Systems and methods for the production of paraffinic kerosene and sustainable aviation fuel using a reforming catalyst

Abstract

Provided herein are systems and methods for converting CO2 and a reduction gas, such as H2 or a hydrocarbon, to a mixture of paraffins for paraffinic aviation fuel, and also to a mixture of paraffins and aromatics suitable for use as aviation fuel. The systems and methods of the present disclosure provide advantages over previous methods related to increased carbon selectivity, as well as improved catalyst stability and longevity.

Description

[0001] SYSTEMS AND METHODS FOR THE PRODUCTION OF PARAFFINIC KEROSENE AND SUSTAINABLE AVIATION FUEL USING A REFORMING CATALYST

[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, U.S. Provisional Patent Application No. 63 / 567,700, filed March 20, 2024, and U.S. Provisional Patent Application No. 63 / 676074, filed July 26, 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 together. 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. In addition, improvements in selectivity and yield of processes are needed.

[0008] SUMMARY OF THE DISCLOSURE

[0009] Disclosed herein is a method for the production of aviation fuel. The method may include: A method of making aviation fuel comprising: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a light hydrocarbon product mixture; and a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture; and contacting the light hydrocarbon product mixture, and optionally at least a portion of the medium hydrocarbon product mixture, with an oligomerization catalyst to provide an oligomerization product mixture; hydrogenating the target hydrocarbon product mixture and the oligomerization product mixture to afford a hydrogenated paraffin product mixture comprising a light paraffin product mixture, a medium paraffin product, and a target paraffin product mixture; contacting the medium paraffin product mixture, and optionally at least a portion of the light paraffin product mixture, with a reforming catalyst to afford a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture; and combining the target aromatic product mixture and the target paraffin product mixture to make aviation fuel.

[0010] 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; (iv) a first separator coupled to the reduction reactor; (v) an oligomerization reactor comprising an oligomerization catalyst;(vi) a hydrogenator; (vii) a second separator coupled to the hydrogenator; and (vii) an aromatic reactor comprising a reforming catalyst.

[0011] The reduction reactor may include a first reduction gas feed inlet, a first carbon source feed inlet, and a mixed 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 system may also include a second reduction gas feed and / or a second carbon source gas feed. The first separator may comprise a mixed hydrocarbon inlet, a light hydrocarbon product outlet and a target hydrocarbon outlet. The mixed hydrocarbon inlet on the first separator may be coupled to the mixed hydrocarbon outlet on the reduction reactor. The oligomerization reactor may have a light hydrocarbon product inlet and an oligomerization product outlet. The light hydrocarbon product inlet on the oligomerization reactor may be coupled to the light hydrocarbon product outlet on the first separator.

[0012] The hydrogenator may comprise an oligomerization product inlet and a hydrogenated paraffin product outlet. The oligomerization product inlet on the hydrogenator may be coupled to the oligomerization product outlet on the oligomerization reactor. The second separator may comprise a hydrogenated paraffin product inlet, a medium paraffin outlet, and a target paraffin outlet. The hydrogenated paraffin product inlet on the second separator may be coupled to the hydrogenated paraffin product outlet on the hydrogenator.

[0013] The aromatic reactor may include a medium paraffin inlet, optionally a second reduction as feed inlet, optionally a second carbon source gas feed inlet, and a mixed aromatic product outlet. The medium paraffin inlet on the aromatic reactor may be coupled to the medium paraffin outlet on the second separator; 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.

[0014] Also disclosed is a system for the production of paraffinic kerosene for aviation fuel. That system includes: (i) a first reduction gas feed; (ii) a first carbon source gas feed; (iii) a reduction reactor comprising a reduction catalyst; (iv) a first separator coupled to the reduction reactor; a second separator coupled to the first separator; (v) an oligomerization reactor comprising an oligomerization catalyst, and coupled to the first separator and to the second separator; and (vi) a third separator having an oligomerization product inlet coupled to the oligomerization product outlet. The system may further comprise a hydrogenator coupled to the third separator configured to receive and hydrogenate a target olefin product mixture and make paraffinic kerosene.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] FIG. 1 is a process flow diagram for a system for making aviation fuel in which an aromatic reactor comprising a reforming catalyst is used in the scheme.

[0017] FIG. 2 is a process flow diagram for a system for making aviation fuel in which an aromatic reactor comprising a reforming catalyst is used in the scheme, and an intermediate quench is provided between two sections of an oligo-alkylation reactor. FIG. 3 is a process flow diagram for a system for making paraffinic kerosene in which an intermediate quench is provided between two sections of an oligomerization reactor.

[0018] FIG. 4 is a process flow diagram for a system for making paraffinic kerosene, which includes two oligomerization reactors.

[0019] DETAILED DESCRIPTION OF THE DISCLOSURE

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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, in certain embodiments, 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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 by oligomerization, alkylation, isomerization, and / or hydrogenation reactor(s), and the ratio of paraffin to aromatics can be adjusted by controlling the feed rate to the aromatics reactor with reforming catalysts to make aromatics. 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.

[0028] Also provided herein are systems and processes for the production of paraffinic kerosene made from CO2. This CCh-derived paraffinic kerosene is comprised primarily of n- paraffins and isoparaffins, with little or no cycloparaffins or aromatics, and may be blended with a traditional Jet A to achieve the desired concentration of cyclic compounds to meet ASTM D1655 specifications.

[0029] An advantage of the scheme disclosed herein is an improved carbon selectivity over previously known processes. By using the methods and systems disclosed herein to make the paraffinic kerosene, the overall carbon selectivity (that is, carbon converted from the first carbon source gas (plus any additional carbon source added in to the system) to the paraffinic kerosene may be over about 50% carbon mole %, over about 60 carbon mole %, over about 65 carbon mole %, over about 67 carbon mole %, or over about 68 carbon mole %. The carbon selectivity may be about 50 carbon mole % to about 80 carbon mole %, about 60 carbon mole % to about 75 carbon mole %, about 62 carbon mole % to about 70 carbon mole %, or about 65 carbon mole %. Unless specifically identified otherwise, selectivity values disclosed herein are in carbon mole%.

[0030] Likewise, by using the methods and systems disclosed herein utilizing the aromatic reactor and reforming catalyst to make the aviation fuel, the overall carbon selectivity (that is, carbon converted from the first carbon source gas (plus any additional carbon source added in to the system) to the target SAF compounds (that is, the target aromatic product mixture comprising one or more C9-14 aromatics plus the target hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins) may be over about 50%, over about 60%, over about 65%, or over about 70%. The overall selectivity in carbon may be about 50% to about 75%, about 55% to about 70%, about 60% to about 68, or about 65%.

[0031] Fuel Compositions

[0032] The present disclosure provides systems and methods for producing paraffinic kerosene and also 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] 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 13.5 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. The fuel composition may comprise about 5 wt% to about 40 wt% iso-paraffins. The fuel composition may comprise from about 15 wt% to about 35 wt% iso-paraffins, or about 25 wt% to about 35 wt% iso-paraffins. The fuel composition may comprise about 15 wt%, about 20 wt%, about 25 wt%, about 28 wt%, about 30 wt%, or about 35 wt% iso-paraffins.

[0039] The fuel composition may be compliant with ASTM D4054 - Tier 1.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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 810 kg / m3at 15 °C, about 785 kg / m3to about 810 kg / m3at 15 °C, or about 800 kg / m3to about 810 kg / m3at 15 °C. In certain embodiments, the composition has a density of about 775 kg / m3, about 780 kg / m3, about 800 kg / m3, or about 810 kg / m3at 15 °C. The composition may have a density of about 800 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.

[0050] 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.

[0051] The fuel composition may be compliant with ASTM DI 655.

[0052] 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.

[0053] 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.

[0054] Systems for Paraffinic Kerosene and Aviation Fuel Production

[0055] 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 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.

[0056] 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] ). Systems for the production of aviation fuel are also disclosed herein. The systems may include: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst; an oligomerization reactor; a hydrogenator; and an aromatic reactor comprising a reforming catalyst. Between the reduction reactor and the aromatic reactor may be one or more separators for separating gases, liquids and / or streams of light, medium, target and / or heavy hydrocarbons, as well as optionally aromatics. The system may include the reduction reactor coupled to a first separator, which may further be coupled to one or more separators (e.g., distillation column or absorber). The first separator may be a three-phase separator. The three-phase separator may be any such separator known for use in the art for separating gas, liquid and wastewater. The first separator may have an aqueous outlet, which may also be referred to herein as a wastewater outlet, a Ce and higher (“Ce+”) hydrocarbon outlet, and a CO2, H, C1-5 hydrocarbon outlet.

