodiments, the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve. In other embodiments, the oligo-alkylation catalyst is selected from the group consisting of: ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, zeolite beta, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. In further embodiments, the oligo-alkylation catalyst is ZSM-5, betazeolite, MCM-22, PSH-3, MCM-49, mordenite zeolite, SAPO-5, or any combination thereof.

[0309] Reduction Gases, Carbon Source Gases, and Ratios Thereo f

[0310] The systems and methods of the present disclosure can be designed to utilize any combination of suitable reduction gases and suitable carbon source gases. Said carbon source and reduction gases may in certain embodiments be provided into the requisite reaction vessels separately, or they may in certain embodiments be pre-mixed (e.g., the first reduction gas feed and the first carbon source gas feed can, in some embodiments refer to the same physical feature, as can the second reduction as feed and the second carbon source gas feed) to provide a single feed stream comprising both a carbon source gas and a reduction gas, which is coupled to the appropriate reactor.

[0311] Additionally, a single gas feed comprising the first reduction gas feed, the first carbon source gas feed, the second reduction gas feed, and the second carbon source gas feed can be pre-mixed to provide a single feed stream comprising both a carbon source gas and a reduction gas, coupled to both the aromatic reactor and the reduction reactor.

[0312] In certain embodiments, the single gas feed may include CO2, H2, CO, C2, C3, CH4, and any combination thereof. The feed stream may contain H2 / CO2, in a range of about 10% to about 95%, and each of CO, C2, C3, and CH4 in the range of about 0% to about 65%. The source of CO, C2, C3, and / or CH4 may be from a recycle stream or may be introduced in the fresh feed stream.

[0313] In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and the fourth reduction gas are independently selected from H2, a hydrocarbon, synthesis gas (CO / H2), or from a gas that is, or is derived from, flare gas, waste gas, or natural gas.

[0314] In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is H2. In further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is synthesis gas. In yet further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In still further embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is, or is derived from, flare gas, waste gas, or natural gas. In certain embodiments, the first reduction gas, the second reduction gas, the third reduction gas, and / or the fourth reduction gas is CH4.

[0315] In certain embodiments, the first carbon source gas and / or the second carbon source gas is CO2. In further embodiments, the first carbon source gas and / or the second carbon source gas comprises CO2. In yet further embodiments, the first carbon source gas and / or the second carbon source gas is CO. In still further embodiments, the first carbon source gas and / or the second carbon source gas comprises CO.

[0316] As will be understood by those of skill in the art, the flow rate of carbon source gas and / or reduction gas, or various product mixtures through the paraffin and / or aromatic reactors (or elsewhere in the disclosed systems and methods) can be adjusted as needed to afford the desired product output characteristics.

[0317] Additionally, as will be understood by those of skill in the art, the carbon source gases and the reduction gases may be provided in any suitable ratio that affords the desired product output characteristics. In certain embodiments, the molar ratio of the first reduction gas to the first carbon source gas is from about 10: 1 to about 1 : 10. In further embodiments, the molar ratio of the first reduction gas to the first carbon source gas is from about 5 : 1 to about 0.5 : 1. In yet further embodiments, the molar ratio of the second reduction gas to the second carbon source gas is from about 10: 1 to about 1 : 10. In still further embodiments, the molar ratio of the second reduction gas to the second carbon source gas is from about 5: 1 to about 0.5: 1.

[0318] Definitions

[0319] Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry, cell and tissue culture, molecular biology, cell and cancer biology, neurobiology, neurochemistry, virology, immunology, microbiology, pharmacology, genetics and protein and nucleic acid chemistry, described herein, are those well known and commonly used in the art.

[0320] The methods and techniques of the present disclosure are generally performed, unless otherwise indicated, according to conventional methods well known in the art and as described in various general and more specific references that are cited and discussed throughout this specification. See, e.g. “Principles of Neural Science”, McGraw-Hill Medical, New York, N.Y. (2000); Motulsky, “Intuitive Biostatistics”, Oxford University Press, Inc. (1995); Lodish et al., “Molecular Cell Biology, 4th ed.”, W. H. Freeman & Co., New York (2000); Griffiths et al., “Introduction to Genetic Analysis, 7th ed.”, W. H. Freeman & Co., N.Y. (1999); and Gilbert et al., “Developmental Biology, 6th ed.”, Sinauer Associates, Inc., Sunderland, MA (2000).

[0321] Chemistry terms used herein, unless otherwise defined herein, are used according to conventional usage in the art, as exemplified by “The McGraw-Hill Dictionary of Chemical Terms”, Parker S., Ed., McGraw-Hill, San Francisco, C.A. (1985).

[0322] All of the above, and any other publications, patents and published patent applications referred to in this application are specifically incorporated by reference herein. In case of conflict, the present specification, including its specific definitions, will control. The term “Log of solubility”, “LogS” or “logS” as used herein is used in the art to quantify the aqueous solubility of a compound. The aqueous solubility of a compound significantly affects its absorption and distribution characteristics. A low solubility often goes along with a poor absorption. LogS value is a unit stripped logarithm (base 10) of the solubility measured in mol / liter.

[0323] The term “monocyclic aromatic(s)” as used herein refer to compounds comprising only one single aromatic ring, which may be substituted or unsubstituted (e.g., alkylbenzenes), and which may optionally be fused with non-aromatic rings (e.g., tetralins and indanes).

[0324] The term “polycyclic aromatic(s)” as used herein refers to compounds 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 aromatics” may be used to refer to a group of compounds comprising naphthalene and / or naphthalene derivatives.

[0325] The term “petroleum-derived” as used herein refers to compounds and compositions that are derived by physical and chemical processes from petroleum feedstocks, but does not include compounds and compositions whose carbon is derived from carbon dioxide or carbon monoxide, even if that carbon dioxide or carbon monoxide was produced from petroleum feedstocks (e.g., by combusting petroleum).

[0326] When the amount of an impurity is specified at a level of "about 0", it is understood by those of skill in the art that such a measurement is accurate to a certain number of significant figures based on the relevant detection method used.

[0327] As used herein, certain components, fractions, and feeds are described in terms of the carbon numbers (e.g., CX-Y) in said component, fraction, feed, etc. These descriptions indicate the possible (non-limiting) carbon numbers of the hydrocarbons present in said component, but do not require the presence of each and every carbon number within the range. For example, a feed described as comprising C9-15 hydrocarbons must comprise at least one component falling within the range of carbon numbers listed.

