Systems and methods for converting carbon dioxide to fuel via methanol

Abstract

Provided herein are systems and methods for converting a carbon source gas into an alcohol mixture containing methanol, followed by conversion of the methanol into mixtures of paraffins and aromatics suitable for use as aviation fuel.

Description

[0001] PATENT Attorney Docket No. : CSW-02925

[0002] SYSTEMS AND METHODS FOR CONVERTING CARBON DIOXIDE TO FUEL VIA METHANOL

[0003] BACKGROUND

[0004] 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 apriority. 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.

[0005] 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 make SAF from vegetable oils, animal fats, and waste oils. However, the SAF made from such 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.

[0006] SUMMARY OF THE INVENTION

[0007] A method for producing aviation fuel from a carbon source gas comprising: contacting a

[0008] reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol; contacting the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture; contacting the medium olefin product mixture, the heavy olefin product mixture, or both of the medium and the heavy olefin product mixtures with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins, and optionally also linear olefins; contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture; contacting the medium olefin product mixture, the heavy olefin product mixture, or

[0009] FH13166046.1Attorney Docket No.: CSW-02925

[0010] both of the medium and the heavy olefin product mixtures, and optionally a portion of the light olefin product mixture, with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and / or naphthenes; and blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

[0011] Other methods for producing aviation fuel from a carbon source gas disclosed herein comprise: contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol; contacting a first portion of the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture; contacting the medium olefin product mixture and the heavy olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins; contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture; either: i) contacting a second portion of the alcohol product stream with an ATA catalyst at an ATA temperature and an ATA pressure to afford an aromatic product mixture, or ii) contacting a second reduction gas and a second carbon source gas with a bi-functional aromatic catalyst to afford an aromatic product mixture; and blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture. The method may further include: contacting a first portion of the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics; and optionally blending the target alkyl arene product mixture with the paraffin product mixture and the aromatic product mixture to afford the blended fuel product mixture. The method may further include: contacting a portion of the aromatic product mixture with the hydrogenation catalyst to afford the paraffin product mixture; and / or contacting at least a portion of the target alkyl arene product mixture with the hydrogenation catalyst to afford the paraffin product mixture, and / or contacting at least a second portion of the light olefin product mixture with the alkylation catalyst to afford the target alkyl arene product mixture.

[0012] The method may further include: processing at least a first portion of the light olefin product mixture via ethylene oligomerization and olefin metathesis to afford long-chain

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[0014] FH13166046.1Attorney Docket No.: CSW-02925

[0015] olefins, and optionally contacting the long-chain olefins with the hydrogenation catalyst to afford the paraffin product mixture.

[0016] Systems for the production of aviation fuel are also disclosed. One system comprises: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst to afford an alcohol product stream; an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet; an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet, optionally a heavy olefin product inlet, and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor; and at least one hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor. The system may also include an aromatic reactor comprising an aromatic catalyst, the aromatic reactor having a heavy olefin product inlet, optionally a medium olefin product inlet, and an aromatic product outlet, and optionally also having a second reduction gas inlet, and a second carbon source feed inlet; an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet, wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; and a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet. The paraffin product outlet of the hydrogenation reactor may be coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor may be coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor may be coupled to the target alkyl arene product inlet of the blender. The system may include a second reduction gas feed and / or a second carbon source feed.

[0017] Another system for the production of aviation fuel comprises: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst to afford an alcohol product stream; an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said - 3 -

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[0019] ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet; an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet, optionally a heavy olefin product inlet, and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor; a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor; an aromatic reactor; an alkylation reactor comprising an alkylation catalyst; and a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet. The alkylation reactor may have an aromatic product inlet and a target alkyl arene outlet. The paraffin product outlet of the hydrogenation reactor may be coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor may be coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor may be coupled to the target alkyl arene product inlet of the blender. The hydrogenation reactor may comprise an aromatic product inlet coupled to the aromatic reactor. The hydrogenation reactor may comprise a target alkyl arene product inlet coupled to the alkylation reactor.

[0020] The system may comprise ethylene oligomerization to afford a long-chain olefin product, which optionally may be directed to the hydrogenation reactor. The ethylene oligomerization may include a shell higher olefin process system having a light olefin product inlet and a long-chain olefin product outlet. The hydrogenation reactor may comprise a long-chain olefin product inlet coupled to the long-chain olefin product outlet.

[0021] In an embodiment thereof, the aromatic reactor comprises a bi-functional aromatic catalyst, said aromatic reactor having an aromatic product outlet, a second reduction gas inlet, and a second carbon source feed inlet, wherein a second reduction gas feed is coupled to the second reduction gas feed inlet, and a second carbon source feed is coupled to the second carbon source feed inlet.

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[0024] In another embodiment, the aromatic reactor comprises an ATA catalyst. The ATA reactor may have an ATA inlet and an aromatic product outlet. The alcohol product stream may be coupled to the ATA inlet.

[0025] BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Fig. 1 shows a process diagram for the production of aviation fuel via that can be directly substituted for Jet-A derived from crude oil, made from CO2 and reduction gas.

[0027] Fig. 2 shows a process diagram for the production of aviation fuel via conversion of carbon dioxide to aromatics and conversion of carbon dioxide to methanol and further to hydrocarbon mixtures.

[0028] Fig. 3 shows another process diagram for the production of aviation fuel via conversion of carbon dioxide to methanol and further to aromatics and hydrocarbon mixtures.

[0029] DETAILED DESCRIPTION OF THE INVENTION

[0030] 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.

[0031] A suitable composition of synthetic aviation fuel (SAF) may include about 8 wt% to about 25 wt% aromatics, about 15 wt% to about 40 wt% cycloparaffins, about 15 wt% to about 30 wt% linear paraffins (also referred to as normal paraffins, or “n-paraffins”) and about 20 wt% to about 40 wt% branched paraffins (also referred to as iso-paraffins). For certain uses, SAF may include about 15% aromatics, about 25% cycloparaffins, and about 60% paraffins, where about 40% to about 50% of these paraffins are n-paraffins and about 50% to about 60%

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[0034] are iso-paraffins. Inventors have developed a process to meet SAF requirements using alcohol-to-olefin (ATO) processing by incorporating the following steps:

[0035] i) Directing at least a portion of the medium olefin product stream and / or heavy olefin product from ATO (or methanol-to-olefm (MTO)) processing to an aromatic reactor for converting the olefins into an aromatic product mixture. Subsequently at least a portion the aromatic product mixture may be hydrogenated to form cycloparaffins.

[0036] ii) Directing at least a portion of the light olefin product stream to ethylene oligomerization using a homogeneous-catalyst driven process, i.e. SHOP process, to produce linear Cs-Ci6 paraffins.

[0037] iii) Directing at least a portion of the medium olefin product stream to an oligomerization reactor over a heterogeneous catalyst, e.g. zeolite, to generate iso-paraffins.

[0038] Blending the products of the three foregoing steps provides drop-in SAF complying with related requirements, including ASTM specifications.

[0039] 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.

[0040] In certain aspects, the present disclosure describes a fully formulated SAF, e.g., Jet A made synthetically from carbon dioxide. The fully formulated synthetic Jet A may be drop in, meaning that the chemical and physical characteristics of the synthetic Jet A are almost identical to those of conventional jet fuel and it can be safely mixed with the latter to varying degrees, use the same supply infrastructure and do not require the adaptation of aircraft or engines. As described herein, the production process assembles aromatic compounds from carbon dioxide. This bottom-up process design substantially reduces the synthetic accessibility of larger molecules. The synthetic Jet A disclosed in the present invention thus contains fewer polycyclic aromatics than Jet A made from petroleum-derived components. In certain

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[0043] embodiments, the SAF of the present disclosure comprises less than about 1 wt% polycyclic aromatics.

[0044] 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 SAF thermochemically from CO2 and H2.

[0045] 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.

[0046] 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.

[0047] The above-described process can produce aviation fuel which can be directly substituted for Jet-A derived from crude oil, since its ratio of iso- to normal paraffins, and aromatics to naphthenes can be controlled in the hydrogenation reactor, and the ratio of paraffin to aromatics can be adjusted by controlling the relative size of the reactors. 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.

[0048] A portion of the effluent from the aromatic reactor may be provided to a hydrogenation reactor loaded witha hydrogenation catalyst, such as Pd or Pt on a supporting material. In the hydrogenation reactor, the portion of the aromatic hydrocarbons from the aromatic reactor will be converted into a mixture of aromatic hydrocarbons and naphthenes (cyclic alkenes and alkanes). This allows the ratio of aromatics to naphthenes to be reduced as desired.

[0049] Separators may be used after the aromatic and / or hydrogenation reactors to separate unconverted hydrogen from the liquid product. The degree of hydrogenation and resultant ratios of aromatics and naphthenes may be adjusted by tuning the reactor conditions (e.g., temperature, pressure) as needed on-site to achieve the desired product distribution.

[0050] The effluents from the hydrogenation reactor (hydrogenated product mixture comprising aromatics and naphthenes, and optionally further including an isomerized product mixture comprising n- and i-paraffins from isomerization, and / or cycloparaffins) are provided - 7 -

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[0052] to and combined in a blender to provide a blended product comprising C9-15 hydrocarbons including linear paraffins, branched paraffins, cycloparaffins and aromatics. The blended product may comprise from about 10% to about 20% aromatics. The ratios of effluents and resultant blended product composition may be adjusted on-site to meet desired product specifications.

[0053] Following the blending step, the blended product may be further processed as necessary to obtain fuel meeting applicable standards, such as 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 napthenes can be controlled in the hydro-isomerization / hydrogenation reactors, respectively, and the ratio of paraffin to aromatics can be adjusted during blending. Those of skill in the art will appreciate that the flexibility of this system design allows these ratios to be adapted for other uses as desired. A particular advantage of the present system and method is that the aromatics and paraffins can be combined prior to purification, resulting in a significant savings in capital expenditure.