[0057] In an embodiment, the first separator is coupled to an absorber having an inlet coupled to the CO2, H, C1-5 hydrocarbon outlet, and the three-phase separator is also coupled to a distillation column having an inlet coupled to the Ce+ hydrocarbon outlet.

[0058] The reduction reactor may have a first reduction gas feed inlet, a first carbon source feed inlet, and a mixed 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.

[0059] The oligomerization reactor comprises an oligomerization catalyst. The oligomerization reactor may comprise an oligomerization product outlet and a light hydrocarbon inlet product inlet coupled to the first separator, or optionally to a distillation column. The oligomerization reactor may be coupled to the first separator and to the third separator. The oligomerization reactor may be configured to receive a light hydrocarbon product mixture from the first separator. The oligomerization reactor may be configured to receive a light aromatic product mixture from the third separator. The light hydrocarbon product mixture may comprise one or more C1-5 paraffins and / or olefins, or one or more C3-5 paraffins and / or olefins. The parameters of the separator may be adjusted as readily understood by one of ordinary skill in the art to shift the carbon ranges of the separated streams (e.g., light, medium, heavy). It may be desirable to shift the carbon range of the paraffins and olefins in the light hydrocarbon product mixture depending on the desired product and to improve yield.

[0060] The oligomerization reactor may comprise two or more sections within a single reactor, with each section comprising the oligomerization catalyst. The oligomerization catalyst in each of the sections of the oligomerization reactor may be the same or different. There may be an intermediate quench supplied between the sections of the oligomerization reactor to reduce the temperature within the bottom section of the reactor. The intermediate quench may be the light aromatic product mixture from the second separator and / or a portion of the light hydrocarbon product mixture from the first separator. The oligomerization reactor may be configured to receive a light aromatic product mixture from the second separator as an intermediate quench. The oligomerization reactor may be configured to receive a part of the light hydrocarbon product mixture from the first separator as an intermediate quench and / or to receive the remainder of the light hydrocarbon product mixture from the first separator at the top thereof such that the remainder of the light hydrocarbon product mixture undergoes dimerization two times within the oligomerization reactor. The system may be configured such that the top section of the oligomerization reactor dimerizes the hydrocarbons provided therein, and then the dimerized hydrocarbon mixture contacts the oligomerization catalyst in the bottom section of the oligomerization reactor to undergo alkylation and dimerization to yield olefins and paraffins in the jet fuel range (i.e., Cio-ie).

[0061] Hydrogenator may be coupled to the oligomerization reactor to saturate the olefins in the oligomerization product to yield an increase of paraffins. The hydrogenator may have an oligomerization product inlet and a hydrogenated paraffin product outlet. The oligomerization product inlet may be coupled to the oligomerization product outlet on the oligomerization reactor. Hydrogenator may be coupled to the second separator and the first separator to improve overall selectivity of the process. The hydrogenator may be configured to receive a light paraffin product mixture from the second separator. The hydrogenator may be configured to receive a target hydrocarbon product mixture from the reduction reactor. The hydrogenator may be coupled to an additional reduction gas feed. The hydrogenator may comprise two sections or it may be two separate reactors with varying temperatures in order to sufficiently saturate the olefins and aromatics as needed to afford the target paraffin product mixture.

[0062] The second separator may be a distillation column, or a separator plus a flash drum. The second separator may be any such equipment or combination of equipment known for use in the art for separating hydrocarbons. The second separator may have a hydrogenated paraffin product inlet coupled to the hydrogenated paraffin product outlet of the hydrogenator. The second separator may have a medium paraffin outlet, and a target paraffin outlet. The second separator may have a light paraffin outlet. The aromatic reactor herein may also be referred to as a reforming unit. The aromatic reactor comprises a reforming catalyst. The aromatic reactor may include a medium paraffin inlet, optionally a second reduction gas feed inlet, optionally a second carbon source gas feed inlet, and a mixed aromatic product outlet. The medium paraffin inlet may be coupled to the medium paraffin outlet on the second separator, 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.

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

[0064] The systems of the disclosure may comprise a first adsorbent bed having a light hydrocarbon inlet and a light hydrocarbon outlet. The light hydrocarbon inlet may be coupled to the first separator, and the light hydrocarbon outlet may be coupled to a distillation column. The first adsorbent bed may have a medium paraffin inlet coupled to the medium paraffin outlet on the second separator.

[0065] The oligomerization reactor may be configured to both convert (also referred to as dimerize) C2-5 olefins to C4-8 olefins, and optionally Ce-io olefins, and then to convert (also referred to as dimerize) C4-8 olefins to Cio-16 olefins. The oligomerization reactor may include two sections with each section comprising the oligomerization catalyst. The oligomerization catalyst in each or the sections may be the same or different. The oligomerization reactor may include an intermediate quench between the two sections. The intermediate quench may be supplied by the first separator, the third separator, or both the first and third separators. The oligomerization reactor may be a stacked bed reactor.

[0066] The systems of the disclosure may comprise an oligo-alkylation reactor in addition to the oligomerization reactor or in the place of the oligomerization reactor. The oligo-alkylation reactor may comprise an oligomerization catalyst and an alkylation catalyst. The oligomerization catalyst and the alkylation catalyst may be stacked and separate, layered, or mixed. The oligo-alkylation reactor may have one or more light hydrocarbon product inlets, a light aromatic product inlet, and an oligomerization product outlet. The light hydrocarbon inlet may be coupled to the light hydrocarbon outlet on the first separator, and the light aromatic product inlet may coupled to the light aromatic product outlet on the aromatic reactor. The oligo-alkylation reactor may be configured to receive a light aromatic product mixture from the second separator as an intermediate quench. While the oligomerization reactor is depicted in the figures as a single oligo-alkylation reactor with one or two sections, it may also be replaced with two separate oligomerization reactors connected in series, or an oligomerization reactor (with one or two sections) and a separate alkylation reactor connected in series, with the oligomerization reactor being upstream from the alkylation reactor. The systems of the disclosure may further comprise a fourth separator configured to separate the target paraffin product mixture comprising one or more Cio-16 paraffins from the heavy paraffin product mixture comprising one or more Cm paraffins. The fourth separator may have a heavy paraffin product outlet, and a target SAF paraffin product outlet. A fourth separator may be coupled to the second separator. A fourth separator may have a target paraffin inlet coupled to the target paraffin outlet on the second separator.

[0067] The system may comprise an alkylation reactor configured to receive at least a portion of the light aromatic product mixture to contact with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics. The alkylated aromatics may be directed to contact with a hydrogenation catalyst to afford cycloparaffins.

[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 paraffin product inlet, and a hydrocracked product outlet. The reduction gas inlet may coupled to the third reduction gas feed; the heavy paraffin product inlet, when present, may be coupled to the heavy paraffin product outlet on the fourth separator.

[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 aromatic product inlet, a target SAF paraffin product inlet, and an aviation fuel outlet. The blender may be configured to blend paraffin products and aromatic products made by the systems disclosed herein in a predetermined ratio to arrive at the desirable aviation fuel.

[0071] Systems for the production of paraffinic kerosene for aviation fuel are disclosed. That system includes: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst; a first separator coupled to the reduction reactor; a second separator coupled to the first separator; an oligomerization reactor comprising an oligomerization catalyst, and coupled to the first separator and to the second separator; and a third separator having an oligomerization product inlet coupled to the oligomerization product outlet. The reduction reactor has a first reduction gas feed inlet, a first carbon source feed inlet, and a mixed hydrocarbon outlet. 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. The first separator has a mixed hydrocarbon inlet coupled to the mixed hydrocarbon outlet on the reduction reactor. The first separator is configured to separate a light hydrocarbon product mixture; from a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture. In some embodiments, the light hydrocarbon product mixture may comprise one or more C1-4 paraffins and / or olefins, while in other embodiments, the light hydrocarbon product mixture may comprise one or more C1-5 paraffins and / or olefins. The parameters of the separator may be adjusted as readily understood by one of ordinary skill in the art to shift the carbon ranges of the separated streams (e.g., light, medium, heavy). It may be desirable to shift the carbon range of the paraffins and olefins in the light hydrocarbon product mixture depending on the desired product and to improve yield.

[0072] The first separator may have an aqueous outlet, which may also be referred to herein as a wastewater outlet, a Ce and higher (“Ce+”) hydrocarbon outlet, and a CO2, H, C1-5 hydrocarbon outlet. The first separator may be configured to separate the light hydrocarbon product mixture into a recycle stream and a remainder light hydrocarbon product mixture comprising one or more C1-5 paraffins and / or olefins. The recycle stream may comprise one or more C1-3 hydrocarbons, CO2, CO, and / or H2, and may be combined with the first reduction gas and / or the carbon source gas prior to contacting with the reduction catalyst. The recycle stream may further comprise oxygenates, for example, C1-3 alcohols.