[0328] As used herein, the term “selectivity” and grammatical variants thereof refer to how selective a particular process or catalyst is for producing a particular product. The term refers to an exemplary selectivity value observed for a reaction performed with suitable reagents under conditions that have been selected, by a person of ordinary skill in the art, to maximize or minimize the production of a given product of interest. A value for selectivity may refer to the proportion of product(s) of interest compared to other products produced (which may not be of interest), or may refer to the proportion of other product(s) produced compared to product(s) of interest. Selectivity may be a function of the catalyst used in a process, and / or may be a function of process design or parameters (e.g., temperature, pressure, reagent concentration, GHSV, etc.), as would be understood by a person of ordinary skill in the art. Those of skill in the art are familiar with how to calculate selectivity for a given product. However, where an explicit calculation for selectivity is provided herein, that calculation method controls.

[0329] As used herein, the term “oligomerization,” and grammatical variants thereof, will be understood by those of skill in the art to refer to a process that may involve dimerization, trimerization, tetramerization, pentamerization, hexamerization, heptamerization, octamerization, nonamerization, decamerization, higher-order oligomerization, and combinations thereof. The extent of oligomerization in a particular reaction will determine the composition of the product stream, and depends on aspects of the reactant stream, as well as the reaction conditions.

[0330] EXAMPLES

[0331] The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of certain aspects and embodiments of the present invention, and are not intended to limit the invention.

[0332] Example 1 : CCh-to-paraffin catalyst compositions

[0333] Certain reduction catalysts of the disclosure comprise a mixed metal oxide. Examples of mixed oxide compositions are given below:

[0334] Mixed oxide composition denoted AaBbFeiooZnxOy: The catalyst is a mixed oxide consisting of iron, zinc oxide with additional promoter metals. The catalyst is donated as AaBbFeiooZnxOywhere a, b, and x represent the atomic composition of each metal and y is the number of oxygen atoms to complement the 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 range of a, b, and x are shown below: a. 0 < a < 20 b. 0 < b < 60 c. 0 < x < 50 Mixed oxide composition denoted AaBbFeiooXc'. The mixed oxide component of the catalyst consists of iron and zinc oxide modified with additional metals which is donated as AaBbFeiooXc: where a, b, and c represent the atomic composition of each metal. A is at least one of K, Cs, Rh, Mg, and Ca; and B is at least one of Na, Cu, Cr, and Mn, and X is at least one of Co, Ru and Ni. The range of a, b, and c are shown below: a. 0 < a < 20 b. 0 < b < 60 c. 0 < c < 50

[0335] Mixed oxide composition denoted AaBbXc'. The mixed oxide component of the catalyst includes cobalt or iron modified with additional metals which is donated as AaBbXioo: 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 range of a, b, and c are shown below: a. 0 < a < 20 b. 0 < b < 90 c. 0 < c < 50

[0336] Example 2: Synthesis of certain CCh-to-paraffin catalyst compositions

[0337] I. Mixed oxide catalyst preparation: An iron oxide and zinc oxide complex was first prepared by co-precipitation using a metal nitrate precursor solution with a 0.5 M concentration. This was then reacted with a 1.2 molar equivalents of sodium carbonate, mixed using parallel addition at 338 K over 1 hour.

[0338] This formed slurry was then aged while continuously stirring at 353K for 1 hour. The precipitate was then obtained by using vacuum filtration and a 0.25 micro filter. Excess Sodium was removed by 3 distilled water washing steps, where each step used 300mL of distilled water. The resulting solid contained less than 0.1% residual sodium. The precipitate was dried at 393 K for 4 hours, then ground to a fine powder.

[0339] Potassium was impregnated with using the incipient wetness impregnation method. In this method a 2 M solution of potassium carbonate was prepared, then sprayed on to the solid iron and zinc complex while blending via a shake table. This was then calcined at 623 K for 6 hours. The resulting catalyst was Nao.el FeiooZnieOy. II. AaBbFeiooXc catalyst preparation: Mined magnetite was ground to 0.25 particle size was impregnated with 5 wt % potassium with respect to iron, using the incipient wetness impregnation method. The impregnation was done with a potassium carbonate solution using enough distilled water to meet 0.2 gram water per gram of magnetite. The impregnation step was carried out dropwise on an ultrasonic bath. After the solution was fully 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, then calcined for 6 hours at 623 K. the resulting catalyst was a FeiooKs

[0340] III. AaBbFeiooXc catalyst preparation: A solution of Fe and Co metals was prepared using metal nitrates as the precursors and a base solution of sodium carbonate at a 2.4 molar equivalent to the metal nitrates was prepared at 0.5 M concentration.

[0341] Enough water to submerge the stirrer was added to a 2 L round bottom flask and heated to 343 K while continuously stirring. The metal and base solutions were transferred to the round bottom flask via peristaltic pump for parallel addition, with targeted flow rates so that the metal solution was completely added with half of the base solution over approximately 1 hour. The temperature was then increased to 353 K for 1 hour of aging. After an hour, the mixture was allowed to cool to room temperature before re-heating it to 343 K. The remaining base solution was added over the course of an hour, and the resulting slurry was aged for another hour at 353 K.

[0342] The precipitate was vacuum filtered using a 0.25 micro filter. The product was then washed 3 times and blended using approximately 300 mL water and filtered at each step to remove excess sodium to less than 0.1%. The resulting precipitate was dried at 393 K for 4 hours before grinding it to a fine powder and calcining for 6 hours at 623 K. The resulting catalyst was FeiooCouKi.

[0343] IV. AaBbXioo catalyst preparation: A solution of Fe and Co metals was prepared using metal nitrates as the precursors. The iron and cobalt were added to the solid materials containing certain metal and support oxide using witness incipient impregnation. After the solution was fully added to the solid material, the slurry was left in the ultrasonic bath for 10 minutes. It was then dried in an oven at 393 K for 4 hours, then calcined for 6 hours at 623 K.