[0054] Methods for Aviation Fuel Production

[0055] 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.

[0056] Provided herein are methods for producing aviation fuel comprising:

[0057] contacting a reduction gas and a carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;

[0058] contacting the alcohol product stream with an ATO catalyst, optionally at an ATO temperature and an ATO pressure, to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;

[0059] contacting the medium olefin product mixture, the heavy olefin product mixture, or both of the medium and heavy olefin product mixtures with an oligomerization catalyst at an - 8 -

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[0061] oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;

[0062] contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;

[0063] contacting the medium olefin product mixture, the heavy olefin product mixture, or both of the medium and heavy olefin product mixtures, and optionally a portion of the light olefin product mixture, with an aromatic catalyst to afford an aromatic product mixture, e.g., comprising one or more aromatics and / or naphthenes;

[0064] blending the paraffin product mixture with at least a portion of the aromatic product mixture to afford a blended fuel product mixture.

[0065] The whole of the alcohol product stream may be directed to contact with the ATO catalyst or it may be divided and a portion thereof processed by another means to improve yield or otherwise utilize the alcohol product stream to make another product by another method. The alcohol product stream may comprise methanol and other alcohols. The alcohol product stream may comprise methanol, ethanol, other alcohols and oxygenates. The alcohol product stream may comprise over about 50 wt%, over about 55 wt%, over about 60 wt%, over about 65 wt%, over about 70 wt%, over about 75 wt%, or over about 80 wt% methanol. The alcohol product stream may comprise about 50 wt% to about 95 wt%, about 55 wt% to about 95 wt%, about 60 wt% to about 90 wt%, about 65 wt% to about 90 wt%, about 70 wt% to about 90 wt%, about 70 wt% to about 95 wt%, about 75 wt% to about 90 wt%, or about 80 wt% to about 90 wt% methanol.

[0066] The oligomerized product mixture may comprise linear and branched olefins. The oligomerized product mixture may comprise long-chain (i.e., Cs-ie) olefins. The oligomerized product mixture may comprise Cs-i6 linear olefins and Cs-i6 branched olefins. The oligomerized product mixture may comprise about 1 wt% to about 10 wt% linear olefins. The oligomerized product mixture may comprise about 80 wt% to about 99 wt%, about 85 wt% to about 98 wt%, or about 90 wt% to about 95 wt% branched olefins. The oligomerized product mixture may comprise paraffins in less than about 5 wt%, less than about 2 wt%, or less than about 1 wt% of the total oligomerized product mixture.

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[0069] The olefin product mixture may be processed in a distillation unit to remove water before further processing. Any known distillation unit, such as a column, may be used with this disclosure.

[0070] The light olefin product mixture may be present in over about 30 wt%, over about 40 wt% or over about 50 wt% of the total olefin product mixture. The medium olefin product mixture may be present in about 30 wt% to about 60 wt%, or about 35 wt% to about 55 wt% of the total olefin product mixture. The heavy olefin product mixture may be present in about 2 wt% to about 10 wt%, or about 3 wt% to about 5 wt% of the total olefin product mixture. The light olefin product mixture may comprise C2 olefins. The medium olefin product mixture may comprise C3 olefins. The heavy olefin product mixture may comprise C4 olefins. The heavy olefin product mixture may comprise C4+ olefins. The heavy olefin product mixture may comprise C4-8 olefins. In an embodiment, the light olefin product mixture comprises C2 olefins, the medium olefin product mixture comprises C3 olefins, and the heavy olefin product mixture comprises C4+ olefins.

[0071] The method may comprise dividing the aromatic product mixture into a first portion of the aromatic product mixture and a second portion of the aromatic product mixture. The method may comprise dividing the aromatic product mixture into a first portion of the aromatic product mixture, a second portion of the aromatic product mixture, and a third portion of the aromatic product mixture. The different portions, or streams, of the aromatic product mixture may be subsequently processed differently (e.g. by alkylation, or hydrogenation), or not at all, before blending to make a fuel product. The aromatic product mixture may be divided equally into the first portion and the second portion or between the first, second and third portions, or in some other distribution as readily understood by one of skill in the art to adjust the streams for blending to meet the desired fuel product characteristics.

[0072] The aromatic product mixture may comprise Ce-s and Cs+ aromatics. The aromatic product mixture may comprise benzene, toluene, and xylene (BTX). The aromatic product mixture may comprise over about 50 wt%, over about 55 wt%, over about 60 wt%, over about 65 wt%, over about 70 wt%, over about 75 wt%, or over about 80 wt% BTX. The aromatic product mixture may comprise about 40 wt% to about 90 wt%, about 50 wt% to about 90 wt%, about 55 wt% to about 90 wt%, about 60 wt% to about 80 wt%, about 70 wt% to about 90 wt%, about 60 wt% to about 75 wt%, ot about 55 wt% to about 75 wt% BTX. The aromatic product - 10 -

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[0074] mixture may comprise BTX, other alkylated aromatics, cycloaromatics and naphthalenes. An embodiment of the method may further comprise separating a first recycle stream from the aromatic product mixture. The first aromatic recycle stream may be directed into the aromatic reactor for contact with the aromatic catalyst to control the reaction heat.

[0075] The method may comprise contacting the first portion of the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics and / or contacting a second portion of the aromatic product mixture with the hydrogenation catalyst to afford a cycloparaffin product mixture. The method may comprise contacting the first portion of the aromatic product mixture with an alkylation catalyst to afford the target alkyl arene product mixture, and contacting a second portion of the aromatic product mixture with the hydrogenation catalyst to afford the cycloparaffin product mixture, and providing a third portion of the aromatic product mixture for direct blending. The first portion may comprise over about 50 wt%, over about 60 wt%, or over about 70 wt % of the aromatic product mixture. The first portion comprising Ce-s aromatics may be directed to an alkylation reactor for contact with an alkylation catalyst. The second portion comprising Cs+ aromatics may be directed to a hydrogenation reactor for contact with a hydrogenation catalyst.

[0076] Hydrogenation can be performed on each of the components directed to the hydrogenation reactor separately or as a combined mixture. Hydrogenation may be performed in a hydrogenation reactor, which may be a fixed bed reactor with multiple reaction zones or a single reaction zone, depending on the feed composition. If the feed is a blend of olefin and aromatics, then a multi-zone reactor may be used having a heterogeneous olefin hydrogenation catalyst loaded into a top zone of the reactor maintained at a lower temperature for converting olefin to paraffins, and a selective heterogeneous catalyst for aromatic hydrogenation loaded into a bottom zone of the reactor maintained at a different, optionally higher, temperature. As readily understood by one of skill in the art, the flow rate, temperature and pressure may be designed to meet the requirements for the formulation of drop-in SAF and desired conversion of the feed stream. Another option is to perform the olefin hydrogenation in one reactor to hydrogenate the olefins to paraffins and hydrogenation of a portion of the aromatics product in another reactor to hydrogenate the aromatics to cycloparaffins.

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[0079] An embodiment of the method may further comprise separating a second recycle stream from the paraffin product mixture. The second recycle stream may be directed back into the hydrogenation process to control the reaction heat.

[0080] The target alkyl arene product mixture may comprise C9-15 hydrocarbons, and optionally have a boiling point between about 150 °C to about 300 °C. The target alkyl arene product mixture may be divided into a first portion and a second portion for different subsequent processing (e.g. by hydrogenation), or not at all, before blending to make a fuel product. The target alkyl arene product mixture may be divided equally into the first portion and the second portion or in some other distribution as readily understood by one of skill in the art to adjust the streams for blending to meet the desired fuel product characteristics.

[0081] The method may include blending at least a portion of the target alkyl arene product mixture with the paraffin product mixture and the aromatic product mixture to afford the blended fuel product mixture. Prior to blending, the method may include dividing the target alkyl arene product mixture into a first portion of the target alkyl arene product mixture comprising C7-8 and a second portion of the target alkyl arene product mixture comprising Cs+ hydrocarbons. The first portion may be directed to hydrogenation and processed under mild conditions. The mild processing conditions are set such that the olefins present in the stream are converted to paraffins. The second portion may be directed to hydrogenation and processed under severe (which may also be referred to as high) conditions. The severe processing conditions are set such that the aromatics in the stream are converted to cycloparaffins.

[0082] Mild processing conditions for hydrogenation may include a mild hydrogenation temperature of about 100 °C to about 350 °C and / or a mild hydrogenation pressure of about 150 psig to about 450 psig. Severe processing conditions for hydrogenation may include a high hydrogenation temperature of about 200 °C to about 400 °C and / or a high hydrogenation pressure of about 250 psig to about 500 psig.

[0083] The light olefin product mixture may be divided into a first portion and a second portion for different subsequent processing (e.g., by aromatization, alkylation or by SHOP), or not at all, before blending to make a fuel product. The light olefin product mixture may be divided equally into the first portion and the second portion or in some other distribution as readily

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[0086] understood by one of skill in the art to adjust the streams for blending to meet the desired fuel product characteristics.

[0087] The method disclosed herein may comprise processing at least a first portion of the light olefin product mixture via ethylene oligomerization and olefin metathesis to afford long-chain olefins. The method may comprise contacting a second portion of the light olefin product mixture with the aromatization catalyst in the aromatics reactor to afford the aromatic product mixture. The method may comprise contacting a second portion of the light olefin product mixture and at least a portion of the aromatic product mixture with the alkylation catalyst in the alkylation reactor to afford the target alkyl arene product mixture.

[0088] The method may further comprise contacting the long-chain (Cs-ie) olefins with the hydrogenation catalyst in a hydrogenation reactor to afford the linear paraffins in the paraffin product mixture.