[0073] The second separator may be configured to separate the heavy hydrocarbon product mixture from the medium hydrocarbon product mixture. The oligomerization reactor has an oligomerization product outlet, and may be configured to receive at least a portion of the light hydrocarbon product mixture from the first separator and the oligomerization reactor may be configured to receive the medium hydrocarbon product mixture from the second separator. The third separator may be configured to receive the heavy hydrocarbon product mixture from the second separator, and may be configured to afford a target olefin product mixture comprising one or more Cio-16 olefins, separated from a heavy olefin product mixture comprising one or more C17+ paraffins and / or olefins.

[0074] In this embodiment, the medium hydrocarbon product mixture may comprise one or more C5-8 paraffins and / or olefins. In certain embodiments, the medium hydrocarbon product mixture may comprise one or more C5-8 paraffins and / or olefins, while in other embodiments, the medium hydrocarbon product mixture may comprise one or more Ce-9 paraffins and / or olefins. The parameters of the separator may be adjusted as readily understood by one of ordinary skill in the art to shift the carbon ranges of the separated streams (e.g., light, medium, heavy). It may be desirable to shift the carbon range of the paraffins and olefins in the medium hydrocarbon product mixture depending on the desired product and to improve yield.

[0075] The oligomerization reactor may be configured to both convert (also referred to as dimerize) C2-5 olefins to C4-8 olefins, and optionally Ce-io olefins, and then to convert (also referred to as dimerize) C4-8 olefins to Cio-16 olefins. The oligomerization reactor may include two sections with each section comprising the oligomerization catalyst. The oligomerization catalyst in each or the sections may be the same or different. The oligomerization reactor may include an intermediate quench between the two sections. The intermediate quench may be supplied by the first separator, the third separator, or both the first and third separators. The oligomerization reactor may be a stacked bed reactor.

[0076] The oligomerization reactor may include two separate oligomerization reactors connected in series, with each oligomerization reactor comprising an oligomerization catalyst.

[0077] The system may further comprise a hydrogenator coupled to the third separator configured to receive and hydrogenate the target olefin product mixture and make paraffinic kerosene. The hydrogenator may be coupled to an additional reduction gas feed.

[0078] In an embodiment, in the place of a third separator may be a hydrogenator and separator such that both of the heavy hydrocarbon product mixture and the oligomerization product mixture are hydrogenated before separation into a target product mixture (e.g., Cio-ie) and a heavy product mixture (e.g., C17+).

[0079] The system may comprise a fourth separator coupled to the third separator to remove naphtha from the heavy hydrocarbon product mixture. The system may comprise a fourth separator coupled to the hydrogenator to remove naphtha from the target olefin product mixture.

[0080] Methods for Aviation Fuel Production

[0081] 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.

[0082] 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.

[0083] 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 light hydrocarbon product mixture; and a target hydrocarbon product mixture; (ii) contacting the light hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas with an oligomerization catalyst to afford an oligomerization product mixture; (iv) hydrogenating the target hydrocarbon product mixture and the oligomerization product mixture to afford a hydrogenated paraffin product mixture comprising a medium paraffin product mixture comprising one or more Ce-9 paraffins, and a target paraffin product mixture comprising one or more Cio-16 paraffins; and (v) contacting the medium paraffin product mixture with a reforming catalyst to afford a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture. The light hydrocarbon product mixture may comprise one or more C1-5 paraffins and / or olefins. The hydrogenated paraffin product mixture may comprise a light paraffin product mixture comprising one or more C1-5, a medium paraffin product mixture comprising one or more Ce-9 paraffins, and a target paraffin product mixture comprising one or more Cio-16 paraffins. The method may further comprise the step of alkylating the light aromatic product mixture with the light hydrocarbon product mixture by contacting light aromatic product mixture and the light hydrocarbon product mixture with an alkylation catalyst to afford a target aromatic product mixture. The method may further comprise the step of hydrogenating at least a portion of the target aromatic product mixture to afford a target cycloparaffin product mixture.

[0084] Another step may include combining the target aromatic product mixture and the target paraffin product mixture to make aviation fuel. The method may include combining the target aromatic product mixture, the target cycloparaffin product mixture, and the target paraffin product mixture to make aviation fuel. The target hydrocarbon product mixture may comprise a medium hydrocarbon product mixture comprising one or more Cio-16 paraffins and / or olefins, and, optionally, a heavy hydrocarbon product mixture comprising one or more C17-40 paraffins and / or olefins.

[0085] 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.

[0086] 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.

[0087] The paraffin pressure may be about 75 psi to about 500 psi. The paraffin pressure may be about 75 psi, about 500 psi, about 325 psi, about 350 psi, about 375 psi, about 400 psi, or about 450 psi.

[0088] In certain embodiments, each of the light hydrocarbon product mixture, the medium product mixture, the heavy hydrocarbon product mixture, and / or the target hydrocarbon product mixture comprises olefins and paraffins. In further embodiments, the ratio of olefins to paraffins in each of the light hydrocarbon product mixture, the medium product mixture, the heavy hydrocarbon product mixture, and / or the target hydrocarbon product mixture is at least about 0.5: 1. The ratio of olefins to paraffins in each of the light hydrocarbon product mixture, and the medium product mixturemay 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 andthe medium 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.

[0089] 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 C2-5 paraffins and / or olefins. In some embodiments, the ratio of C2-5 olefins to C2-5 paraffins in the light hydrocarbon product mixture is at least about 5 : 1. In further embodiments, the ratio of C2-5 olefins to C2-5 paraffins in the light hydrocarbon product mixture is at least about 8: 1. In certain embodiments, the ratio of C2-5 olefins to C2-5 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 C2-5 olefins to C2-5 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.

[0090] In some embodiments, the medium hydrocarbon product mixture comprises one or more Ce-9 paraffins and olefins. In certain embodiments, the ratio of Ce-9 olefins to Ce-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 Ce-9 olefins to Ce-9 paraffins in the medium hydrocarbon product mixture is about 3: 1 to about 12: 1. In certain embodiments, the ratio of Ce-9 olefins to Ce-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.

[0091] 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.

[0092] In some embodiments, contacting the medium paraffin product mixture, optionally the second reduction gas, and optionally the second carbon source gas, with a reforming catalyst occurs at an aromatic temperature from about 200 °C to about 650 °C, about 400 °C to about 650 °C, or about 500 °C to about 600 °C. In certain embodiments, contacting the medium paraffin product mixture, optionally a second reduction gas, and optionally a second carbon source gas, with a reforming catalyst occurs at an aromatic pressure from about 20 psi to about 800 psi, about 20 psi to about 1000 psi, about 20 psi to about 500 psi, or about 20 psi to about 200 psi.

[0093] Methods of the disclosure may further comprise passing the light hydrocarbon product mixture through an adsorbent bed or a distillation column prior to contacting with the oligomerization catalyst.

[0094] Methods of the disclosure may further comprise passing the medium paraffin product mixture through an adsorbent bed or a distillation column prior to contacting with the reforming catalyst.

[0095] The medium paraffin product mixture may be split into streams, with the first stream being contacted with the reforming catalyst and the second stream being combined with the target hydrocarbon product mixture to again undergo hydrogenation. In certain embodiments, contacting the medium paraffin product mixture with the reforming catalyst further affords a light aromatic product mixture comprising one or more Ce- 8 aromatics. The method may then further comprise contacting the light aromatic product mixture with the oligomerization catalyst, alkylation catalyst or both of the foregoing catalysts in a single oligomerization step to afford alkylated aromatics in the oligomerization product mixture. When the light aromatic product is supplied to the oligo-alkylation reactor, alkylated aromatics, optionally comprising one or more C9-14 aromatics, may be formed and incorporated into the oligomerization product mixture.

[0096] Methods of the disclosure may comprise contacting the light hydrocarbon product mixture with an oligomerization catalyst to afford an oligomerization product mixture. The method may further comprise applying an intermediate quench to the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst. The intermediate quench may be the light aromatic product mixture. The intermediate quench may be a part of the light hydrocarbon product mixture and / or the light aromatic product mixture.

[0097] 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.

[0098] The temperature at which this oligomerization may be carried out can range from about 50 °C to about 400 °C as needed to tailor the degree of oligomerization based on the desired product length and distribution. The oligomerization temperature may be about 40 °C to about 400 °C, about 30 °C to about 300 °C, about 50 °C to about 250 °C, about 100 °C to about 250 °C, or about 120 °C to about 250 °C. The oligomerization temperature may be about 50 °C, about 100 °C, about 110 °C, about 120 °C, about 150 °C, about 180 °C, about 190 °C, about 200 °C, about 220 °C, about 230 °C, or about 250 °C. When the oligomerization reactor has a top section and a bottom section, each of the top section and the bottom section has an oligomerization temperature that may be the same or different.