[0344] Example 3 : General procedure for conversion of CO2 to paraffins and olefins

[0345] Paraffin formation from CO2 and hydrogenation is carried out in a fixed bed flow reactor. The flow reactor is loaded with 1 kg of CoRu / In on alumina catalyst. The catalyst is reduced in situ in a hydrogen environment at 250 °C for 2 hours. The reactor is heated to 250 °C after pretreatment. A feed mixture of 80% hydrogen and 20% CO2 is introduced to the reactor at 500 psi and a gas hourly space velocity of 9,000 h'1. The CO2 is converted into a mixture of paraffins and olefins with a selective range of carbon chain numbers (C6-C40).

[0346] Example 4: Exemplary Procedure I for conversion of CO2 to paraffins and olefins

[0347] Catalyst made by the method from Example 1, e.g., Nao.el FeiooZnieOy was granulated to 40-60 mesh size and pretreated with H2 at 623K, 150 PSIG, GHSV 1200 for 5 hours. It was later conditioned with syngas (H2 / CO = 2), at GHSV 600 at 623 K. The catalyst was then tested for CO2 hydrogenation to produce a paraffinic portion of SAF with hydrocarbon range C10-C16. The CO2 conversion to SAF was measured in a fixed bed reactor under the conditions of 623 K, GHSV 1500, 450 PSIG using feed gas H2= 72 mol %, CO2= 24 mol % and N2= 4 mol % as internal standard.

[0348] Table 1.: Product distribution obtained by exemplary procedure I for conversion of CO2 to paraffins.

[0349] The higher molecular weight products in the SAF product range (Cio-Cie) were analyzed for Carbon type distribution. The distribution per carbon number is summarized in Table 2 below, where others include isoparaffins and cycloparaffins.

[0350] Table 2.: C 10-C16 hydrocarbon distribution obtained by exemplary procedure I for conversion of CO2 to paraffins. Example 5: Procedure II for conversion of CO2 to paraffins and olefins

[0351] Catalyst made by the method from Example 1, e.g., FeiooKs was granulated to 40-60 mesh size and pretreated under H2 at 150 PSIG at 623K and GHSV 400 for 10 hours. After the hydrogen treatment the CO2 conversion to SAF was carried out in a fixed bed reactor under the conditions 623K, GHSV 1500, 450 PSIG using feed gas H2 = 63 mol %, CO2 = 23 mol % and N2 = 4 mol % as internal standard.

[0352] Table 3: Product distribution obtained by procedure II for conversion of CO2 to paraffins and olefins.

[0353] The higher molecular weight products in the SAF product range (Cio-Cie) were analyzed for Carbon type distribution. The distribution per carbon number is summarized in Table 4, below, where others include isoparaffins and cycloparaffins.

[0354] Table 4: C 10-C16 hydrocarbon distribution obtained by procedure II for conversion of CO2 to paraffins and olefins.

[0355] Example 6: Procedure III for conversion of CO2 to paraffins and olefins

[0356] Catalyst made by the method of example 1, e.g., FeiooCouKi was granulated to 40-60 mesh size and pretreated under H2 at 150 PSIG at 623 K and GHSV 200 for 5 hours. After the hydrogen treatment the catalyst was conditioned with syngas (H2 / CO = 2) at 145 PSIG, 623 K and GHSV 600 for 1 hour. The CO2 conversion to SAF was measured in a fixed bed reactor under the conditions 623 K, GHSV 1500, 450 PSIG using feed gas of H2=63 mol %, CO2 = 23 mol % and N2 = 4 mol % as internal standard. Table 5: Product distribution obtained by procedure III for conversion of CO2 to paraffins and olefins.

[0357] The higher molecular weight products in the SAF product range (Cio-Cie) were analyzed for Carbon type distribution. The distribution per carbon number is summarized in Table 6, below, where others include isoparaffins and cycloparaffins.

[0358] Table 6: C 10-C16 hydrocarbon distribution obtained by procedure III for conversion of CO2 to paraffins and olefins.

[0359] %

[0360] Olefin Paraffin

[0361] C10 45.1 54.9 Cn 46.7 53.3 C12 45.7 37.9 C13 40.5 59.5 C14 35.6 64.6

[0362] C15 35.8 64.2 C16 38.0 62.0

[0363] Example 7: Procedure IV for conversion of CO2 to paraffins and olefins

[0364] Catalyst made by the method of Example 1, e.g., AaBbXioo'was granulated to 40-60 mesh size and pretreated under diluted H2 in nitrogen at 150 PSIG at 623 K and GHSV 200 for 15 hours. The CO2 conversion to SAF was measured in a fixed bed reactor under the conditions 623 K, GHSV 1500, 450 PSIG using feed gas of H2=63 mol %, CO2= 23 mol % and N2= 4 mol % as internal standard.

[0365] Table 7: Product distribution obtained by procedure IV for conversion of CO2 to paraffins and olefins. The higher molecular weight products in the SAF product range (Cio-Cie) were analyzed for Carbon type distribution. The distribution per carbon number is summarized in Table 8, below, where others include isoparaffins and cycloparaffins.

[0366] Table 8: C 10-C16 hydrocarbon distribution obtained by procedure IV for conversion of CO2 to paraffins and olefins.

[0367] %

[0368] Olefin Paraffin

[0369] C10 0 100 Cn 0 100 C12 0 100 C13 0 100 C14 0 100

[0370] C15 0 100 C16 0 100

[0371] Example 8: General procedure for separation of target range hydrocarbons

[0372] A feed mixture of 50% CCE-to-paraffins products and 50% CCE-to-aromatic products is introduced into a distillation system under ambient pressure N2 atmosphere. The fraction cut of 150 °C - 300 °C is collected.

[0373] Example 9: General Procedure for Hydrocracking

[0374] The collected fraction from the separation step (e.g., from Example 4) is fed into a hydrocracking reactor loaded with 1 kg of Pt on Y zeolite catalyst (0.5 wt% Pt). The reaction is carried out at 750 psi, with a mole ratio of hydrogen over hydrocarbons set at 20, and a liquid weight hourly space velocity of 1.0 h'1. The fraction is converted into a mixture of saturated n- paraffin, iso-paraffin, and olefins with a selective range of carbon chain number between Cs and C15.