[0089] The paraffin product mixture may comprise linear paraffins, branched paraffins, and cycloparaffins. The paraffin product mixture may comprise about 40 wt% to about 65 wt% linear paraffin, about 20 wt% to about 45 wt% branched paraffin, and about 5 wt% to about 40 wt% cycloparaffins. The paraffin product mixture may comprise about 40 wt% to about 65 wt% linear paraffin, about 20 wt% to about 45 wt% branched paraffin, and about 10 wt% to about 40 wt% cycloparaffins. The paraffin product mixture may comprise about 45 wt% to about 55 wt% linear paraffin, about 35 wt% to about 45 wt% branched paraffin, and about 10 wt% to about 25 wt% cycloparaffins. The paraffin product mixture may comprise C9-15 paraffins.

[0090] The alcohol product stream and / or aromatic product mixture may comprise unreacted carbon source and / or reduction gas. In certain embodiments, the method comprises separating the unreacted CO2 and / or reduction gas from the alcohol product stream and / or aromatic product mixture. In other embodiments, the separating comprises a high pressure separation, a low pressure separation, or a combination thereof. In certain embodiments, said separating comprises a high pressure separation and a low pressure separation. High pressure separation and low pressure separation may be accomplished by any means and with any elements known for use in the art.

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[0093] In certain embodiments, the methods further comprise combining the unreacted CO2 and / or reduction gas with one or more of the first reduction gas, the first carbon source gas, the second reduction gas, and the second carbon source gas.

[0094] In certain embodiments, methods of the disclosure further comprise contacting the oligomerized product mixture and a second reduction gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to afford an isomerized product mixture comprising linear paraffins, branched paraffins, and / or naphthenes; wherein the isomerized product mixture is blended with the aromatic product mixture, or, when present, the hydrogenated mixture to afford the blended product mixture.

[0095] In certain embodiments, methods of the disclosure further comprise contacting the aromatic product mixture and a third reduction gas with a hydrogenation catalyst at a hydrogenation temperature and a hydrogenation pressure to afford a hydrogenated product mixture comprising cycloparaffins and naphthenes, wherein the hydrogenated product mixture is blended with the oligomerized product mixture, or, when present, the isomerized product mixture to afford the blended product mixture.

[0096] In an embodiment, the method includes processing at least a portion of the light olefin product mixture via ethylene oligomerization followed by olefin metathesis. Ethylene oligomerization is known to play a crucial role in producing linear a-olefins with diverse applications in industry. More than 3 million tons of linear a-olefins (LAO) are produced each year and used as intermediates for the production of detergents and lubricants and as comonomers in polyethylene. Several different LAO processes exist, for example: i) the shell higher olefin process (SHOP), which generates a range of a-olefins from C4 (1 -butene) to C20+, ii) Ethylene Dimerization: The IFP / Sabic Alphabutol process selectively produces 1 -butene; iii) Ethylene Trimerization: Chevron-Phillips operates a chromium-based process to produce 1-hexene; and iv) Ethylene Tetramerization: e.g., a chromium-based process for 1-octene production. Late transition metal catalysts (e.g., zirconium, titanium, chromium) facilitate ethylene oligomerization operating via a linear chain growth alkene insertion mechanism (i.e., Cossee-Arlman mechanism). Metal hydride species coordinate with ethylene, leading to longer metal alkyl species.

[0097] In certain embodiments, the method includes ethylene oligomerization using homogeneous metal catalyst for converting light olefin products, e.g., ethylene, produced from - 14 -

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[0099] ATO (or, more specifically in certain embodiments, MTO, or FT) to LAO that subsequently are contacted with a hydrogenation catalyst in a hydrogenation reactor to produce linear paraffins. The linear paraffins may comprise C9-16. In other embodiments, the method of ethylene oligomerization is the Shell higher olefin process (SHOP). The linear paraffins produced in this step may be blended with iso-paraffins and cycloparaffins, and further blended with aromatics to yield the fuel product mixture, e.g., drop-in SAF.

[0100] The Shell higher olefin process (SHOP) is a chemical process for the production of linear alpha olefins (also referred to herein as long-chain olefins) via ethylene oligomerization and olefin metathesis invented and exploited by Royal Dutch Shell. The SHOP includes 3 steps: 1) Oligomerization of ethylene; 2) Isomerization of C4-C10 and >620; and 3) Metathesis. The process is readily understood by those of skill in the art. In the first step, ethylene reacts by the catalyst to give longer chains. Unlike the Ziegler-Natta process, which aims to produce very long polymers, the oligomer stops growing after addition of 1-10 repeating units of ethylene. In certain embodiments, the light olefin product stream is directed to the SHOP, wherein the olefins are processed using a homogeneous-catalyst driven process, i.e. SHOP process, to produce long-chain linear Cs-Ci6 olefins. See, e.g., Wilhelm Keim, “Oligomerization of Ethylene to a-Olefins: Discovery and Development of the Shell Higher Olefin Process (SHOP),” Angew. Chem. Int. Ed. 2013, 52, 2-7, available at: https: / / engineeringness.com / an-in-depth-guide-to-the-shop-process / .

[0101] The first step in this process may be ethylene oligomerization of a mixture of even-numbered a-olefins at about 80 °C to about 120 °C and about 70 bar to about 140 bar (7 to 14 MPa) catalyzed by a nickel-phosphine complex. Such catalysts may be prepared from diarylphosphino carboxylic acids, such as (CeHs^PCThCChH. The generally accepted mechanism follows a step growth process starting from a nickel-hydride complex that results from activation of the precatalytic species.

[0102] The active nickel hydride species may be generated in different ways. For example, it may be formed in situ according to a two-step sequence: (i) oxidative addition of a keto-stabilized phosphorus ylide or a phosphanyl-hydroxy ligand on a nickel(0) complex such as [Ni(cod)2]; followed by (ii) reaction with ethylene. An alternative method may be reacting ethylene with a procatalytic complex of the type [Ni(P,O)R(L)] (R = aryl, L = two electron donor), that is a complex in which the anionic, chelating PIII,0 unit is already present. For a number of such - 15 -

[0103] FH13166046.1Attorney Docket No.: CSW-02925

[0104] complexes, the R / L couple is eliminated after reaction with ethylene, resulting then (after ethylene insertion and subsequent P-elimination) in an active hydride, [Ni(P,O)H(ethylene). This is, for example, the case for R / L = Ph / olefin or R / L = r|3 -allyl or r|5-Cp.28 According to the nature of the R / L couple, the activation temperature and induction time may change. Thus, while the allyl moiety of [Ni(Ph2PCH[double bond, length as m-dash]C(O)Ph)(allyl)] is displaced at about 50 °C within about 5 min, activation of [Ni(Ph2PCH[double bond, length as m-dash]C(O)Ph)(Cp)] requires about 20 min at about 120 °C.

[0105] In other methods for producing aviation fuel from a carbon source gas, the aromatics needed to make jet fuel may be produced by processing steps and / or reactors other than from the heavy olefin product mixture, as disclosed above.

[0106] In an embodiment, the method comprises: dividing the alcohol product stream into a first portion and a second portion; contacting a first portion of the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford the olefin product mixture; and contacting a second portion of the alcohol product stream with an ATA catalyst at an ATA temperature and an ATA pressure to afford an aromatic product mixture. This method may comprise:

[0107] contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;

[0108] contacting a first portion of the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;

[0109] contacting the medium olefin product mixture and the heavy olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;

[0110] contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;

[0111] contacting a second portion of the alcohol product stream with an ATA catalyst at an ATA temperature and an ATA pressure to afford an aromatic product mixture; and

[0112] - 16 -

[0113] FH13166046.1Attorney Docket No.: CSW-02925

[0114] blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

[0115] Any known ATA (alcohol-to-aromatics) or, in certain embodiments, MTA (alcohol-to-aromatics), process for converting an alcohol to aromatics, or methanol to aromatics, respectively, may be used in accordance with this disclosure, in particular with respect to the selection of ATA temperature, ATA pressure and ATA catalyst for improved selectivity of alcohols, for example, in accordance with the disclosures of Ono, Y., et al., “Selective Conversion of Methanol into Aromatic Hydrocarbons over Zinc-exchanged ZSM-5 Zeolites,” J. Chem. Soc., Faraday Trans. 7, 1988, 84(4), 1091-1099, or Yarulina, I., etal., “Recent trends and fundamental insights in the methanol -to-hydrocarbons process,” Nat. Catalysis, 2018, 1, 398-411.

[0116] In another embodiment, the method comprises: contacting a second reduction gas and a second carbon source gas with a bi-functional aromatic catalyst to afford an aromatic product mixture. This method for producing aviation fuel may include:

[0117] contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;

[0118] contacting the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;

[0119] contacting the medium olefin product mixture and the heavy olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;

[0120] contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;

[0121] contacting a second reduction gas and a second carbon source gas with a bi-functional aromatic catalyst to afford an aromatic product mixture; and

[0122] blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

[0123] In each of the foregoing embodiments, the method may comprise contacting the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture. In some embodiments, the method may comprise dividing the aromatic product - 17 -

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[0125] mixture into a first portion of the aromatic product mixture and a second portion of the aromatic product mixture. The method may comprise dividing the aromatic product mixture into a first portion of the aromatic product mixture, a second portion of the aromatic product mixture, and a third portion of the aromatic product mixture. The different portions, or streams, of the aromatic product mixture may be subsequently processed differently (e.g. by alkylation, or hydrogenation), or not at all, before blending to make a fuel product. The aromatic product mixture may be divided equally into the first portion and the second portion or between the first, second and third portions, or in some other distribution as readily understood by one of skill in the art to adjust the streams for blending to meet the desired fuel product characteristics. The aromatic product mixture may comprise Ce-s and Cs+ aromatics.