[0099] The pressure at which this oligomerization may be carried out can range from about 0 psi to about 2000 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 2000 psi, about 500 psi to about 2000 psi, about 0 psi to about 1000 psi, about 100 psi to about 1000 psi, or about 300 psi to about 1500 psi. The oligomerization pressure may be about 0 psi, about 30 psi, about 250 psi, about 500 psi, about 750 psi, about 1000 psi, about 1250 psi, about 1500 psi, about 1750 psi, or about 2000 psi.

[0100] Methods of the disclosure may further comprise passing the light hydrocarbon product mixture through an adsorbent bed prior to contacting with the oligomerization catalyst, alkylation catalyst or both of the foregoing catalysts.

[0101] Methods of the disclosure may further comprise removing impurities from the light hydrocarbon product mixture prior to contacting with the oligomerization catalyst. The impurities may be removed by any means known in the art, including, for example, by reactive chemistry, absorption, or other processing. The impurities may comprise oxygenates, sulfur, metals, or a combination thereof.

[0102] In certain embodiments, contacting the light hydrocarbon product mixture and / or the light aromatic product mixture with the oligomerization catalyst further affords an oligomerized product mixture comprising a medium oligomerized product mixture comprising one or more Ce-9 hydrocarbons, a target oligomerized product mixture comprising one or more Cio-16 paraffins and / or olefins, and a heavy oligomerized product mixture comprising one or more C17-40 paraffins and / or olefins.

[0103] In certain embodiments, contacting the light hydrocarbon product mixture with the oligomerization catalyst further affords a medium oligomerized product mixture comprising one or more Ce-9 hydrocarbons.

[0104] 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.

[0105] 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.

[0106] The oligomerization product mixture may include: a light oligomerized product mixture comprising one or more C1-2 hydrocarbons, a medium oligomerized product mixture comprising one or more C3-7 hydrocarbons, a target oligomerized product mixture comprising one or more Cs-i6 hydrocarbons, and / or a heavy oligomerized product mixture comprising one or more C17-25 paraffins and / or olefins. The oligomerization product mixture may include a mixed target product mixture comprising one or more C9-14 aromatics and one or more Cio-16 paraffins and / or olefins.

[0107] 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 to about 500 °C, about 50 °C to about 400 °C, or about 100 °C to about 350 °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.

[0108] The light hydrocarbon product mixture and the light aromatic product mixture may be contacted with an alkylation catalyst before contacting with, or concurrently with the oligomerization catalyst. The alkylation catalyst and the oligomerization catalyst may be mixed or layered within an oligo-alkylation reactor.

[0109] 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 50 psig to about 1000 psig.

[0110] Methods of the disclosure may comprise hydrogenating the target hydrocarbon product mixture and the oligomerization product to afford a hydrogenated paraffin product mixture comprising a light paraffin product mixture, a medium paraffin product mixture, and a target paraffin product mixture. Hydrogenating the target hydrocarbon product mixture and the oligomerization product may also afford a heavy paraffin product mixture. In certain embodiments, the light paraffin product mixture comprises one or more C1-5 paraffins, a medium paraffin product mixture comprises one or more Ce-9 paraffins, a target paraffin product mixture comprises one or more Cio-16 paraffins, and a heavy paraffin product mixture comprises one or more C17+ paraffins. The hydrogenated paraffin product mixture may further comprise less than about 10%, or less than about 5%, of aromatics.

[0111] The method may comprise separating the light paraffin product mixture, the medium paraffin product mixture, and the target paraffin product mixture. The method may comprise separating the target paraffin product mixture from the heavy paraffin product mixture. Once separated from the rest of the product, the light paraffin product mixture may be recycled and reintroduced into the system by hydrogenating the light paraffin product mixture to make the hydrogenated paraffin product mixture. Optionally, the light paraffin product mixture may be contacted with a fourth reduction gas before hydrogenating.

[0112] Methods of the disclosure may further comprise contacting the light hydrocarbon product mixture and the light aromatic product mixture with an oligomerization catalyst, and optionally also an alkylation catalyst, to afford the oligomerization product mixture. Methods of the disclosure may further comprise two steps of contacting the light hydrocarbon product mixture and the light aromatic product mixture with an oligomerization catalyst, and optionally also an alkylation catalyst, to afford the oligomerization product mixture, with each step comprising dimerizing the olefins present in the stream in contact with the oligomerization catalyst.

[0113] In an embodiment, the light hydrocarbon product mixture may be separated into two parts, whereby the first part of the light hydrocarbon product mixture contacts the oligomerization catalyst twice such that the olefins present in the mixture are dimerized twice. In this embodiment, the second part of the light hydrocarbon product mixture contacts the oligomerization catalyst once such that the olefins present in the mixture are dimerized once. As such, the method may include contacting the light hydrocarbon product mixture with the oligomerization catalyst may comprise two steps: dimerizing one or more C2-5 olefins in the light hydrocarbon product mixture to make C4-10 olefins; followed by dimerizing the C4-10 olefins to make C10-20 olefins. When contacting the light hydrocarbon product mixture with the oligomerization catalyst comprises two steps, the oligomerization temperature in each of the steps may be the same or different, with each oligomerization temperature being between about 120 °C and about 250 °C.

[0114] In some embodiments, the medium hydrocarbon product mixture may in part or in entirety be contacted with the oligomerization catalyst. The step of contacting the medium hydrocarbon product mixture with the oligomerization catalyst may comprise: dimerizing the one or more Ce-9 olefins to make C12-18 olefins.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] Methods of the disclosure may further comprise hydrogenating the light aromatic product mixture, for example, to make cycloparaffins. Optionally, this may further include contacting the light aromatic product mixture with a fourth reduction gas before hydrogenating.

[0120] Methods for Paraffinic Kerosene Production

[0121] A method for the production of paraffinic kerosene for aviation fuel is disclosed. The method includes: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a light hydrocarbon product mixture comprising one or more C2-4 paraffins and / or olefins; heavy hydrocarbon product mixture; and a medium hydrocarbon product mixture. Next steps may be contacting the light hydrocarbon product mixture and the medium hydrocarbon product mixture with an oligomerization catalyst in an oligomerization reactor to provide an oligomerization product mixture, and combining the heavy hydrocarbon product mixture and the oligomerization product mixture to afford a combined product mixture. The method also includes separating the combined product mixture into a target olefin product mixture comprising one or more Cio-16 olefins, and a heavy olefin mixture comprising one or more C17+ paraffins and / or olefins. The target olefin product mixture may include one or more Cio-16 paraffins and one or more Cio-16 olefins. The heavy olefin mixture comprising one or more C17+ paraffins and / or olefins may subsequently be hydrogenated. In an embodiment, the combined product mixture undergoes hydrogenation and separation in a combined step. The next step includes hydrogenating the target olefin product mixture to afford paraffinic kerosene. In another embodiment, the target olefin product mixture and the heavy olefin mixture may be combined, and passed through a hydrogenation reactor comprising a hydrogenation catalyst to saturate the olefins. The saturated hydrogenation product may be separated into paraffinic kerosene and a heavy paraffin product mixture comprising one or more C17-25 paraffins which may be recovered and processed as diesel fuel.

[0122] The paraffinic kerosene made by the processes herein may include about 30 wt% to about 60 wt% Cio-16 / -paraffins, about 30 wt% to about 60 wt% C10-16 isoparaffins, with less than about 5 wt% cycloparaffins and less than about 1 wt% aromatics. The paraffinic kerosene made by the processes herein may include about 35 wt% to about 55 wt% C10-16 / - paraffins, about 35 wt% to about 55 wt% C10-16 isoparaffins, with less than about 5 wt% cycloparaffins and less than about 1 wt% aromatics. The paraffinic kerosene may include about 0 wt% aromatics. The paraffinic kerosene may include less than about 1 wt% cycloparaffins. The paraffinic kerosene may include about 40 wt% to about 50 wt% C10-16 / - paraffins, about 40 wt% to about 50 wt% C10-16 isoparaffins. The paraffinic kerosene may include about 40 wt% to about 50 wt% C 10-16 / / -paraffins, about 40 wt% to about 50 wt% C10- 16 isoparaffins, about 0 wt% aromatics, and less than about 1 wt% cycloparaffins.