[0375] Example 10: Preparation of Fe / Zn-Na reducti on cataly st

[0376] A solution of Fe and Zn metals was prepared using metal nitrates as the precursors. A base solution containing sodium carbonate at a 2.4 molar equivalent to the metal nitrates was prepared at 0.5 M concentration. To a 2 L round bottom flask, enough water was added to submerge the stirrer and it was heated to 343 K while continuously stirring. The metal and base solutions were transferred to the round bottom flask via peristaltic pump for parallel addition, with targeted flow rates so that the metal solution was completely added with half of the base solution over approximately 1 hour. The temperature was then increased to 353 k for 1 hour of aging. After an hour, the mixture was allowed to cool to room temperature before re-heating it to 343 K. The remaining base solution was added over the course of an hour, and the resulting slurry was aged for another hour at 353 K.

[0377] The precipitate was vacuum filtered using a 0.25 micro filter. The product was then washed 3 times and blended using approximately 300 mL water and filtered at each step to remove excess sodium to less than 0.1%. The resulting precipitate was dried at 393 K for 4 hours before grinding it to a fine powder and calcining for 6 hours at 623 K. The resulting catalyst was FeZn with 0.5%Na. The ratio of iron and zinc components can be adjusted as readily understood by one of skill in the art. For example, catalysts having the following ratio of Fe:Zn have been synthesized according to the processes above: 1 : 1, 2: 1, 3: 1, 4: 1, 6: 1 with 0.5% by weight Na.

[0378] Example 11 : Catalyst evaluation for CO2 hydrogenation.

[0379] Catalysts was made by the method of Example 1 and 10, FeZn, with the molar ratio of iron to zinc being about 6: 1, but with different metal promoters, i.e., Na, Rh or Cs. The catalyst was granulated to 40-60 mesh size and pretreated with EE at 623K, 150 PSIG, GHSV 1200 for 5 hours. It was later conditioned with syngas (H2 / CO = 2), at GHSV 600 at 623 K. The catalyst was then tested for CO2 hydrogenation to produce a target hydrocarbon product mixture comprising C10-C16 paraffins and / or olefins. The CO2 conversion to C10-C16 paraffins and / or olefins for each of the different catalysts was measured in a fixed bed reactor under the conditions of 623 K, GHSV 1500, 450 PSIG using feed gas H2 = 72 mol %, CO2 = 24 mol % and N2 = 4 mol % as internal standard.

[0380] Table 7: Product Distribution by Catalyst FeZn with Group IA or IIA metal

[0381] Methane production is a factor of the effectiveness of the catalyst, as methane production is undesirable. Accordingly, the lower the methane production (SCi), the better the catalyst. O / P is the ratio of olefins to paraffins generated by the reaction between the feed and the catalyst. In this case, FeZnNa catalyst affords a product stream with less methane, higher olefin to paraffin ratio, and a greater amount of C5+ products than the FeZnRh and FeZnCs catalysts.

[0382] While this example was conducted with the FeZnNa catalyst having a molar ratio of about 6Fe: IZn, it was found through other experiments that adjusting the molar ratio of iron to zinc from 1 : 1 to about 7: 1 does not significantly affect the product distribution.

[0383] After selecting FeZn- 0.5%Na as the catalyst, the molar ratio of Fe:Zn was adjusted to 2.25: 1, and the partial pressure of the hydrogen feed was adjusted to determine the effect on methane production and O / P selectivity.

[0384] Table 8: Product distribution with reduced H2 partial pressure

[0385] It was found that, by reducing the H2 / CO2 from 3 to 2, methane selectivity (SCi) lowered and O / P increased— improvements in both regards. In addition, the test demonstrated that there was no significant difference between the product selectivity for 6Fe: lZn and 2.25Fe: lZn.

[0386] Example 12: Catalyst evaluation of CO2 hydrogenation using Olefin and CP rich feed

[0387] Catalyst made by the method from Example 10, FeZnNa was granulated to 40-60 mesh size and pretreated with H2 at 623K, 150 PSIG, GHSV 1200 for 5 hours. It was later conditioned with syngas (H2 / CO = 2), at GHSV 600 at 623 K. The catalyst was then tested for CO2 hydrogenation to produce a target hydrocarbon product mixture comprising C10-C16 paraffins and / or olefins. The CO2 conversion to C10-C16 paraffins and / or olefins measured in a fixed bed reactor under the conditions of 623 K, GHSV 1500, 450 PSIG using feed gas H2 = 47 mol %, CO2= 23.8 mol, CO = 3 mol %, CH4= 15 mol %, C2H4 = 2.2 mol %, C2H6=2.4 mol%, C3H6 = 2.3 mol%, C3H8 = 0.3% and N2 = 4 mol % as internal standard will be evaluated. It is anticipated that the production of C5+ paraffins and / or olefins will increase and methane production will decrease. Table 9: Expected Product Distribution with Mixed Hydrocarbon Feed

[0388] Example 13: Method of extrudate synthesis - Sodium Aluminate binder

[0389] 80g powder catalyst (FeZnNa) from Example 10, 20g sodium aluminate and 1g STEROTEX® were blended using a nutri-bullet to form a well-mixed dry powder. Nitric acid was added dropwise to 15.7951g de-ionized water to form solution A. Solution A was added dropwise to the powder at constant stirring rate. An additional 10.2g of de-ionized water was added to the slurry to achieve an extrudable dough. The prepared dough was extruded at 45Hz to 1.6 mm diameter extrudates. The first extrudates were discarded. Successful extrudates were collected separately. Extrudates were dried at 120°C for 2 hours and then calcined at 350°C for 4 hours to make a formed catalyst.

[0390] Example 14: Method of extrudate synthesis- Sodium Silicate binder

[0391] 80g powder catalyst (FeZnNa) from Example 10, 20g sodium silicate and 1g STEROTEX® were blended using a nutri-bullet to form a well mixed dry powder. Nitric acid was added dropwise to 16.0213g de-ionized water to form solution A. Solution A was added dropwise to the powder at constant stirring rate. An additional 9.3138g of de-ionized water was added to the slurry to achieve an extrudable dough. The prepared dough was extruded at 45Hz to 1.6 mm diameter extrudates. The first extrudates were discarded. Successful extrudates were collected separately. Extrudates were dried at 120°C for 2 hours and calcined at 350°C for 4 hours to make a formed catalyst.