[0126] The method may comprise contacting the first portion of the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more alkylated aromatics and / or contacting a second portion of the aromatic product mixture with the hydrogenation catalyst to afford cycloparaffins in the paraffin product mixture. The method may comprise contacting the first portion of the aromatic product mixture with an alkylation catalyst to afford the target alkyl arene product mixture, and contacting a second portion of the aromatic product mixture with the hydrogenation catalyst to afford cycloparaffins, and providing a third portion of the aromatic product mixture for blending. The first portion may comprise over about 50 wt%, over about 60 wt%, or over about 70 wt % of the aromatic product mixture. The first portion comprising Ce-s aromatics may be further processed via alkylation. The second portion comprising Cs+ aromatics may be further processed via hydrogenation.

[0127] The target alkyl arene product mixture may be divided into a first portion and a second portion for different subsequent processing (e.g. by hydrogenation), or not at all, before blending to make a fuel product. The target alkyl arene product mixture may be divided equally into the first portion and the second portion or in some other distribution as readily understood by one of skill in the art to adjust the streams for blending to meet the desired fuel product characteristics.

[0128] The method may include blending at least a portion of the target alkyl arene product mixture with the paraffin product mixture, and optionally with the aromatic product mixture to afford the blended fuel product mixture. Prior to blending, the method may include dividing - 18 -

[0129] FH13166046.1Attorney Docket No.: CSW-02925

[0130] the target alkyl arene product mixture into a first portion of the target alkyl arene product mixture comprising C7-8 and a second portion of the target alkyl arene product mixture comprising Cs+. The first portion may be contacted with a hydrogenation catalyst and processed under mild conditions. The mild processing conditions are set such that the olefins present in the stream are converted to paraffins. The second portion may be directed to hydrogenation and processed under severe (which may also be referred to as high) conditions. The severe processing conditions are set such that the aromatics in the stream are converted to cycloparaffins.

[0131] Each of the terms used in these embodiments has the same meaning as defined as above.

[0132] Systems for Aviation Fuel Production

[0133] In certain aspects, provided herein are systems for the conversion of carbon source gases and reduction gases to aviation fuel. In the present disclosure, 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. The coupling of one component to another can also accommodate discontinuous processes, such as batch processes where a reaction in one component is permitted to progress, e.g, to completion, followed by transfer of the product mixture to the next coupled component.

[0134] Additionally, as will be appreciated, various system components are described as “having” certain features. For example, in certain embodiments the aromatic reactor

[0027] is described as having a second reduction gas inlet

[0030] , a carbon source feed inlet

[0031] , and an aromatic product outlet

[0028] , 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 - 19 -

[0135] FH13166046.1Attorney Docket No.: CSW-02925

[0136] 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.

[0137] Further, the various systems and methods of the present disclosure 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] ), which correspond to components shown in Fig. 1.

[0138] Systems for the production of aviation fuel are disclosed herein. The systems may include: a first reduction gas feed; a first carbon source gas feed; a reduction reactor comprising a reduction catalyst to afford an alcohol product stream; an alcohol to olefins (ATO) reactor comprising an ATO catalyst; an oligomerization reactor comprising an oligomerization catalyst; a hydrogenation reactor comprising a hydrogenation catalyst; and an aromatic reactor comprising an aromatic catalyst. The system may also comprise an alkylation reactor comprising an alkylation catalyst. The system may also comprise a blender to afford the fuel product mixture.

[0139] A system for the production of aviation fuel disclosed herein comprises:

[0140] a first reduction gas feed;

[0141] a first carbon source gas feed;

[0142] a reduction reactor comprising a reduction catalyst to afford an alcohol product stream;

[0143] an alcohol to olefins (ATO) reactor comprising an ATO catalyst;

[0144] an oligomerization reactor comprising an oligomerization catalyst;

[0145] a hydrogenation reactor comprising a hydrogenation catalyst;

[0146] optionally a second reduction gas feed;

[0147] optionally a second carbon source feed;

[0148] an aromatic reactor having an aromatic product outlet;

[0149] optionally an alkylation reactor comprising an alkylation catalyst; and

[0150] - 20 -

[0151] FH13166046.1Attorney Docket No.: CSW-02925

[0152] a blender having a paraffin product inlet, an aromatic product inlet, and optionally a target alkyl arene product inlet and a fuel product outlet.

[0153] The ATO reactor may have an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet. The alcohol product stream may be coupled to the alcohol inlet.

[0154] The oligomerization reactor may have a medium olefin product inlet and an oligomerized product outlet. The medium olefin product outlet on the ATO reactor may be coupled to the medium olefin product inlet of the oligomerization reactor.

[0155] The hydrogenation reactor may have an oligomerization product inlet and a paraffin product outlet. The oligomerization product outlet on the oligomerization reactor may be coupled to the oligomerization product inlet of the hydrogenation reactor. In certain embodiments, the hydrogenation reactor is coupled to the aromatic reactor and, when present, the alkylation reactor. In certain embodiments, the hydrogenation reactor is coupled to the alkylation reactor. In certain embodiments, there is more than one hydrogenation reactor with the oligomerization reactor being coupled to a first hydrogenation reactor, the aromatic reactor and optionally the alkylation reactor being coupled to a second hydrogenation reactor. In certain embodiments, the oligomerization reactor is coupled to a first hydrogenation reactor, the aromatic reactor is coupled to a second hydrogenation reactor, and the alkylation reactor being is to a third hydrogenation reactor.

[0156] When the aromatic reactor is loaded with an ATA catalyst, the aromatic reactor comprises an ATA inlet coupled to the alcohol product stream. When the aromatic reactor is loaded with an aromatic catalyst, the aromatic reactor comprises a heavy olefin product inlet coupled to the heavy olefin product outlet on the ATO reactor. When the aromatic reactor is loaded with a bi-functional catalyst, the aromatic reactor comprises a second reduction gas inlet, and a second carbon source feed inlet.

[0157] When present, the alkylation reactor may have an aromatic product inlet and a target alkyl arene outlet, and the aromatic product inlet may be coupled to the aromatic product outlet of the aromatic reactor.

[0158] On the blender, the paraffin product outlet of the hydrogenation reactor may be coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor may be coupled to the aromatic product inlet of the blender; and when present, the target alkyl - 21 -

[0159] FH13166046.1Attorney Docket No.: CSW-02925

[0160] arene product outlet of the alkylation reactor may be coupled to the target alkyl arene product inlet of the blender.

[0161] In certain aspects, provided herein are systems for the production of aviation fuel comprising:

[0162] a first reduction gas feed;

[0163] a first carbon source gas feed;

[0164] a reduction reactor comprising a reduction catalyst to afford an alcohol product stream;

[0165] an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;

[0166] an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;

[0167] a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;

[0168] an optional second reduction gas feed;

[0169] an optional second carbon source feed;

[0170] an aromatic reactor comprising an aromatic catalyst, said aromatic reactor having a heavy olefin product inlet and an aromatic product outlet, and optionally also having a second reduction gas inlet, and a second carbon source feed inlet,

[0171] wherein the heavy olefin product inlet is coupled to the heavy olefin product outlet of the ATO reactor; and

[0172] wherein optionally the aromatic reactor may include a light olefin product inlet coupled to the heavy light product outlet of the ATO reactor;

[0173] an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet,

[0174] - 22 -

[0175] FH13166046.1Attorney Docket No.: CSW-02925

[0176] wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; and

[0177] a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

[0178] The oligomerization reactor may have a heavy olefin product inlet, wherein the heavy olefin product outlet on the ATO reactor is coupled to the heavy olefin product inlet of the oligomerization reactor. The aromatic reactor may have a medium olefin product inlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the aromatic reactor.

[0179] In certain embodiments, the hydrogenation reactor further comprises an aromatic product inlet coupled to the aromatic reactor. In other systems, the hydrogenation reactor further comprises a target alkyl arene product inlet coupled to the alkylation reactor.

[0180] The hydrogenation reactor may be a fixed bed reactor with multi heating zones or a single heating zone, depending on the feed composition. The hydrogenation reactor may comprise a plurality of fixed-bed reactors. When the system includes a plurality of fixed-bed reactors for hydrogenation, one hydrogenation reactor may be coupled to the aromatic reactor, a second hydrogenation reactor may be coupled to the SHOP process, and optionally a third hydrogenation reactor may be coupled to the alkylation reactor.

[0181] In certain embodiments, the alkylation reactor comprises two target alkyl arene product outlets, one such outlet being coupled to a target alkyl arene product inlet on the hydrogenation reactor and the other outlet being coupled to the target alkyl arene product inlet on the blender.

[0182] In certain embodiments, the aromatic reactor comprises three aromatic product outlets, with one of each outlet being coupled to the aromatic product inlet of the blender, the aromatic product inlet of the hydrogenation reactor and the aromatic product inlet of the alkylation reactor. In an embodiment, a C7-8 aromatic product outlet may be coupled to an aromatic product inlet of a first hydrogenation reactor operating at mild conditions; and a Cs+ aromatic

[0183] - 23 -

[0184] FH13166046.1Attorney Docket No.: CSW-02925

[0185] product outlet may be coupled to an aromatic product inlet of a second hydrogenation reactor operating at severe conditions.

[0186] In certain embodiments, the system includes ethylene oligomerization followed by olefin metathesis, wherein these processes combined may be known as a SHOP system, wherein the SHOP system may have a light olefin product inlet and a long-chain olefin product outlet; and the hydrogenation reactor comprises a long-chain olefin product inlet coupled to the long-chain olefin product outlet of the SHOP system.

[0187] In certain embodiments, systems of the present disclosure further comprise:

[0188] a third reduction gas feed; and

[0189] the hydrogenation reactor having a third reduction gas feed inlet, wherein the third reduction gas feed is coupled to the third reduction gas feed inlet; and the mixed paraffin product outlet is coupled to the blender.

[0190] In certain embodiments, systems of the present disclosure further comprise a separator having an aromatic product inlet, optionally a recycle gas outlet, and a separated product outlet, wherein the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet [not shown] of the separator and the separated product outlet is coupled to the aromatic product inlet of the hydrogenation reactor.

[0191] In certain embodiments, systems of the present disclosure further comprise a recycle stream outlet on the hydrogenation reactor coupled to a recycle gas inlet on the same or another hydrogenation reactor.