[0123] The step of contacting the light hydrocarbon product mixture with the oligomerization catalyst may comprise two steps: dimerizing one or more C2-4 paraffins and / or olefins in the light hydrocarbon product mixture to make one or more C4-8 paraffins and / or olefins; followed by dimerizing the C4-8 paraffins and / or olefins to make Cio-16 paraffins and / or olefins. The step of contacting the medium hydrocarbon product mixture with the oligomerization catalyst may comprise: dimerizing the one or more C5-8 paraffins and / or olefins to make Cio-16 paraffins and / or olefins. The target and heavy paraffins and / or olefins may make up the majority (that is, over 50 wt%) of the oligomerization product mixture. The oligomerization product mixture may comprise about 0 wt% to about 8 wt% of a light oligomerized product mixture comprising C1-5 hydrocarbons, about 0 wt% to about 8 wt% of a medium oligomerized product mixture comprising Ce-9 hydrocarbons, about 10 wt% to about 50 wt% of a heavy oligomerized product mixture comprising C17+ hydrocarbons, and about 30 wt% to about 80 wt% of a target oligomerized product mixture comprising C10-C16 hydrocarbons. The selectivity of the oligomerization catalyst may vary depending on the residence time in the reactor, as readily understood by one of ordinary skill in the art. For example, higher residence time will result in a higher selectivity to the heavy oligomerized product mixture.

[0124] The oligomerization reactor may comprise two or more sections within a single reactor, with each section comprising the oligomerization catalyst. The oligomerization catalyst in each of the sections of the oligomerization reactor may be the same or different. There may be an intermediate quench supplied between the sections of the oligomerization reactor to reduce the temperature within the bottom section of the reactor. In an embodiment, the method further includes applying an intermediate quench to the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst.

[0125] While the oligomerization reactor is depicted in the figures as a single reactor with two sections, it may also be replaced with two separate oligomerization reactors arranged in series.

[0126] The temperature at which this oligomerization may be carried out can range from about 50 °C to about 400 °C as needed to tailor the degree of oligomerization based on the desired product length and distribution. The oligomerization temperature may be about 40 °C to about 400 °C, about 30 °C to about 300 °C, about 50 °C to about 250 °C, about 100 °C to about 250 °C, or about 120 °C to about 250 °C. The oligomerization temperature may be about 50 °C, about 100 °C, about 110 °C, about 120 °C, about 150 °C, about 180 °C, about 190 °C, about 200 °C, about 220 °C, about 230 °C, or about 250 °C. When the oligomerization reactor has a top section and a bottom section, each of the top section and the bottom section has an oligomerization temperature that may be the same or different.

[0127] The pressure at which this oligomerization may be carried out can range from about 0 psi to about 2000 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 2000 psi, about 500 psi to about 2000 psi, about 0 psi to about 1000 psi, about 100 psi to about 1000 psi, or about 300 psi to about 1500 psi. The oligomerization pressure may be about 0 psi, about 30 psi, about 250 psi, about 500 psi, about 750 psi, about 1000 psi, about 1250 psi, about 1500 psi, about 1750 psi, or about 2000 psi.

[0128] The method may further comprise removing impurities from the light hydrocarbon product mixture prior to contacting with the oligomerization catalyst. The impurities may be removed by any means known in the art, including, for example, by reactive chemistry, absorption, or other processing. The impurities may comprise oxygenates, sulfur, or a combination thereof.

[0129] Catalysts for Conversion of Carbon Sources to Olefins and Paraffins

[0130] 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.

[0131] Any suitable reduction catalyst may be used in accordance with this disclosure.

[0132] 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.

[0133] Reduction catalysts of the disclosure may comprise copper, iron, zinc, cobalt, or some combination thereof. The reduction catalyst may comprise copper. Copper catalysts are known to be among the most efficient reduction catalysts, producing oxygenates as the major products. Such catalysts may include copper as the primary catalytic component with one or more additional metal promoters including but not limited to zinc, zirconium, aluminum, chromium, alkali metals and alkaline earth metals. Such additional components of the catalysts (including additional metal promoters, metal alloys, and / or metal oxides) provide electronic and structural support to better tune the reactivity and selectivity of carbon dioxide hydrogenation.

[0134] Reduction catalysts of the disclosure 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 catalysts comprising copper, iron- and cobalt-containing catalysts may comprise one or more additional metal promoters to improve both carbon dioxide adsorption and selectivity of the hydrogenation. The one or more additional metal promoters may be selected from zinc, manganese, molybdenum, copper, nickel, an alkali metal and an alkaline earth metal.

[0135] 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.

[0136] 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 olefins, predominantly, as well as paraffins and / or other hydrocarbons in a minority amount.

[0137] 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.

[0138] 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, 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.

[0139] 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, 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.

[0140] 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.

[0141] 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 about 1 :2.5: 1. In some embodiments, the molar content of zinc is preferably 0.3 - 1 times the molar content of the copper. In some embodiments, the molar content of cobalt is preferably 0.1 - 1 times the molar content of the copper.

[0142] 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 (Fe2O3), 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 (Fe^Cf) and hematite (Fe2O3).

[0143] 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 about 1 :2.3 :2.3. In some embodiments, the molar content of zinc is preferably about 0.3 to about 1 times the molar content of the copper. In some embodiments, the molar content of iron is about 0.5 to about 5 the molar content of the copper.

[0144] In addition to the one or more first elements described above, the reduction catalyst may comprise one or more second elements selected from transition metals, a 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.

[0145] 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 may 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.

[0146] 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.

[0147] 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.

[0148] 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. 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 sodium and / or cesium. In some embodiments, the one or more Group IA or IIA metals comprise sodium and cesium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In certain embodiments, the one or more Group IA or IIA metals comprise cesium. In some embodiments, the one or more Group IA or IIA metals consist of sodium and / or cesium. In certain embodiments, the one or more Group IA or IIA metals consist of sodium and cesium. In some embodiments, the one or more Group I A or IIA metals consist of sodium. In certain embodiments, the one or more Group I A or IIA metals consist of cesium.

[0149] 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, or about 0.40 to about 0.50 relative to copper.

[0150] 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.

[0151] 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 1.0 relative to copper.

[0152] 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.

[0153] 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 The reduction catalyst may comprise alumina.

[0154] 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 introduced in-situ, e.g., during formation of the catalyst, as a component of the reduction catalyst, e.g. from aluminum nitrate co-precipitation with first element, copper, and zinc precursors.

[0155] 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.

[0156] 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.

[0157] The elemental composition of the reduction catalyst material may be Cu(ZnO)CoA / Al2O3, Cu(ZnO)CoFeA / Al2O3, Cu(ZnO)CoNbA / Al2O3,

[0158] Cu(ZnO)CoNiA / Al2O3, Cu(ZnO)CoMoA / Al2O3 wherein A is an alkali metal and further wherein the relative amounts of the elemental components are as described above.

[0159] 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 / Al2O3, wherein the relative amounts of the elemental components are as described above.

[0160] 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 AhOs, wherein the relative amounts of the elemental components are as described above.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] In some embodiments, the reduction catalyst support is selected from SiA10x, 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.

[0172] 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.

[0173] In some embodiments, the reduction catalyst support is modified with molybdenum, chlorine, and / or sulfur.

[0174] 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”).

[0175] In some embodiments, the reduction catalyst support has a mesopore volume from about 0.01 to about 3.0 cc / g.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] In certain embodiments described throughout the present disclosure, reduction catalysts of the disclosure comprise iron. In such embodiments, the iron is preferably in the form of an iron oxide. In certain such embodiments, the iron oxide is magnetite (FesC ), hematite (Fe20s), or a combination thereof. In further such embodiments, the iron oxide is magnetite (FesCU). In yet further such embodiments, the iron oxide is a combination of magnetite (FesC ) and hematite (Fe20s).

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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. 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.

[0187] In certain embodiments, the reduction catalyst comprises: iron;

[0188] K, Cs, Mg, Rh, Ca, or a combination thereof, at a molar ratio of from 0 to about 0.20 relative to iron;

[0189] Na, Cu, Cr, Mn, or a combination thereof, at a molar ratio of from 0 to about 0.60 relative to iron;

[0190] Co, Ru, Ni, or a combination thereof, at a molar ratio of from 0 to about 0.50 relative to iron.

[0191] 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.

[0192] 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).

[0193] 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.

[0194] 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).

[0195] 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), FesCU (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

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] Another reduction catalyst may comprise iron and zinc, one or more second elements selected from Group IA, IIA, and X metals, and a binder. When the reduction catalyst includes a binder, it may also be referred to as a 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

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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

[0207] 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.

[0208] (1) 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.

[0209] 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 (Fe^CU) and hematite (Fe20s).

[0210] The reduction catalyst may comprise: iron; zinc; a first element selected from copper, cobalt, or combinations thereof; optionally one or more second elements selected from Group I A, IIA and X metals; and a binder.