[0392] Example 15: Detailed Method of extrudate synthesis- Potassium Silicate binder

[0393] 80g powder catalyst (FeZnNa) from Example 10, 20g potassium silicate and 1g STEROTEX® were blended using a nutri-bullet to form a well-mixed dry powder. Nitric acid was added dropwise to 30.3788g de-ionized water to form solution A. Solution A was added dropwise to the powder at constant stirring rate. An additional 10.2g of de-ionized water was added to the slurry to achieve an extrudable dough. The prepared dough was extruded at 45Hz to 1.6 mm diameter extrudates. The first extrudates were discarded. Successful extrudates were collected separately. Extrudates were dried at 120 °C for 2 hours and calcined at 350 °C for 4 hours to make a formed catalyst. Example 16: Catalyst evaluation of CO2 hydrogenation

[0394] Powder catalyst samples were prepared according to the procedures set forth in Example 10 having a final composition of molar ratio Fe:Zn = 2: 1 with 0.61 wt % Na. The powder catalyst was divided and finished according to the procedure in Example 11, except that different binders were incorporated to make the extrudates. Sample 2 was made with nondoped Alumina binder. Sample 3 was made with Na-doped Alumina binder. Sample 4 was made with K-doped Alumina binder. Sample 5 was made with non-doped Silica binder (LUDOX®). Sample 6 was made with non-doped Silica binder (Hi-Sil). Sample 7 was made with Na-doped Silica binder. Sample 8 was made with K-doped Silica binder.

[0395] The effluent, or liquid product from the conversion reaction, was collected after steady state was reached. Steady state may be gauged by passage of time on stream (TOS), or it may be tested by collecting samples about every 24 hours and testing the concentration of metals in the sample to determine at which time steady state is reached. In a typical experiment the liquid products (hydrocarbons and aqueous phase) were collected every 24 h and analyzed for trace amounts of Fe, Zn and Na. In this example, after 200 hours TOS, the effluent was collected and divided into an aqueous product and an oil (hydrocarbons) product. The oil product was dissolved in Aqua regia acid and then analyzed using ICP-MS. Separately, a sample the aqueous product was injected into the instrument wherein the plasma ionizes the sample to provide a mass spectrometry readout. The MS data was analyzed for concentration of metals and the amount calculated for each of the samples was added to account for a total concentration. The total concentration of metals in both aqueous and oil phase was added and reported as total metal leaching in Table 10.

[0396] Table 10: Examples of the effect of binder on the active metal catalyst performance

[0397] The results of the samples of formed catalyst having different binder compositions were compared. The performance of sample 2 having a non-doped binder was compared to the performance of the catalyst with the Na-aluminate binder in sample 3. Both the methane selectivity and the selectivity for C5+ hydrocarbons improved significantly with the doped binder. That is, between sample 2 and 3, SCi decreased by 37.5% and SC5+ increased by 61%.

[0398] The performance of samples 4 and 5 having a non-doped binder was compared to the performance of the catalysts with the Na- and K-silicate binder in samples 6 and 7. Both the methane selectivity and the selectivity for C5+ hydrocarbons improved significantly with the doped binders. That is, between non-doped sample 4, and doped samples 6 and 7, SCi decreased by 49%, and SC5+ increased by 36% and 38%, respectively. That is, between nondoped sample 5, and doped samples 6 and 7, SCi decreased by 53% and 52%, respectively and SC5+ increased by 70% and 72%, respectively.

[0399] Example 17: Leaching Rates of Different Metals During Time on Stream

[0400] Powder catalyst from Example 1 having a final composition of molar ratio Fe:Zn = 2: 1 with 0.61 wt % Na, and a formed catalyst extrudate of Sample 3 were tested leaching rates after different times on stream. The metal leaching of the catalysts was analyzed using ICP-MS. The liquid products (hydrocarbons / oil and aqueous phase) were collected at the various time intervals, separated into the oil portion and the aqueous portion, and analyzed for trace amounts of Fe, Zn and Na. For the formed catalyst, the effluent was divided into the aqueous and the oil portion, and only the aqueous portion was analyzed for metal leaching because the reaction had reached steady state and the amount of metal in the oil portion would be less than 1 ppm. Table 11 shows metal leaching rates of the powder catalyst and Table 12 shows metal leaching rate of the formed catalyst. The introduction of the binder showed reduced metal leaching rates when comparing similar time on stream. Table 11 : FeZn =2 mole ratio, 1% wt Na Powder catalyst

[0401] Table 12: FeZn =2 mole ratio, 1% wt Na with Na- Aluminate binder extrudate

[0402] Example 18: Toluene alkylation with 1- hexene over alkylation catalyst beta-zeolite

[0403] In this example, the alkylation catalyst comprises a beta-zeolite. H form of beta-zeolite was pelletized, crushed, and sieved to a particle size of 0.25-0.4 mm. 2.6 g of this pelletized sample was diluted with silicon carbide (0.4 mm-0.25 mm) to obtain a bed volume of 10 cm3. The mixture was loaded into a down-flow stainless-steel fixed bed reactor, and toluene and 1- hexene at a mole ratio of 4 was fed at a temperature of 200° C, a pressure of 35 bar, and WHS V= 1.6 h-1 based on total feed. The liquid product that was withdrawn from the pot after 18 hours was analyzed by GC-FID to determine its composition. 96% hexene conversion was obtained. Among these, 99% reacted by alkylation and 1% by oligomerization. The mono alkylated product selectivity was 96% and the dialkylated product selectivity was 4%. Example 19: oligomerization of 1- hexene over PSH-3. catalyst

[0404] In this example, the oligomerization catalyst comprises PSH-3. H form of PSH-3, was pelletized, crushed, and sieved to a particle size of 0.25-0.4 mm. 1.25 g of this pelletized sample was diluted with silicon carbide (0.4 mm-0.25 mm) to obtain a bed volume of 10 cm3. The mixture was loaded into a down-flow stainless-steel fixed bed reactor, and 1 -hexene feedstock was processed at a temperature of 190° C, a pressure of 35 bar, and WHSV=1 h-1 based on 1- hexene. The liquid product that was withdrawn from the pot after 20 hours was analyzed by GC-FID to determine its composition. It was found that 81%, by weight of the 1 -hexene feed was converted into dimers and trimers of hexene, with 85% by weight of the oligomerization reaction product being dimers of hexene.