[0192] In an embodiment, the carbon source feed is coupled to a CO2 outlet of an industrial alcohol production facility, such as a fuel ethanol plant or a biorefinery.

[0193] Other systems may include: an alcohol-to-aromatics reactor or an aromatic reactor configured to convert a carbon source gas and a reduction gas to aromatics.

[0194] An embodiment is a system for the production of aviation fuel comprising:

[0195] a first reduction gas feed;

[0196] a first carbon source gas feed;

[0197] a reduction reactor comprising a reduction catalyst to afford an alcohol product stream;

[0198] an alcohol to olefins (ATO) reactor comprising an ATO catalyst;

[0199] - 24 -

[0200] FH13166046.1Attorney Docket No.: CSW-02925

[0201] an oligomerization reactor comprising an oligomerization catalyst, wherein the oligomerization reactor has a medium olefin product inlet and an oligomerized product outlet;

[0202] a hydrogenation reactor comprising a hydrogenation catalyst;

[0203] a second reduction gas feed;

[0204] a second carbon source feed;

[0205] an aromatic reactor comprising a bi-functional aromatic catalyst, said aromatic reactor having an aromatic product outlet, a second reduction gas inlet, and a second carbon source feed inlet, wherein the second reduction gas feed is coupled to the second reduction gas feed inlet, and the second carbon source feed is coupled to the second carbon source feed inlet; and

[0206] an alkylation reactor comprising an alkylation catalyst; and

[0207] a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

[0208] Another system for the production of aviation fuel described herein comprises:

[0209] a first reduction gas feed;

[0210] a first carbon source gas feed;

[0211] a reduction reactor comprising a reduction catalyst to afford an alcohol product stream;

[0212] an alcohol to olefins (ATO) reactor comprising an ATO catalyst;

[0213] an oligomerization reactor comprising an oligomerization catalyst, wherein the oligomerization reactor has a medium olefin product inlet and an oligomerized product outlet;

[0214] a hydrogenation reactor comprising a hydrogenation catalyst;

[0215] an aromatic reactor comprising an ATA catalyst, said ATA reactor having an ATA inlet and an aromatic product outlet, wherein the alcohol product stream is coupled to the ATA inlet;

[0216] an alkylation reactor comprising an alkylation catalyst; and

[0217] - 25 -

[0218] FH13166046.1Attorney Docket No.: CSW-02925

[0219] a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

[0220] The ATO reactor may have an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet. The alcohol product stream may be coupled to the alcohol inlet. The medium olefin product outlet on the ATO reactor may be coupled to the medium olefin product inlet of the oligomerization reactor. The ATO catalyst may be selected for high selectivity of methanol to olefins.

[0221] The system of the disclosure may include a distillation column configured to receive the olefin product mixture from the ATO reactor and to remove water from the effluent.

[0222] Another system for the production of aviation fuel disclosed herein comprises:

[0223] a first reduction gas feed;

[0224] a first carbon source gas feed;

[0225] a reduction reactor comprising a reduction catalyst to afford an alcohol product stream;

[0226] an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;

[0227] an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;

[0228] a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;

[0229] - 26 -

[0230] FH13166046.1Attorney Docket No.: CSW-02925

[0231] an aromatic reactor comprising an ATA catalyst, said ATA reactor having an ATA inlet and an aromatic product outlet, wherein the alcohol product stream is coupled to the ATA inlet;

[0232] an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet,

[0233] wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; and

[0234] a blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

[0235] When the aromatic reactor comprises an ATA catalyst and is configured to convert alcohols, such as methanol, to aromatics, it may also be referred to as an ATA (alcohol-to- aromatic) reactor or an MTA (methanol-to-aromatic) reactor. The ATA catalyst may be selected for high selectivity of methanol to aromatics.

[0236] The hydrogenation reactor may have an oligomerization product inlet and a paraffin product outlet, and / or the oligomerization product outlet on the oligomerization reactor may coupled to the oligomerization product inlet of the hydrogenation reactor.

[0237] The alkylation reactor may have an aromatic product inlet and a target alkyl arene outlet, and the aromatic product inlet may be coupled to the aromatic product outlet of the aromatic reactor.

[0238] Each of the terms used in these embodiments has the same meaning as defined as above. Examples of certain systems of the invention are depicted in FIGS. 1-3 of the application, each of which depicts a different means of aromatics conversion and providing aromatics to the process. In FIG. 1, a carbon source gas, here CO2, and reduction gas, here EE, are provided to a reduction reactor 11 for conversion of CO2 to methanol. The methanol is processed in an MTO reactor 13 to afford an olefin product mixture. It is understood that the olefin product mixture may optionally be processed through a distillation unit (not shown) to remove water. The olefins are divided. A portion of the C2 olefins are processed by via ethylene oligomerization and olefin - 27 -

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[0240] metathesis in the SHOP system 15 for conversion to long-chain olefins (Cs-Cie), while another portion of the C2 olefins are directed to aromatization in the aromatic reactor 19 and alkylation 20, along with the heavy olefins (C4 and heavier) to make the target alkyl arenes, as required in drop-in SAF. It is readily understood that in certain embodiments all or a portion of the medium olefins will also be directed to the aromatic reactor. It is also readily understood that the target alkyl arene may be divided and a first portion fed to the hydrogenation reactor 17 (not shown), if desired, while the second portion is fed to the blender 18 to be mixed with the paraffin product mixture from hydrogenation to make SAF. The medium olefins (e.g., here, C3) are directed to the oligomerization reactor 16 for conversion to long-chain olefins (Cs-Cie). It is readily understood that in certain embodiments all or a portion of the heavy olefins will also be directed to the oligomerization reactor. The long-chain olefins are also processed in the hydrogenation reactor 17 which provides a paraffin product mixture comprising linear paraffins, branched paraffins, and cycloparaffins. The paraffin product mixture is blended with aromatics and target alkyl arenes in the blender 18 to make 100% drop-in SAF.

[0241] In FIG. 2, a schematic is depicted in which a second carbon source gas feed and reduction gas are provided in the system and fed into an aromatic reactor 22 to convert CO2 and H2 into aromatics. The aromatics may be provided directly to an alkylation reactor 24, as shown. In other embodiments, a portion of the aromatics may be provided directly to the blender 28 or directly to the hydrogenation reactor 27 (not shown). Like FIG. 1, a carbon source gas, here CO2, and reduction gas, here H2, are provided to a reduction reactor 21 for conversion of CO2 to methanol. The methanol is processed in an MTO reactor 23 to afford an olefin product mixture, which is processed through a distillation unit 29 to remove water, and then the olefins are divided. In FIG. 2, the C2 olefins are processed by via ethylene oligomerization and olefin metathesis in the SHOP system 25 for conversion to long-chain olefins (Cs-Cie). The aromatics and a portion of the light olefins (C2 olefins) from the MTO effluent are combined in the alkylation reactor 24 to afford a target alkyl arene. The target alkyl arene is divided and a first portion is fed to the hydrogenation reactor 27, while the second portion is fed to the blender 28 to be mixed with the paraffin product mixture from hydrogenation to make SAF. The medium olefins (e.g., here, C3, C4 and heavier) are directed to the oligomerization reactor 26 for conversion to long-chain olefins (Cs-Cie). The long-chain olefins from SHOP and from oligomerization are also processed in the hydrogenation reactor 27 which provides a paraffin - 28 -

[0242] FH13166046.1Attorney Docket No.: CSW-02925

[0243] product mixture comprising linear paraffins, branched paraffins, and cycloparaffins. The paraffin product mixture is blended with aromatics in the blender 28 to make 100% drop-in SAF.

[0244] In FIG. 3, a schematic is depicted which incorporates MTA into the system. Like FIG.

[0245] 1, a carbon source gas, here CO2, and reduction gas, here H2, are provided to a reduction reactor 31 for conversion of CO2 to methanol. The methanol is divided and a first portion of the methanol is processed in an MTO reactor 33 to afford an olefin product mixture, which is processed through a distillation unit 39 to remove water, and then the olefins are divided. A second portion of the methanol is processed in an MTA reactor 32 to afford aromatics. In this figure, the C2 olefins are processed by via ethylene oligomerization and olefin metathesis in the SHOP system 35 for conversion to long-chain olefins (Cs-Cie). The medium olefins (e.g., here, C3, C4 and heavier) are directed to the oligomerization reactor 36 for conversion to long-chain olefins (Cs-Cie). The long-chain olefins from SHOP and from oligomerization are processed in the hydrogenation reactor 37 which provides a paraffin product mixture comprising linear paraffins, branched paraffins, and cycloparaffins. The aromatics from MTA are combined with a portion of the light olefins (C2 olefins) in the alkylation reactor 34 to afford a target alkyl arene. In other embodiments, a portion of the aromatics may be provided directly to the blender 38 or directed to the hydrogenation reactor 37 (not shown). The target alkyl arene is divided and a first portion is fed to the hydrogenation reactor 37, while the second portion is fed to the blender 38 to be mixed with the paraffin product mixture to make 100% drop-in SAF.

[0246] Conversion o f CO 2 to Alcohols

[0247] The conversion of carbon dioxide into alcohols may be performed by any means known in the art, for example, any method or system disclosed in US Patent No. 11919841, the entirety of which is incorporated herein by reference.

[0248] In certain embodiments, the reaction of carbon dioxide with hydrogen to produce alcohols occurs in a one-step process, i.e., one reactor is used to conduct the multiple chemical reactions required to produce alcohols from carbon dioxide. According to such embodiments, the systems of the present disclosure comprise: (1) optionally, an air capture system for collection of carbon dioxide from air, (2) a system that produces hydrogen from water using an electrolyzer, (3) a hydrogenation system that (a) combines the hydrogen produced from the - 29 -

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[0250] electrolyzer with carbon dioxide from the air capture system to produce carbon monoxide and (b) combines hydrogen produced from the electrolyzer with the carbon monoxide to produce a mixture of alcohols.