[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), Fe^CU (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] (2) 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: l; about 2:2 to about 6: 1, about 1 : 1 to about 4: 1, about 1 : 1 to about 3: l, or about 2: 1 to about 3: 1. 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] (3) 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] 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.CEL 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.

[0221] Eq. 1: Selectivity for methane (SCi) = [Cmol.CEL / Cmol.CChfeed - Cmol.CChproduct)]

[0222] 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 C2 to C4 hydrocarbons (SC2-C4) of greater than about 15, greater than about 20, greater than about 25, greater than about 30, greater than about 35, or greater than about 35 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.

[0223] Eq. 2: Selectivity for hydrocarbon Cx(SCX) = [Cmol.Cx / (Cmol.CChfeed -

[0224] Cmol .

[0225] 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.

[0226] 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%.

[0227] 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.

[0228] 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%.

[0229] 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.

[0230] 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. 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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. In certain aspects, the reduction catalyst further comprises 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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 aboutlOO to about500 nm. In certain embodiments, the particles not subjected to agglomeration are 100-500 nm in particle size.

[0241] 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 and / or argon) before the production.

[0242] 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.

[0243] 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.

[0244] 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:

[0245] • improves methane selectivity;

[0246] • the acidity improves hydrocarbon yield;

[0247] • creates meso-porosity to the formed catalyst which may improve product selectivity; and

[0248] • reduces metal leaching.

[0249] 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.

[0250] When a promoter is added to the binder, performance (e.g., in terms of SCi and SC5+) of the catalyst may improve 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.

[0251] 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. 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.

[0252] 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.

[0253] Catalysts for Conversion of Carbon Sources to Aromatics

[0254] The systems and methods of the present disclosure may include a reforming catalyst. As used herein, the term “reforming catalyst” refers to a catalyst used for the conversion of carbon sources to aromatics, such as benzene, toluene and xylenes (together referred to as “BTX”), and heavy aromatics, but which does not necessarily itself comprise aromatics. Use of a reforming catalyst may also produce other hydrocarbons in a lesser amount.

[0255] Reforming catalysts may convert naphthenes to aromatics. Naphtha feeds contain both five-membered and six-membered naphthene rings (cyclopentane, alkyl-cyclopentanes, cyclohexane, and alkyl-cyclohexanes). The six-carbon ring cyclohexanes, for example, can be directly dehydrogenated to produce aromatics and hydrogen on metallic sites. This is a very fast reaction that produces significant endotherms in the lead reactors due to the large amount of six-carbon ring naphthenes typically in the naphtha feed. Under reforming conditions, this reaction greatly favors aromatics thermodynamically. To convert five-membered ring alkyl cyclopentanes to an aromatic, they are first hydroisomerized to give a cyclohexane intermediate prior to dehydrogenation to aromatics. The conversion of an alkylcyclopentane ring to an aromatic requires both reactions to occur in series and therefore requires both the acid and the metal function of the reforming catalyst. Paraffins are dehydrogenated on the platinum sites to form olefins that can then isomerize over the acid function of the catalyst to provide higher octane branched paraffins. Within a given carbon number, the concentrations of normal paraffins, branched paraffins, and their corresponding olefins tend to be at or near equilibrium at the reactor outlet. Although olefins are normally at relatively low levels in the reformate product, they also contribute positively to the octane compared with paraffins. Another function of the reforming catalyst is for paraffins to cyclize to cyclohexanes and cyclopentanes (dehydrocyclization). The reforming catalyst may include both metal sites for dehydrogenation reactions and acid sites for isomerization and cyclization reactions. Reforming catalysts may comprise platinum supported on an alumina support, optionally modified, for example, a chlorinated alumina support. The reforming catalyst may also include an additional metal component to modify either the acidic or metallic sites. The reforming catalyst may be modified and used with a fixed bed and be semi -regenerative or cyclic or continuously regenerating reforming. The support used for reforming catalysts may be a high surface area gamma (y) alumina of the formula AhCh ftFhO with a porous structure forming a complex network of interconnected channels. Reforming catalysts are explained in detail in Egolf, B., et al., “The Honeywell UOP CCR Platforming™ Process for BTX Production (Case Study),” Industrial Arene Chemistry, Chapter 10, 2023, pp. 269-294 is incorporated by reference herein in its entirety.

[0256] The reforming catalyst may comprise a molecular sieve. The reforming catalyst may comprise a zeolite. The reforming catalyst may comprise any such catalysts known for this use in the art, for example those developed and sold by UOP, including but not limited to UOP R- 560, UOP R-364, and any combination thereof.

[0257] The reforming catalyst may comprise platinum (Pt), palladium (Pd), or a combination thereof. The reforming catalyst may comprise platinum, and an optionally modified support. The reforming catalyst may comprise platinum, an optionally modified alumina support, and an additional metal component. The reforming catalyst may comprise platinum, a chlorinated alumina support, and an additional metal component. The reforming catalyst may comprise a bimetallic formulation of Pt with Iridium or Rhenium supported on alumina (AI2O3).

[0258] In certain embodiments, reforming catalysts of the disclosure, such as those described above, are active in the conversion of a carbon source gas, such as CO2 or naphtha, to aromatics, such at BTX.

[0259] Catalysts for Hydrocracking

[0260] 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.

[0261] 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.

[0262] 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.

[0263] 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.

[0264] In some embodiments, the hydrocracking 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.

[0265] 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.

[0266] 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, 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. In some embodiments, the hydrocracking support is modified with molybdenum, chlorine, and / or sulfur.

[0267] 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.

[0268] 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.

[0269] Catalysts for Alkylation of Aromatics

[0270] 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.

[0271] 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. Catalysts for Oligomerization

[0272] 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, and MCM-56, and any combination thereof. The oligomerization catalyst may be ZSM-5, beta-zeolite, MCM-22, MCM-49, mordenite, SAPO- 5, or a combination thereof. The oligomerization catalyst may be selected from ZSM-5, ZSM-

[0273] 11, ZSM-22, ZSM-23, ZSM-35, MCM-22, MCM-49, PSH-3, and any combination thereof. The oligomerization catalyst may be ZSM-5.

[0274] 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 from about 0.1 g of reactant per 1 g of catalyst per hour (0.1 h'1) to about 50 h’1, from about 0.5 h'1to about 20 h’1, or from about 0.5 h'1to about 5 h’1.

[0275] When the oligomerization reactor has two oligomerizing sections, the top section comprises an oligomerization catalyst that is the same or different as the oligomerization catalyst in the bottom section. In an embodiment, the top section of the oligomerization reactor comprises a first oligomerization catalyst wherein the light hydrocarbons supplied therein are dimerized, and then the dimerized hydrocarbon mixture contacts a second oligomerization catalyst in the bottom section of the oligomerization reactor to undergo further dimerization to yield olefins and paraffins in the jet fuel range (i.e., Cio-ie). The first oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-12, ZSM-57, ZSM-35, or a combination thereof. The first oligomerization catalyst may be selected from ZSM-11, ZSM-

[0276] 12, ZSM-57, or a combination thereof. The second oligomerization catalyst may be selected from a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

[0277] When two oligomerization reactors are used in sequence, the first reactor may comprise an oligomerization catalyst that is the same or different as the oligomerization catalyst in the second reactor. The first reactor, that is the reactor that is upstream from the second reactor, may comprise a first oligomerization catalyst selected from ZSM-5, ZSM-11, ZSM-22, ZSM- 23, ZSM-12, ZSM-57, ZSM-35, or a combination thereof. The first reactor may comprise a first oligomerization catalyst selected from ZSM-11, ZSM-12, ZSM-57, or a combination thereof. The second reactor may comprise a second oligomerization catalyst selected from a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM- 56, and any combination thereof.

[0278] When an oligo-alkylation reactor is used in the systems and methods herein, one or more alkylation catalysts and one or more oligomerization catalysts may be stacked, mixed, or otherwise combined within the oligo-alkylation reactor. The one or more alkylation catalysts and the one or more oligomerization catalysts may be mixed, layered within the reactor optionally with an intermediate quench. When an oligo-alkylation reactor having two separate sections is used, the top section comprises an oligomerization catalyst, and the bottom section comprises an alkylation catalyst, and optionally an oligomerization catalyst that is the same or different as the oligomerization catalyst in the top section. In an embodiment thereof, the top section of the oligomerization reactor comprises a first oligomerization catalyst wherein the light hydrocarbons supplied therein are dimerized, and then in the bottom section, the dimerized hydrocarbon mixture contacts a second oligomerization catalyst to undergo further dimerization to yield olefins and paraffins in the jet fuel range (i.e., Cio-ie), and the light aromatic product mixture contacts the alkylation catalyst to yield alkylated aromatics (e.g., C9- 14).