[0405] Example 20: oligomerization / alkylation of 1- hexene and toluene over PSH-3 and beta catalysts

[0406] In this example, the alkylation catalyst comprises beta-zeolite and the_oligomerization catalyst comprises PSH-3. H form of PSH-3or beta-zeolite or a combination of these catalysts using stacked bed catalyst concept were pelletized, crushed, and sieved to a particle size of 0.25-0.4 mm. 1.25 g of this pelletized sample was diluted with silicon carbide (0.4 mm-0.25 mm) to obtain a bed volume of 10 cm3. The mixture was loaded into a down-flow stainless- steel fixed bed oligo-alkylation reactor, and a mixture of 1 -hexene and aromatic source at different ratios of feedstock was processed at a temperature of 190° C, a pressure of 35 bar, and WHSV=1 h-1 based on the mixture. The liquid product that was withdrawn from the pot after 20 h was analyzed by GC-FID to determine its composition. GC analytical data will indicate high conversion of hexene and toluene and both products by aromatic alkylation and hexene oligomerization will be obtained.

[0407] Example 21 : Aromatic catalyst selectivity evaluation

[0408] Zn modified ZSM-5 was synthesized by ion exchange method and its selectivity for the conversion of olefins to aromatics was evaluated. Reaction conditions were set to:

[0409] 2g of catalyst, 500C, 50 psi,

[0410] 140 seem of mixture of N? and propylene (N2:propylene = 3.4:1).

[0411] The reaction products were analyzed, and the results presented in Tables 9 and 10. All propylene conversion was greater than 95%. Table 13: Selectivity of Zn-modified catalysts (mol%)

[0412] *Zn concentration in the solution used in synthesis via ion exchange method

[0413] Table 14: Distribution of Aromatic of Zn-modified catalyst (wt%)

[0414] *Zn concentration in the solution used in synthesis via ion exchange method

[0415] In addition, all propylene conversion is greater than 95%.

[0416] Example 22: Aromatic Catalyst Stability Evaluation

[0417] Zn modified ZSM-5 was synthesized by ion exchange method and its stability for the conversion of olefins to aromatics was evaluated. Reaction conditions were set to:

[0418] 2g of catalyst, 500C, 50 psi,

[0419] 140 seem of mixture of CO2, N2 and propylene (CO2:N2:propylene = 1.4: 1 : 1).

[0420] The reaction products were analyzed over time on stream. The results are presented in Figure 7. As shown by a review of the figure, the selectivity for aromatics remained substantially constant from about 10 hours on stream to about 50 hours on stream. In addition, each of the listed hydrocarbons remained below 10% and substantially constant.

[0421] Example 23: Examples of Fuel Compositions

[0422] A renewable fuel was produced by contacting carbon dioxide and hydrogen gas with catalysts to produce a mixture of n-paraffins, isoparaffins, cycloparaffins, and aromatics. This product was analyzed by gas chromatography with mass spectrometry (GC-MS) and further characterized according to each of the standard methods specified in Table 15 below.

[0423] Table 15. Analysis results for exemplary fuel composition

[0424] Analysis Method Value

[0425] Density ASTM D4052 0.78 kg / L

[0426] Flash Point ASTM D93 42 °C

[0427] Total Acidity ASTM D3242 0.07 mg KOH / g

[0428] Total Sulfur ASTM D2622 0.000 mass % Sulfur Mercaptan ASTM D3227 0.00 mass % Freeze Point ASTM D5972 -51 °C

[0429] Heat of Combustion ASTM D4809 43.4 MJ / kg

[0430] Smoke Point ASTM D1322 36 mm

[0431] Viscosity ASTM D445 3.2 mm2 / s at -20 °C Filter Pressure Drop ASTM D3241 0 mm Hg Tube Deposit Rating ASTM D3241 1 VTR Color Code Lubricity ASTM D5001 0.52 mm WSD n-Paraffins GC-MS 19.5 % Isoparaffins GC-MS 40.8 %

[0432] Cycloparaffins GC-MS 25.8 % Aromatics GC-MS 13.9 %

[0433] Example 24: Comparison of Aviation Fuel Produced by the Disclosed Methods with

[0434] Traditional Aviation Fuel

[0435] A comparison of synthetic Jet A made according to the process described above with conventional (petroleum-based) Jet A was made on a small turbojet engine. The two fuels were tested consecutively at the same facility using the same engine and instrumentation. The test engine was first operated on the conventional Jet A with the addition of a 5% oil mix to provide the necessary lubricity. The test fuel was fed from a temporary nitrogen pressured 2 gallon liquid dispensing tank. After completion of the conventional Jet A run, the fuel tank and fuel lines were drained and replaced with the synthetic jet fuel with the added 5% oil mix and the test was repeated. The engine was operated at multiple speeds and was held at each different operating condition for 1.5 minutes to stabilize the operating temperatures. Engine speed and exhaust gas temperature were recorded during the last 20 seconds of each operating condition. The measured data was averaged and reported as data points.

[0436] An engine start time comparison of both fuels was also conducted. After completing the above performance runs, the engine was shut down and allowed to cool for 15 minutes and to allow the start battery to recharge. The engine was then started and the engine acceleration versus time was recorded for each fuel until stable idle speed was attained.

[0437] The test results showed no difference between the recorded engine speeds, exhaust gas temperatures, and start times between the two fuels. INCORPORATION BY REFERENCE

[0438] All publications and patents mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control.

[0439] EQUIVALENTS

[0440] While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims below.

[0441] The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

Claims

CLAIMS1. A method for the production of aviation fuel comprising: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a medium hydrocarbon product mixture comprising one or more C4-9 paraffins and / or olefins; and a target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins; and contacting the medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an aromatic catalyst to afford a target aromatic product mixture comprising one or more C9-16 aromatics.

2. The method of claim 1, wherein the reduction catalyst comprises: one or more first elements selected from iron or cobalt ; optionally one or more second elements selected from copper and zinc; and optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives.

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

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

5. The method of claim 1, wherein the reduction catalyst comprises: iron;a first element selected from copper, zinc, cobalt, or a combination thereof; and optionally one or more second elements selected from Group IA and 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 of claim 5, wherein the first element is zinc; and wherein the catalyst does not contain copper or cobalt.

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

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

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

11. The method of claim 10, wherein the one or more Group IA or IIA metals is 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 at a molar ratio of from 0 to about 0.20 relative to iron, and / or Na at a molar ratio from 0 to about 0.60 relative to iron.

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

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

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

16. The method of claim 1, wherein the reduction catalyst comprises: iron; zinc; one or more second elements selected from Group IA, IIA and X metals; and a binder selected from boehmite, silica-alumina hydrate, aluminate, silica, silicate, pseudoboehmite alumina, bentonite clay, montmorillinite clay, zirconate, tungsten, or any combination thereof.