[0251] In certain embodiments, the system that produces hydrogen using electrolysis for later use (such as in the systems and methods disclosed herein) is a polymer electrolyte membrane (PEM) electrolyzer, an alkaline electrolyzer, or a high-temperature solid oxide electrolyzer. Electricity used to drive this process may be obtained from any suitable source, preferably from a renewable resources that do not generate additional carbon dioxide, allowing for a truly carbon-negative solution to our increasing carbon dioxide emissions.

[0252] Any suitable system for providing carbon dioxide may be used. In some embodiments, carbon dioxide is supplied from an air capture system that uses a sorbent to output carbon dioxide at concentrations above 25%, 50%, 75%, 95%, or 99% in air. In other embodiments, carbon dioxide is purchased in its pure form and is source-agnostic. In the case of carbon dioxide that is sourced at concentrations lower than 99%-100%, the hydrogenation system may be modified with catalysts that are capable of selectively hydrogenating carbon dioxide in air, selectively hydrogenating carbon dioxide in air, or selectively hydrogenating carbon dioxide or carbon monoxide in any number of air-derived product streams that contain carbon dioxide, carbon monoxide, or a combination thereof, at any concentration.

[0253] In certain embodiments of the present disclosure, carbon dioxide is hydrogenated with hydrogen gas into alcohols.

[0254] In certain embodiments, the reduction reactor operates with selectivity for the alcohol of greater than 10%. In certain embodiments, the selectivity for the alcohol is greater than 30%. The selectivity may be provided by suitable selection of catalyst.

[0255] The reduction reactor comprises a reduction catalyst. The reduction catalyst may be any known catalyst in the art used to produce small molecule alcohols. The reduction catalyst may comprise platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or alloys or combinations thereof. In certain embodiments, the reduction catalyst comprises nanoparticles comprising CuZn, CuZnFeK, CuZnFeKC, CuZnFeAlK, CuZnFeNa, CuZnFeCoK, CuZnFeCoNaK, CuCoAl, CoMoSK, CuZnK, CuCoMn, CuZnAl, CuAl, ZnAl, ZnZr, CuZr, RhRu, PdCuFe, Rh, or RhFeSi, optionally on an alumina support. In certain embodiments, the reduction catalyst comprises nanoparticles comprising CoMoSK,

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[0258] optionally on an alumina support. In certain embodiments, the reduction catalyst comprises nanoparticles comprising rhodium, optionally on a high surface area support.

[0259] The reduction catalyst may be selected from alloys of copper and zinc in nanoparticulate form, copper nanoparticles, cobalt nanoparticles, iron nanoparticles, and other nanoparticles or high surface area materials with particle or pore sizes ranging from 0.5 nm-10 nm, that are embedded on a high surface are support such as carbon black, silica, or titanium dioxide. The reduction catalyst may be selected from alloys of copper, zinc, and iron in nanoparticulate form, combinations of cobalt metal and molybdenum sulfide in nanoparticulate form, rhodium nanoparticles, rhodium selenide nanoparticles, palladium nanoparticles, platinum nanoparticles, platinum / cobalt nanoparticles, palladium / copper nanoparticles, and other nanoparticles or high surface area materials with particle or pore sizes ranging from 0.5 nm-10 nm, that are embedded on a high surface are support such as carbon black, silica, or titanium dioxide. In some cases, the support is comprised of high surface area alumina, in others it is approximately 15-30 nm average particle size of mixed phase titanium dioxide (anatase and rutile). In others, the support is purely one phase of either titania or alumina. In others, the support is comprised of nanoparticles 10 nm, 20 nm, 50 nm, 100 nm, 500 nm, and higher. The support can be made using a variety of oxides, including but not limited to AI2O3, ZrCh, SnCh, SiC>2, ZnCh, TiC>2, and others. It can also be comprised of mesoporous silica or a variety of carbon allotropes. Silicates, nitrides, fluorides, and other compounds can also be used as support materials.

[0260] Variations in reduction catalyst formulation include ratios of Cu:Zn between 1:0, 10:1, and 100:1, or Mo :Fe between 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, or 5:1, or Co:Cu between 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, or 5:1. For Cu:Zn usable ratios are between 1:1, 2:1, 3:1, 5:1, and higher for Zn, and 1:2, 1:3, 1:5, and higher for Cu.

[0261] Variations in reduction catalyst formulation include ratios of Cu:Zn:Fe between 1:1:1:, 100:1:1, 1:100:1, 1:1:100 and between. These may be present in oxide form, or metal form upon production. Other variants include Co:MoS2 between 1:100, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, or 100:1, Co:MoS:K between 1:1:100, 1:1:5, 1:3:2, 1:2:2, 1:1:1, 2:1:1, 3:1:3, 1:5:1, or 1:100:1. Rh:Se between 1:0, 10:1, and 100:1, or Pt:Cu between 5:1, 3:1, 2:1, 1:1, 2:1, 3:1, or 5:1, or Pt:Co between 5:1, 3:1, 2:1, 1:1, 2:1, 3:1, or 5:1. For Pd:Cu usable ratios are between 1:1, 2:1, 3:1, 5:1, and higher for Pd, and 1:2, 1:3, 1:5, and higher for Cu. In some cases,

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[0264] additional compounds can be introduced to the particles or can be made into separate catalysts themselves, which can include one or more of the following: Pt, Ru, Rh, Ir, Au, Ni, Co, Li, Na, Fe, Zn, K, Se, Ca, Mg, Mn, Sr, Ba, Ag, Sm, La, Ti, V, Zr, Nb, Mo, Re, Sn, Ce, or other elements. Substitution of platinum, palladium, copper, cobalt, selenium, rhodium, or iron with other elements in its group or with similar valence configurations are also methods of producing catalysts as described in this disclosure. In certain embodiments, the catalyst comprises nanoparticles comprising CuZnFeK, CuZnFeKC, CuZnFeAlK, CuZnFeNa, CuZnFeCoK, CuZnFeCoNaK, CuCoAl, CoMoSK, CuZnK, CuCoMn, RhRu, PdCuFe, Rh, or RhFeSi.

[0265] Reduction reactions such as are described herein use heat and pressure to react hydrogen gas with a low-energy carbon-based reactant, in this case carbon dioxide. This reaction is performed with a heterogeneous catalyst present inside the reactor, wherein the reactant products bind to the surface of the catalyst and are rearranged depending on the surface properties of the catalyst. The use of heat allows for reduction of CO2 to either CO or directly to alcohols, enabling bond formation to overcome activation barriers present on the surface of the catalyst, while pressure improves the rate of reaction. Selectivity of the process is controlled by the catalyst, on which both heat and pressure have an effect. In preferred embodiments, the reaction directly converts CO2 to alcohols without intermediate production of CO. The reduction reactors described in this step have selectivity for CO of 5%, 10%, 25%, 50%, 75%, 80%, 85%, 90%, 95%, 99%, 99.9%, or higher.

[0266] In some embodiments of the present disclosure, carbon dioxide is fed into a reduction reactor to reduce it to an intermediate step prior to alcohol production. In some cases, this intermediate step is production of carbon monoxide and water from carbon dioxide and hydrogen as is noted in this step. Temperature and pressure help tune reaction conditions. In some embodiments of the present disclosure, the pressure vessel is able to withstand pressures up to 10 psi, 100 psi, 500 psi, 1000 psi, 1500 psi, 2000, psi, 3000 psi, 5000 psi, 10,000 psi, and higher. The ratio of pressures between hydrogen gas and carbon dioxide, for example, can also affect selectivity and yield of the process. In some embodiments, the partial pressure of carbon dioxide gas is about 50 psi to about 800 psi, about 10 psi to about 700 psi, or about 200 psi to about 600 psi. The partial pressure of hydrogen is typically higher than that of carbon dioxide, and in some embodiments the partial pressure of hydrogen is about 100 psi to about 5000 psi, about 300 psi to about 2000 psi, about 500 psi to about 1000

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[0269] psi, or about 900 psi to about 1000 psi.. In some embodiments, the carbon dioxide is present in the liquid phase, in which the partial pressure of the liquid is higher than 860 psi at room temperature (25° C ). Pressures can include about 1000 psi, about 2000 psi, about 5000 psi, or higher. Temperatures that this reaction can be accomplished at using a reduction catalyst described herein are from about 100° C. to about 700° C, about 100° C, to about 500° C., about 100° C, to about 400° C., about 150° C. to about 350° C, about 200° C. to about 250° C. When the reactant gases are introduced to a chemical reactor at these temperatures and the aforementioned pressures with the catalysts described herein, carbon monoxide and / or alcohols can be produced.

[0270]

[0271] The alcohol product stream may comprise one or more alcohols and water. The alcohol product stream may comprise methanol and water. In certain embodiments, the alcohol product stream may comprise methanol and ethanol. Optionally, the ethanol may be removed before further processing of the methanol. The alcohol product stream may be present as or condensed into a liquid. In some embodiments, the alcohol product stream is passed into the second reactor in the vapor phase. In some embodiments, the liquid alcohol and water mixture is heated to over 100 °C so that all components of it are vaporized for introduction into the alcohol to olefin reactor.

[0272] Catalysts for the conversion of alcohols to olefins which are suitable for the presently disclosed systems and methods are disclosed in the following patents, each of which is incorporated by reference in its entirety: EP Patent No. 0,096,996; US Patents 4,499,327; 5,191,141; 5,126,308; 5,714,662; and 4,440,871.