[0279] 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 / AICI3), 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, and MCM-56, and any combination thereof. In further embodiments, the oligo-alkylation catalyst is ZSM-5, betazeolite, MCM-22, MCM-49, PSH-3, mordenite zeolite, SAPO-5, or any combination thereof.

[0280] Reduction Gases, Carbon Source Gases, and Ratios Thereo f

[0281] 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.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] 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. 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.

[0287] 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.

[0288] Definitions

[0289] 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.

[0290] 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).

[0291] 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). 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.

[0292] 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.

[0293] 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).

[0294] 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.

[0295] 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).

[0296] 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.

[0297] 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.

[0298] 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.

[0299] 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.

[0300] EXAMPLES

[0301] 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.

[0302] EXAMPLE 1 : System for the production of aviation fuel

[0303] A system may be constructed according to the flow scheme in Figure 1. When CO2 and H2 are supplied into the system, the carbon selectivity for the conversion of CO2 to SAF, being a blend of paraffins and aromatics of C10-16, is calculated to be 67wt%. Table 1 shows the calculated molar flow rates for each of the reactions and molecular conversions in the system.

[0304] TABLE 1

[0305] EXAMPLE 2: System for the production of paraffinic kerosene

[0306] A system may be constructed according to the flow scheme in Figure 3. When CO2 and H2 are supplied into the system, the carbon selectivity for the conversion of CO2 to paraffinic kerosene, being a blend of C10-16 paraffins, is calculated to be about 70wt%. Table 2 shows the calculated molar flow rates for each of the reactions and molecular conversions in the system.

[0307] TABLE 2

[0308] EXAMPLE 3: Preparation of Fe / Zn-Na reduction catalyst.

[0309] 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.

[0310] 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.

[0311] EXAMPLE 4: Catalyst evaluation for COg hydrogenation.

[0312] Catalysts were made by the method of Example 3, 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.

[0313] TABLE 3: Product Distribution by Catalyst FeZn with Group IA or IIA metal

[0314] 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.

[0315] 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.

[0316] 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. TABLE 4: Product distribution with reduced H2 partial pressure

[0317] 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.

[0318] EXAMPLE 5: Catalyst evaluation of CO2 hydrogenation using Olefin and CH4rich feed

[0319] Catalyst made by the method from Example 3, FeZnNa 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 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%, CsH8= 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.

[0320] TABLE 5: Expected Product Distribution with Mixed Hydrocarbon Feed

[0321] EXAMPLE 6: Method of extrudate synthesis - Sodium Aluminate binder

[0322] 80g powder catalyst (FeZnNa) from Example 3, 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.

[0323] EXAMPLE 7: Method of extrudate synthesis- Sodium Silicate binder

[0324] 80g powder catalyst (FeZnNa) from Example 3, 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.

[0325] EXAMPLE 8: Detailed Method of extrudate synthesis- Potassium Silicate binder

[0326] 80g powder catalyst (FeZnNa) from Example 3, 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.

[0327] EXAMPLE 9: Catalyst evaluation of CO2 hydrogenation

[0328] Powder catalyst samples were prepared according to the procedures set forth in Example 3 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 2, 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.

[0329] 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 6.

[0330] TABLE 6: Examples of the effect of binder on the active metal catalyst performance

[0331] 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%.

[0332] 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.

[0333] EXAMPLE 10: Leaching Rates of Different Metals During Time on Stream

[0334] Powder catalyst from Example 3 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 7 shows metal leaching rates of the powder catalyst and Table 8 shows metal leaching rate of the formed catalyst. The introduction of the binder showed reduced metal leaching rates when comparing similar time on stream.

[0335] TABLE 7: FeZn =2 mole ratio, 1% wt Na Powder catalyst

[0336] TABLE 8: FeZn =2 mole ratio, 1% wt Na with Na-Aluminate binder extrudate

[0337] INCORPORATION BY REFERENCE 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. EQUIVALENTS

[0338] 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. 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 of making aviation fuel comprising: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a light hydrocarbon product mixture; and a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture; and contacting the light hydrocarbon product mixture with an oligomerization catalyst to provide an oligomerization product mixture; hydrogenating the target hydrocarbon product mixture and the oligomerization product mixture to afford a hydrogenated paraffin product mixture comprising a light paraffin product mixture, a medium paraffin product, and a target paraffin product mixture; contacting the medium paraffin product mixture with a reforming catalyst to afford a reformer product mixture comprising a target aromatic product mixture and a light aromatic product mixture; and combining the target aromatic product mixture and the target paraffin product mixture to make aviation fuel.

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

3. The method of claim 2, wherein the recycle stream comprises one or more C1-3 hydrocarbons, CO2, CO, and / or H2.

4. The method of claim 3, further comprising: combining the recycle stream with the first reduction gas and / or the carbon source gas prior to contacting with the reduction catalyst.

5. The method of any one of the preceding claims, wherein the light hydrocarbon product mixture comprises one or more C1-5 paraffins and / or olefins; wherein the medium hydrocarbon product mixture comprises one or more Ce-9 paraffins and / or olefins; andwherein the heavy hydrocarbon product mixture comprises one or more Cs-i6 paraffins and / or olefin.

6. The method of any one of the preceding claims, wherein the light paraffin product mixture comprises one or more C1-5 paraffins, wherein the medium paraffin product mixture comprises one or more Ce-9 paraffins, and wherein the target paraffin product mixture comprises one of more Cio-16 paraffins.

7. The method of any one of the preceding claims, further comprising: separating the light paraffin product mixture from the hydrogenated paraffin product mixture, and hydrogenating the light paraffin product mixture.

8. The method of claim 7, further comprising contacting the light paraffin product mixture with a fourth reduction gas before hydrogenating.

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

10. The method of any one of the preceding claims, where contacting the light hydrocarbon product mixture with the oligomerization catalyst comprises two steps: dimerizing one or more C2-5 paraffins and / or olefins in the light hydrocarbon product mixture to make one or more C4-10 paraffins and / or olefins; followed by dimerizing the one or more C4-10 paraffins and / or olefins to make C10-20 paraffins and / or olefins.

11. The method of any one of the preceding claims, wherein the step of contacting the light hydrocarbon product mixture, and optionally the light aromatic product mixture, with the oligomerization catalyst further comprises: contacting the light hydrocarbon product mixture, and optionally the light aromatic product mixture, with an alkylation catalyst before, after, or concurrently with the oligomerization catalyst.

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

13. The method of claim 12, wherein the intermediate quench is the light aromatic product mixture and / or a portion of the light hydrocarbon product mixture.

14. The method of any one of the preceding claims, 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.

15. The method of any one of the preceding claims, 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.

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

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

18. The method of any one of the preceding claims, wherein contacting the medium paraffin product mixture, optionally the second reduction gas, and optionally the second carbon source gas, with the reforming catalyst occurs at an aromatic temperature from about 200 °C to about 650 °C.

19. The method of any one of the preceding claims, wherein contacting the medium paraffin product mixture, optionally the second reduction gas, and optionally the second carbon source gas, with the reforming catalyst occurs at an aromatic pressure from about 20 psi to about 800 psi.

20. The method of any one of the preceding claims, comprising passing the medium paraffin product mixture through an adsorbent bed prior to contacting with the reforming catalyst.

21. The method of any one of the preceding claims, wherein the hydrogenated paraffin product mixture further comprises a heavy paraffin product mixture comprising one or more C17-25 paraffins.

22. The method of claim 21 further comprising: contacting a third reduction gas and the heavy paraffin product mixture with a hydrocracking catalyst to afford a hydrocracked product mixture comprising one or more Ci-is paraffins and / or olefins.

23. The method of any of the preceding claims, wherein the reduction catalyst comprises: iron; optionally 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.

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

25. The method of claim 23, wherein the first element is zinc; and wherein the catalyst does not contain copper or cobalt.

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

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

28. The method of any one of claims 23-27, 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.

29. The method of claim 28, 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.

30. The method of claim 28, 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.

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

32. The method of any one of claim 23-31, wherein the iron is in the form of an iron oxide, and the iron oxide is magnetite (FesC ).

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

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

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

36. The method of any one of the preceding claims, further comprising: dividing the medium paraffin product mixture into a first stream and a second stream; contacting the first stream of the medium paraffin product mixture with the reforming catalyst; and combining the second stream of the medium paraffin product mixture with the target hydrocarbon product mixture.

37. The method of any one of the preceding claims, wherein the hydrogenated paraffin product mixture further comprises aromatics.