17. The method of claim 16, wherein the binder comprises a promoter element selected from Na, K, Cs, Li, Rb, or a combination thereof.

18. The method of claim 17, wherein the binder is selected from Na-aluminate, K- aluminate, Na-silicate, K-silicate, Na-zirconate, K-zirconate, Na-tungsten, K-tungsten, , or a combination thereof.

19. The method of any one of claims 1-18, wherein contacting the first reduction gas and the first carbon source gas with the reduction catalyst occurs at a paraffin temperature from about 100 °C to about 600 °C.

20. The method of any one of claims 1-19, wherein contacting the first reduction gas and the first carbon source gas with the reduction catalyst occurs at a paraffin pressure from about 50 psi to about 4000 psi.

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

22. The method of claim 21, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49,MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof.

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

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

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

26. The method of any one of claims 21-25, 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 a combination thereof.

28. The method of 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 of any one of claims 24-26, 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 of any one of claims 1-29, wherein contacting the medium hydrocarbon product mixture, optionally the second reduction gas, and optionally the second carbon source gas with the aromatic catalyst occurs at an aromatic temperature from about 100 °C to about 450 °C.

31. The method of any one of claims 1-30, wherein contacting the medium hydrocarbon product mixture, optionally the second reduction gas, and optionally the second carbon source gas with the aromatic catalyst occurs at an aromatic pressure from about 50 psi to about 1000 psi.

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

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

34. The method of any one of claims 1-33, wherein the ratio of olefins to paraffins in the medium hydrocarbon product mixture is at least about 3.

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

36. The method of any one of claims 1-35, wherein contacting the first reduction gas and the carbon source gas with a reduction catalyst further affords: a light hydrocarbon product mixture comprising one or more C2-4 paraffins and / or olefins.

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

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

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

40. The method of any one of claims 1-39, wherein contacting the medium hydrocarbon product mixture with the aromatic catalyst further affords: a light aromatic product mixture comprising one or more Ce-8 aromatics.

41. The method of claim 40, further comprising: contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics.

42. The method of any one of claims 40-41, further comprising: contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford: a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins.

43. The method of claim 40, further comprising: contacting the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst and an oligomerization catalyst to afford a mixed target product mixture comprising one or more C9-16 aromatics and one or more Cio-16 paraffins and / or olefins.

44. The method of any one of claims 41-43, wherein the alkylation catalyst is an acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AICI3), tungsten, platinum, or a zeolite.

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

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

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

48. The method of any one of claims 41-47, wherein contacting the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst occurs at an alkylation temperature from about 50 °C to about 300 °C.

49. The method of any one of claims 41-47, wherein contacting the light hydrocarbon product mixture and the light aromatic product mixture with the alkylation catalyst occurs at an alkylation pressure from about 0 psig to about 1000 psig.

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

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

52. The method of any one of claims 42-50, wherein the oligomerization catalyst comprises a zeolite selected from ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, beta-zeolite, faujasites, mordenite zeolite, SAPO-5, SAPO-11, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, or a combination thereof.

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

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

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

56. The method of any one of claims 42-55, wherein contacting the light hydrocarbon product mixture with an oligomerization catalyst occurs at an oligomerization pressure from about 0 psi to about 500 psi.

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

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

59. The method of any one of claims 42-58, wherein contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords: a light oligomerized product mixture comprising one or more C1-2 hydrocarbons.

60. The method of claim 59, further comprising: combining the carbon source gas with the light oligomerized product mixture prior to contacting with the reduction catalyst.

61. The method of any one of claims 42-60, wherein contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords: a medium oligomerized product mixture comprising one or more C3-7 hydrocarbons.

62. The method of claim 61, further comprising: combining the light hydrocarbon product mixture with the medium oligomerized product mixture prior to contacting with the oligomerization catalyst.

63. The method of any one of claims 41-62, wherein contacting the light hydrocarbon product mixture and / or the light hydrocarbon product mixture with the oligomerization catalyst further affords: a heavy oligomerized product mixture comprising one or more C17-25 paraffins and / or olefins.

64. The method of any one of claims 1-63, wherein contacting the first reduction gas and the carbon source gas with a reduction catalyst further affords: a heavy hydrocarbon product mixture comprising one or more C17-25 paraffins and / or olefins.

65. The method of claim 63 or 64, further comprising: contacting a third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with a hydrocracking catalyst to afford a hydrocracked product mixture comprising one or more Ci-is paraffins and / or olefins.

66. The method of claim 65, wherein contacting the third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with the hydrocracking catalyst occurs at a hydrocracking temperature from about 250 °C to about 450 °C.

67. The method of claim 65 or 66, wherein contacting the third reduction gas and the heavy oligomerized product mixture and / or the heavy hydrocarbon product mixture with the hydrocracking catalyst occurs at a hydrocracking pressure from about 0 psig to about 1000 psig.

68. The method of any one of claims 1-65, wherein contacting the first reduction gas and the carbon source gas with a reduction catalyst further affords: a recycle mixture comprising one or more C1-2 hydrocarbons, CO2, CO, and / or H2.

69. The method of claim 67, further comprising: combining the recycle mixture with the first reduction gas and / or the carbon source gas prior to contacting with the reduction catalyst.

70. The method of any one of claims 1-69, further comprising: blending the target hydrocarbon product mixture, the target aromatic product mixture, the target oligomerized product mixture, the target alkyl arene product mixture, and / or the target product mixture to produce aviation fuel.

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

72. The method of any one of claims 1-71, wherein the first reduction gas, the second reduction gas, and the third reduction gas are independently selected from H2, a hydrocarbon,synthesis gas (CO / H2), or from a gas that is, or is derived from, flare gas, waste gas, or natural gas.

73. The method of any one of claims 1-71, wherein the first reduction gas, the second reduction gas, and the third reduction gas is H2.

74. The method of any one of claims 1-71, where the first reduction gas, the second reduction gas, and the third reduction gas is a hydrocarbon, such as CH4, ethane, propane, or butane.

75. The method of any one of claims 1-71, wherein the first reduction gas, the second reduction gas, and the third reduction gas is, or is derived from, flare gas, waste gas, or natural gas.