[0273] The alcohol to olefin (ATO) reactor is typically a fixed bed flow reactor, but may be one of several other reactor types, including a trickle bed reactor, a fluidized bed reactor, an ebullated bed reactor, a continuously stirred tank reactor, or others. The ATO reactor may also be referred to as a methanol to olefins (MTO) reactor. The ATO reactor includes an ATO catalyst that converts methanol into olefins such as ethylene, propylene, butylenes, and others at elevated temperature and ambient to low pressures. In certain embodiments, the ATO temperature is from about 260 °C to about 510 °C. In further embodiments, the ATO temperature is from about 315 °C to about 370 °C. In yet further embodiments, the ATO - 33 -

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[0275] temperature is about 315 °C. In certain preferred embodiments, the ATO temperature is about 325 °C. In certain embodiments, the ATO temperature is about 335 °C. In further embodiments, the ATO temperature is about 345 °C. In yet further embodiments, the ATO temperature is about 355 °C. In still further embodiments, the ATO temperature is about 365 °C. In certain embodiments, the ATO temperature is about 370 °C.

[0276] In certain embodiments, the ATO pressure is from about 100 kPa to about 515 kPa. In certain preferred embodiments, the ATO pressure is about 100 kPa. In certain embodiments, the ATO or pressure is about 200 kPa. In further embodiments, the ATO pressure is about 300 kPa. In yet further embodiments, the ATO pressure is about 400 kPa. In still further embodiments, the ATO pressure is about 500 kPa. In certain embodiments, the ATO pressure is about 515 kPa.

[0277] Over about 85%, or over about 90% of methanol may be converted to olefins. In some embodiments, about 90% to about 100% of the methanol is converted to olefins. In some embodiments, ethylene is the preferred product of the ATO reaction.

[0278] The ATO reaction may afford a product comprising ethylene, propylene, and C4+ hydrocarbons. The ATO reaction may afford a product comprising about 30 wt% to about 60 wt% ethylene, about 30 wt% to about 60 wt% propylene, about 0 wt% to about 30 wt% C4+ hydrocarbons. The C4+ hydrocarbons in the product is over about 50 wt%, over about 60 wt%, over about 70 wt% olefin. In some embodiments, the reaction is performed at ambient pressure. The resulting olefins are separated from byproduct water and purified by distillation, membrane separation, or any other technique for separating olefins known to those skilled in the art.

[0279] Fuel Compositions

[0280] In certain aspects, the present disclosure provides systems and methods for producing fuel compositions from a carbon source gas (e.g., CO2) and a reduction gas (e.g., H2). The fuel compositions produced by these systems and / or methods, e.g., the compositions described below, exhibit certain unique properties and compositional features. For example, these compositions have low total sulfur content because they (or their major components) are produced synthetically from CO2. As another example, the systems and processes disclosed herein for preparing the aromatic component heavily favor the creation of monocyclic aromatics, and disfavor the creation of polycyclic aromatics. These compositional features - 34 -

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[0282] (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.

[0283] In some aspects, provided herein are fuel compositions comprising: monocyclic aromatics; cycloparaffin; linear paraffins; and branched paraffins,. The composition may comprise less than about 2 wt%, or less than about 1 wt% polycyclic aromatics.

[0284] The fuel composition may comprise less than about 0.5 wt% polycyclic aromatics. The fuel composition may comprise from about 0 wt% to about 1 wt%, 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.

[0285] 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.

[0286] In certain embodiments, essentially all of the aromatic compounds present in fuel composition of the present disclosure are monocyclic aromatics.

[0287] The fuel composition may comprise about 5 wt% to about 25 wt% monocyclic aromatics. The fuel composition may comprise about 8 wt% to about 15 wt% monocyclic aromatics. The fuel composition may comprise about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, or about 14 wt% monocyclic aromatics. The fuel composition may comprise about 14.5 wt% monocyclic aromatics.

[0288] The fuel composition may comprise about 15 wt% to about 65 wt% cycloparaffins The fuel composition may comprise from about 15 wt% to about 35 wt% cycloparaffins. The fuel composition may comprise about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, or about 35 wt% cycloparaffins. The fuel composition may comprise about 29 wt% cycloparaffins.

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[0291] The fuel composition may comprise about 5 wt% to about 40 wt% iso-paraffins. The fuel composition may comprise from about 5 wt% to about 15 wt% iso-paraffins. The fuel composition may comprise about 5 wt%, about 7 wt%, about 9 wt%, about 11 wt%, about 13 wt%, or about 15 wt% iso-paraffins. The fuel composition may comprise about 8.8 wt% isoparaffins.

[0292] The fuel composition may be compliant with ASTM D4054 - Tier 1.

[0293] 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.

[0294] In certain embodiments, the composition comprises less than about 0.3 wt% total sulfur, for example as measured by ASTMD2622. 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.

[0295] 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.

[0296] The fuel composition may have a density from about 775 kg / m3to about 840 kg / m3at 15 °C. In some embodiments, the composition has a density from about 775 kg / m3to about 785 kg / m3at 15 °C. In certain embodiments, the composition has a density of about 775 kg / m3, about 778 kg / m3, about 780 kg / m3, about 782 kg / m3, or about 785 kg / m3at 15 °C. In further embodiments, the composition has a density of about 780 kg / m3at 15 °C.

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[0299] 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.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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.

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[0308] The fuel composition may be compliant with ASTM DI 655.

[0309] 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, cycloparaffins, linear paraffins, and branched paraffins, are not petroleum-derived. In other embodiments, the monocyclic aromatics, cycloparaffins, linear paraffins, and branched paraffins are derived from CO2.

[0310] 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.

[0311] Oligomerization o f Olefins to Higher Olefins and Paraffins

[0312] In some embodiments, it is desirable to oligomerize the olefins produced from the alcohol to olefins process 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 or olefins will refer to hydrocarbons or olefins with a higher number of carbons than a precursor. Exemplary higher hydrocarbons and olefins include, but are not limited to Cs-Ci6 hydrocarbons and / or olefins. Exemplary precursors may be mixtures of short chain olefins and short chain paraffins (e.g., C2-C5). In certain embodiments, these precursors are the effluent from an ATO reactor of the disclosure and the effluent is used in oligomerization without further purification. In other embodiments, any suitable known process for purification of a feed stream may be performed prior to oligomerization.

[0313] Said oligomerization process can be carried out in a fixed bed flow reactor, or any other suitable reactor type. In certain embodiments, the oligomerization process is performed with a fixed bed type reactor. In some embodiments, the oligomerization process is performed in a batch type reactor The temperature at which this oligomerization can be carried out can range from about 50 °C to about 500 °C as needed to tailor the degree of oligomerization based on the desired product length and distribution. In certain embodiments, the oligomerization temperature is from about 50 °C to about 350 °C. In further embodiments, the oligomerization temperature is about 50 °C. In yet further embodiments, the oligomerization temperature is about 150 °C. In certain preferred embodiments, the oligomerization temperature is about 250 °C. In certain embodiments, the oligomerization temperature is about 350 °C.

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[0316] The pressure at which this oligomerization can be carried out can range from about 0 psi (ambient pressure) to about 2000 psi as needed to tailor the degree of oligomerization based on the desired product length and distribution. In certain embodiments, the oligomerization pressure is from about 0 psi to about 2000 psi. In further embodiments, the oligomerization pressure is about 0 psi. In further embodiments, the oligomerization pressure is about 0 psi. In certain preferred embodiments, the oligomerization pressure is about 30 psi. In certain embodiments, the oligomerization pressure is about 250 psi. In further embodiments, the oligomerization pressure is about 500 psi. In yet further embodiments, the oligomerization pressure is about 750 psi. In still further embodiments, the oligomerization pressure is about 1000 psi. In certain embodiments, the oligomerization pressure is about 1250 psi. In further embodiments, the oligomerization pressure is about 1500 psi. In yet further embodiments, the oligomerization pressure is about 1750 psi. In still further embodiments, the oligomerization pressure is about 2000 psi.

[0317] The oligomerized product mixture produced during the oligomerization step may comprise from about lwt% to about 20 wt% aromatics by volume, and preferably less than about 5wt% aromatics by volume, or less than about 2wt% aromatics by volume.

[0318] As will be appreciated by one of skill in the art, measurement of pressure in the unit “pounds per square inch” (psi) can refer to either the pressure measured on a gauge (psig), where 0 psi corresponds to atmospheric pressure, or the absolute pressure (psia), where 0 psi corresponds to a perfect vacuum. As used herein, unless the contrary is explicitly specified, the unit “psi” refers to gauge pressure (psig).

[0319] Catalysts for Conversion of Alcohols to Olefins

[0320] In certain aspects, the systems and methods of the present disclosure involve the use of catalysts for the conversion of alcohols to products comprising olefins, e.g., the conversion of ethanol to a mixture comprising ethylene.

[0321] In some embodiments, the alcohol to olefin (ATO) catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate. In further embodiments, the ATO or MTO catalyst comprises SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, or ZSM-34. In other embodiments, the silicoaluminophosphate may contain other atoms, such as +2 or +4 metals,

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[0324] e.g., Mn, Co, Ge, Sn, etc In yet further embodiments, the ATO catalyst comprises alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

[0325] In some embodiments, the ATO catalyst comprises a transition metal-promoted silicoaluminophosphate, such as Ni-SAPO-34. In some embodiments, the ATO catalyst comprises KIT-6 or transition metal-promoted KIT-6. In some embodiments, the ATO catalyst is an acidic catalyst with active sites that assist in the coordination and insertion of methanol to selectively produce olefins with water as a byproduct. In some embodiments, nickel or other transition metals are used to promote oligomerization.

[0326] In some embodiments, the ATO catalyst is an ethanol dehydration catalyst. In some embodiments, the ethanol dehydration catalyst is gamma AI2O3. In some embodiments, the ethanol dehydration catalyst is one of those described in Zhang, M. & Yu, Y., Dehydration of Ethanol to Ethylene, Ind. Eng. Chem. Res. 2013, 52, 9505-9514 (appended hereto as Appendix A).

[0327] In certain embodiments, the ATO reactor is configured such that a suspension of vaporized ethanol and the fluid catalyst particles pass upwardly through a dispersed catalyst contact and reaction zone.