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

39. The method of any one of the preceding claims, wherein the oligomerization catalyst is an aluminosilicate zeolite.

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

41. The method of any one of the preceding claims, wherein contacting the light hydrocarbon product mixture with the oligomerization catalyst occurs at an oligomerization pressure from about 0 psi to about 2000 psi.

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

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

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

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

46. The method of any one of the preceding claims, wherein the first reduction gas, the second reduction gas, the third reduction gas, when present, and the fourth reduction gas, when present, 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.

47. The method of any one of claims 1-46, where the first reduction gas, the second reduction gas, the third reduction gas, and the fourth reduction gas comprise a hydrocarbon, such as CH4, ethane, propane, or butane.

48. The method of any one of claims 1-46, wherein the first reduction gas, the second reduction gas, the third reduction gas, and the fourth reduction gas is, or is derived from, flare gas, waste gas, or natural gas.

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

50. The method of any one of claims 1-48 wherein the first carbon source gas and / or the second carbon source gas comprise CO.

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

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

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

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

55. 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, and a mixed 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 a first separator having a mixed hydrocarbon inlet, a light hydrocarbon product outlet and a target hydrocarbon outlet, wherein the mixed hydrocarbon inlet is coupled to the mixed hydrocarbon outlet on the reduction reactor; an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a light hydrocarbon product inlet and an oligomerization product outlet, wherein the light hydrocarbon product inlet is coupled to the light hydrocarbon product outlet on the first separator; a hydrogenator having an oligomerization product inlet and a hydrogenated paraffin product outlet, wherein the oligomerization product inlet is coupled to the oligomerization product outlet on the oligomerization reactor; a second separator having a hydrogenated paraffin product inlet, a medium paraffin outlet, and a target paraffin outlet, wherein the hydrogenated paraffin product inlet is coupled to the hydrogenated paraffin product outlet on the hydrogenator; and an aromatic reactor comprising a reforming catalyst, said aromatic reactor having a medium paraffin inlet, optionally a second reduction as feed inlet, optionally a second carbon source gas feed inlet, and a mixed aromatic product outlet; wherein the medium paraffin inlet is coupled to the medium paraffin outlet on the second separator, 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.

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

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

58. The system of claim 57, further comprising a blender having a target paraffin inlet coupled to the target paraffin outlet on the second separator, and the blender having a target aromatic inlet coupled to the target aromatic outlet on the third separator.

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

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

61. The system of claim 60, where the alkylation catalyst and the oligomerization catalyst are mixed or layered within the oligo-alkylation reactor.

62. The system of any one of claims 55-59, wherein the oligomerization reactor comprises two sections, with each section comprising the oligomerization catalyst, and wherein the oligomerization reactor comprises an intermediate quench between the sections.

63. The system of claim 55, further comprising: a first adsorbent bed having a second medium paraffin inlet and a light hydrocarbon outlet; wherein the second medium paraffin inlet is coupled to the medium paraffin outlet on the second separator, and the light hydrocarbon outlet is coupled to the mixed hydrocarbon inlet on the first separator.

64. The system of claim 63, wherein the first adsorbent bed further comprises: a recycle stream outlet coupled to the first carbon source gas feed.

65. The system of any one of claims 55-64, further comprising:an oligo-alkylation reactor comprising at least one catalyst selected from: an oligo-alkylation catalyst, an alkylation catalyst, the oligomerization catalyst, or a combination thereof, wherein said oligo-alkylation reactor is coupled to the oligomerization product outlet on the oligomerization reactor, and configured to receive an oligomerization product mixture from the oligomerization reactor and provide a further dimerized oligomerization product mixture to the hydrogenator.

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

67. The system of claim 66, further comprising: a third reduction gas feed; a hydrocracking reactor comprising a hydrocracking catalyst, said hydrocracking reactor having a third reduction gas inlet, a heavy paraffin product inlet and / or a heavy hydrocarbon inlet, and a hydrocracked product outlet; wherein the third reduction gas inlet is coupled to the third reduction gas feed, the heavy paraffin product inlet, when present, is coupled to the heavy paraffin product outlet on the fourth separator, and the heavy hydrocarbon inlet, when present, is coupled to the heavy hydrocarbon outlet on the first separator.

68. The system of any one of claims 55-67, 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.

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

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

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

72. The system of any one of claims 55-71, wherein the oligomerization catalyst is an aluminosilicate zeolite.

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

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

75. A method of making paraffinic kerosene for aviation fuel comprising: contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a light hydrocarbon product mixture; a medium hydrocarbon product mixture; and a heavy hydrocarbon product mixture; and contacting the light hydrocarbon product mixture and the medium hydrocarbon product mixture with an oligomerization catalyst in an oligomerization reactor to provide an oligomerization product mixture; combining the heavy hydrocarbon product mixture and the oligomerization product mixture to afford a combined product mixture; separating the combined product mixture into a target olefin product mixture comprising one or more Cio-16 olefins, and a heavy olefin product mixture comprising one or more C17+ paraffins and / or olefins; and hydrogenating the target olefin product mixture to afford paraffinic kerosene.

76. The method of claim 75, further comprising separating the light hydrocarbon product mixture into a recycle stream and a remainder light hydrocarbon product mixture comprising one or more C3-4 paraffins and / or olefins.

77. The method of claim 76, wherein the recycle stream comprises one or more C1-2 hydrocarbons, CO2, CO, and / or H2.

78. The method of any one of claims 75-77, wherein the light hydrocarbon product comprises one or more C1-4 paraffins and / or olefins; the medium hydrocarbon product comprises one or more C5-8 paraffins and / or olefins; and the heavy hydrocarbon product mixture comprises one or more C9-16 paraffins and / or olefins.

79. The method of any one of claims 75-78, wherein the step of contacting the light hydrocarbon product mixture with the oligomerization catalyst comprises two steps: dimerizing one or more C2-4 paraffins and / or olefins to C4-8 paraffins and / or olefins; and dimerizing the C4-8 paraffins and / or olefins to Cio-16 paraffins and / or olefins.

80. The method of any one of claims 75-79, wherein the step of contacting the medium hydrocarbon product mixture with the oligomerization catalyst comprises dimerizing the one or more C4-8 paraffins and / or olefins to Cio-16 paraffins and / or olefins.

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

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

83. The method of claim 82, wherein the medium hydrocarbon product mixture is supplied as the intermediate quench between the two or more sections within the reactor.

84. The method of any one of claims 75-83, wherein the paraffinic kerosene comprises: about 35 wt% to about 55 wt% C 10-16 / / -paraffins, about 35 wt% to about 55 wt% Cio-16 isoparaffins, less than about 5 wt% cycloparaffins, and less than about 1 wt% aromatics.

85. The method of claim 84, wherein the paraffinic kerosene comprises: about 40 wt% to about 50 wt% Cio-i6«-paraffins, and about 40 wt% to about 50 wt% Cio-16 isoparaffins86. The method of any one of claims 75-85, wherein conversion of the carbon gas source to paraffinic kerosene has a carbon selectivity of over about 64 wt%.

87. A system for the production of paraffinic kerosene for 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, and a mixed 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; a first separator coupled to the reduction reactor, said first separator having a mixed hydrocarbon inlet coupled to the mixed hydrocarbon outlet on the reduction reactor, wherein the first separator is configured to separate a light hydrocarbon product mixture from a target hydrocarbon product mixture comprising a heavy hydrocarbon product mixture and a medium hydrocarbon product mixture; a second separator coupled to the first separator, wherein the second separator is configured to separate the heavy hydrocarbon product mixture from the medium hydrocarbon product mixture; an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having an oligomerization product outlet, wherein the oligomerization reactor is coupled to the first separator and to the second separator, and wherein the oligomerization reactor is configured to receive at least a portion of the light hydrocarbon product mixture from the first separator and the oligomerization reactor is configured to receive the medium hydrocarbon product mixture from the second separator; and a third separator having an oligomerization product inlet coupled to the oligomerization product outlet, wherein said third separator is configured to receive the heavyhydrocarbon product mixture from the second separator, and wherein the third separator is configured to separate a target olefin product mixture comprising one or more Cio-16 olefins, from a heavy olefin product mixture comprising one or more C17+ paraffins and / or olefins.

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

89. The system of claim 87 or 88, wherein the oligomerization reactor includes two sections with each section comprising the oligomerization catalyst; and wherein the oligomerization reactor includes an intermediate quench between the two sections.

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

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

92. The system of any one of claims 87-91, wherein the light hydrocarbon product comprises one or more C1-4 paraffins and / or olefins; the medium hydrocarbon product comprises one or more C5-8 paraffins and / or olefins; and the heavy hydrocarbon product mixture comprises one or more C9-16 paraffins and / or olefins.

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