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

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

78. A system for the production of aviation fuel comprising: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst, said reduction reactor having a first reduction gas feed inlet, a first carbon source feed inlet, a target hydrocarbon outlet, and a medium hydrocarbon outlet; wherein the first reduction gas feed inlet is coupled to the first reduction gas feed, and the first carbon source gas feed inlet is coupled to the first carbon source gas feed; optionally, a second reduction gas feed; optionally, a second carbon source gas feed; and an aromatic reactor comprising an aromatic catalyst, said aromatic reactor having a medium hydrocarbon inlet, optionally a second reduction as feed inlet, optionally a second carbon source gas feed inlet, and a target aromatic product outlet; wherein themedium hydrocarbon inlet is coupled to the medium hydrocarbon outlet on the reduction reactor, the second reduction gas feed inlet, when present, is coupled to the second reduction gas feed, and the second carbon source gas feed inlet, when present, is coupled to the second carbon source gas feed.

79. The system of claim 78, wherein the reduction catalyst comprises: iron; a first element selected from copper, zinc, cobalt, or a combination thereof; and one or more second elements selected from Group IA and 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 of claim 80 or 81, wherein the molar ratio of iron to the first element is about 1 : 1 to about 7: 1.

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

84. The system of any one of claims 80-83, wherein the one or more Group IA or IIA metals is selected from magnesium, calcium, potassium, sodium, cesium, or a combination thereof.

85. The system of claim 84, wherein the one or more Group IA or IIA metals is 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 of any one of claims 80-85, wherein the iron is in the form of an iron oxide, and the iron oxide comprises magnetite (FesCU), hematite (Fe2O3), or a combination thereof.

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

88. The system of claims 87, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof.

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

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

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

92. The system of any one of claims 87-91, 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 a combination thereof.

94. The system of 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 of any one of claims 87-94, 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.

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

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

98. The system of any one of claims 78-97, wherein aromatic reactor further comprises a light aromatic product outlet.

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

100. The system of any one of claims 98-99, further comprising: an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a light hydrocarbon inlet and a target oligomerized product outlet; wherein the light hydrocarbon inlet is coupled 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, said 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 coupled to the light hydrocarbon outlet on the reduction reactor, and the light aromatic product inlet is coupled to the light aromatic product outlet on the aromatic reactor.

102. The system of any one of claims 99-101, wherein the alkylation catalyst is an acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), tungsten, platinum, or a zeolite.

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

104. The system of claim 100 or 101, wherein the oligomerization catalyst is a zeolite or molecular sieve.

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

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

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

108. The system of any one of claims 100-107, wherein the oligomerization reactor and / or the oligo-alkylation reactor further comprises a medium oligomerized product outlet.

109. The system of claim 108, wherein the oligomerization reactor, the alkylation reactor, and / or the oligo-alkylation reactor further comprises: a medium oligomerized product inlet, wherein the medium oligomerized product inlet is coupled to the medium oligomerized product outlet on the oligomerization reactor and / or the oligo-alkylation reactor.

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

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

112. The system of claim 111, further comprising: a third reduction gas feed; a hydrocracking reactor comprising a hydrocracking catalyst, said hydrocracking reactor having a reduction gas inlet, a heavy oligomerized product inlet and / or a heavy hydrocarbon inlet, and a hydrocracked product outlet; wherein the reduction gas inlet is coupled to the third reduction gas feed, the heavy oligomerized product inlet, when present, is coupled to the heavy oligomerized product outlet on the oligomerization reactor and / or the oligo-alkylation reactor, and the heavy hydrocarbon inlet, when present, is coupled to the heavy hydrocarbon outlet on the reduction reactor.

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

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

115. A reduction catalyst composition comprising: iron; zinc; one or more second elements selected from Group IA, IIA and X metals; anda binder selected from boehmite, silica-alumina hydrate, aluminate, silica, silicate, pseudoboehmite alumina, bentonite clay, montmorillinite clay, zirconate, 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 a combination thereof.

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

118. The reduction catalyst composition of any one of claims 115-117, wherein the reduction catalyst maintains activity at over about 75% for over about one year.

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

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

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

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

123. The reduction catalyst composition of any one of claims 115-122, wherein the one or more second elements is the Group IA or IIA metal selected from magnesium, calcium, potassium, sodium, cesium, or a combination thereof.

124. The reduction catalyst composition of claim 123, comprising the Group IA metal selected from potassium, sodium, or a combination thereof.

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

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

127. The reduction catalyst composition of any one of claims 115-126, wherein when the catalyst is contacted with a continuous flow of fluid 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 of any one of claims 115-127, wherein the reduction catalyst has a selectivity for C5+ hydrocarbons greater than about 28 carbon mole%.

129. An aromatic catalyst comprises an optionally modified zeolite, wherein the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA- 114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, wherein the aromatic catalyst has a selectivity for aromatics of over about 50 carbon mole%; and wherein the aromatic catalyst has a selectivity for methane of less than about 8 carbon mole%.

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

131. The aromatic catalyst of any one of claim 129 or 130, wherein the zeolite has a silicon to aluminum ratio (SAR) of about 30 to about 400.

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

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

134. The aromatic catalyst of claim 133, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt, or a combination thereof.

135. The aromatic catalyst of 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 of 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 of any one of claims 129-136, wherein the selectivity for aromatics is over about 55 carbon mole%.

138. The aromatic catalyst of any one of claims 129-137, wherein the selectivity for aromatics is over about 60 carbon mole%.

139. The aromatic catalyst of any one of claims 129-138, wherein the aromatic catalyst has a selectivity for C9-14 aromatics of about 5 carbon mole% to about 20 carbon mole%.

140. An oligo-alkylation catalyst for converting a light aromatic product mixture to a mixed target product mixture comprising one or more C9-14 aromatics and one or more Cio-16 paraffin, the oligo-alkylation catalyst comprising: a liquid acid, a Friedel -Crafts alkylation catalyst (e.g., HF / AICI3), an amorphous heterogeneous acid catalyst, a heterogeneous acid catalyst, such as a zeolite or a molecular sieve, and a combination thereof.

141. The oligo-alkylation catalyst of claim 140, wherein the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve.

142. The oligo-alkylation catalyst of claim 140, wherein the oligo-alkylation catalyst is selected from the group consisting of: ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM- 12, ZSM-57, ZSM-35, zeolite beta, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

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