[0328] Catalysts for Conversion of Alcohols to Aromatics

[0329] In certain aspects, the systems and methods of the present disclosure involve the use of catalysts for the conversion of alcohols to aromatics. In certain embodiments, the systems and methods of the present disclosure involve the use of catalysts for the conversion of methanol to aromatics. Any known catalyst for use in converting alcohols, in particular methanol, to aromatics may be used in accordance with this disclosure.

[0330] The alcohol to aromatic (ATA) catalyst may comprise a molecular sieve, and optionally Group 8-14 element, or combination of metals from the same group of the Periodic Table. The ATA catalyst may optionally further comprise phosphorus and / or lanthanum and / or other elements from Group 1-2 and / or Group 13-16 of the Periodic Table that provide structural stabilization

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[0333] The alcohol to aromatic (ATA) catalyst may comprise a molecular sieve, or a metal-substituted molecular sieve. The metal may be selected from the group consisting of Zn, Ga, Cd, Ag, Cu, P, La, or combinations thereof. In a preferred embodiment, the metal is Zn, Ga, Ag, or a combination thereof.

[0334] As used herein the term “molecular sieve” refers to crystalline or non-crystalline materials having a porous structure. Microporous molecular sieves typically have pores having a diameter of about 2.0 nm. Mesoporous molecular sieves typically have pores with diameters of about 2 to about 50 nm. Macroporous molecular sieves have pore diameters of >50.0 nm.

[0335] Particular molecular sieves are zeolites. Some zeolites are aluminosilicates comprising [SiO4] and [A1O4] units. Other zeolites are aluminophosphates (A1PO) having structures comprising [A1O4] and [PO4] units. Still other zeolites are silicoaluminophosphates (SAPO) comprising [SiO4], [A1O4], and [PO4] units.

[0336] Non-limiting examples of SAPO and A1PO molecular sieves useful herein include one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, A1PO-5, A1PO-11, A1PO-18, A1PO-31, A1PO-34, A1PO-36, A1PO-37, A1PO-46, and metal containing molecular sieves thereof. Of these, particularly useful molecular sieves are one or a combination of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, A1PO-18, A1PO-34 and metal containing derivatives thereof, such as one or a combination of SAPO-18, SAPO-34, A1PO-34, A1PO-18, and metal containing derivatives thereof, and especially one or a combination of SAPO-34, A1PO-18, and metal containing derivatives thereof.

[0337] Additionally or alternatively, the molecular sieves useful herein may be characterized by a ratio of Si to Al. In particular embodiments, the molecular sieves suitable herein include those having a Si / Al ratio of about 0.05 to 0.5.

[0338] Particular molecular sieves useful in this invention include, but are not limited to, ZSM-5 (U.S. Pat. No. 3,702,886 and Re. 29,948); ZSM-11 (U.S. Pat. No. 3,709,979); ZSM-12 (U.S. Pat. No. 3,832,449); ZSM-22 (U.S. Pat. No. 4,556,477); ZSM-23 (U.S. Pat. No. 4,076,842); ZSM-34 (U.S. Pat. No. 4,079,095) ZSM-35 (U.S. Pat. No. 4,016,245); ZSM-48 (U.S. Pat. No.

[0339] 4,397,827); ZSM-57 (U.S. Pat. No. 4,046,685); and ZSM-58 (U.S. Pat. No. 4,417,780). The entire contents of the above references are incorporated by reference herein. Other useful - 41 -

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[0341] molecular sieves include MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49 or MCM-56, with MCM-22. Still other molecular sieves include Zeolite T, ZK5, erionite, and chabazite.

[0342] The zeolite may include at least one ring channel based on a 10-m ember ring. In such aspects, the zeolite does not have any ring channels based on a ring larger than a 10-member ring. Examples of suitable framework structures having a 10-member ring channel but not having a larger size ring channel include EUO, FER, IMF, LAU, MEL, MFI, MFS, MTT, MWW, NES, PON, SFG, STF, STI, TON, TUN, MRE, and PON.

[0343] The ATA catalyst may optionally include at least one metal selected from Group 8-14 of the Periodic Table, such as at least two metals (i.e., bimetallic) or at least three metals (i.e., trimetallic). The total weight of the Group 8-14 elements may be from about 0.1 to 10 wt. % based on the total weight of the ATA catalyst, preferably from about 0.1 to 2.0 wt. %, and more preferably from about 0.1 to 1.0 wt. %.

[0344] Additionally or alternatively, the ATA catalyst may include at least one of phosphorous and / or lanthanum and / or other elements from groups 1-2 and / or group 13-16, such as at least two such elements or at least three such elements. Typically, the total weight of the phosphorous and / or lanthanum and / or other elements from groups 1-2 and / or groups 13-16 is about 0.1 to 1.0 wt. % based on the total weight of the ATA catalyst.

[0345] For the purposes of this description and claims, the numbering scheme for the Periodic Table Groups corresponds to the current IUPAC numbering scheme. Therefore, a “Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0346] The molecular sieve used herein may be a SAPO molecular sieve, or metal-substituted SAPO molecular sieves. In particular embodiments, one or more Group 1 elements (e.g., Li, Na, K, Rb, Cs, Fr) and / or Group 2 elements (e.g., Be, Mg, Ca, Sr, Ba, and Ra) and / or phosphorous and / or Lanthanum may be used. One or more Group 7-9 element (e.g., Mn, Tc, Re, Fe, Ru, Os, Co, Rh, and Ir) may also be used. Group 10 elements (Ni, Pd, and Pt) are less commonly used in applications for forming olefins and aromatics, as the combination of a Group 10 element in the presence of hydrogen can tend to result in saturation of aromatics and / or olefins. In some embodiments, one or more Group 11 and / or Group 12 elements (e.g., Cu, Ag, Au, Zn, and Cd) may be used. In still other embodiments, one or more Group 13 elements (B, Al, Ga, In, and Tl) and / or Group 14 elements (Si, Ge, Sn, Pb) may be used. In a preferred embodiment, the metal is selected from the group consisting of Zn, Ga, Cd, Ag, Cu,

[0347] - 42 -

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[0349] P, La, or combinations thereof. In another preferred embodiment, the metal is Zn, Ga, Ag, or a combination thereof.

[0350] Particular molecular sieves and Group 2- 13 -containing derivatives thereof have been described in detail in numerous publications including for example, U.S. Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871 (SAPO), European Patent Application EP-A-0 159624 (El APSO where El is Be, B, Cr, Co, Ga, Fe, Mg, Mn, Ti, or Zn), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217, 4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti, orZn), U.S. Pat. No. 4,310,440 (A1PO4), U.S. Pat. No. 5,057,295 (BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos.

[0351] 4,759,919, and 4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038, 5,434,326, and 5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,686,092, 4,846,956, and 4,793,833 (MnAPSO), U.S. Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No.

[0352] 4,737,353 (BeAPSO), U.S. Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617, and 4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236, and 4,605,492 (TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No. 4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, where Q is framework oxide unit [QO2]), as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,241,093, 5,493,066, and 5,675,050, all of which are herein fully incorporated by reference.

[0353] The molecular sieve substituted by the Group 8-14 element and / or a Group 1-2, Group 13-16, lanthanum, and / or phosphorous may be metal-substituted ZSM-5.

[0354] Various methods for synthesizing molecular sieves or modifying molecular sieves are described in U.S. Pat. No. 5,879,655 (controlling the ratio of the templating agent to phosphorus), U.S. Pat. No. 6,005,155 (use of a modifier without a salt), U.S. Pat. No.

[0355] 5,475,182 (acid extraction), U.S. Pat. No. 5,962,762 (treatment with transition metal), U.S. Pat. Nos. 5,925,586 and 6,153,552 (phosphorus modified), U.S. Pat. No. 5,925,800 (monolith supported), U.S. Pat. No. 5,932,512 (fluorine treated), U.S. Pat. No. 6,046,373 (electromagnetic wave treated or modified), U.S. Pat. No. 6,051,746 (polynuclear aromatic modifier), U.S. Pat. No. 6,225,254 (heating template), International Patent Application WO 01 / 36329 published May 25, 2001 (surfactant synthesis), International - 43 -

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[0357] Patent Application WO 01 / 25151 published Apr. 12, 2001 (staged acid addition), International Patent Application WO 01 / 60746 published Aug. 23, 2001 (silicon oil), U.S. Patent Application Publication No. 2002-0055433 published May 9, 2002 (cooling molecular sieve), U.S. Pat. No. 6,448,197 (metal impregnation including copper), U.S. Pat. No. 6,521,562 (conductive microfilter), and U.S. Patent Application Publication No. 2002-0115897 published Aug. 22, 2002 (freeze drying the molecular sieve), which are all herein incorporated by reference in their entirety.

[0358] The alcohol to aromatic (ATA) catalyst may comprise a molecular sieve selected from ZSM-5, ZSM-11, SAPO-34, SAPO-5, and SSZ-24, and optionally metal-substituted. The alcohol to aromatic (ATA) catalyst may comprise ZSM-5, ZSM-11, SAPO-34, SAPO-5, SSZ-24, or any combination thereof, substituted with a metal selected from Zn, Ga, Cd, Ag, Cu, P, La, or any combination thereof. The metal may be Zn or Ga.

[0359] The alcohol to aromatic (ATA) catalyst may comprise ZSM-5, optionally metal-substituted with Zn, Ga or a combination thereof.

[0360] Optionally, the ATA catalyst may also include a filler or binder and may be combined with a carrier to form slurry. Any filler or binder known for use in the art may be used herein.

[0361] In various aspects, the molecular sieve comprises sMO.O wt. % of the ATA catalyst, such about 10.0 to 100.0 wt. %, preferably about 25.0 to 95.0 wt. %, and more preferably about 50.0 to 90.0 wt. %.

[0362] The alcohol to aromatics (ATA) reactor is typically a fixed bed flow reactor, but may be one of several other reactor types, including a trickle bed reactor, a fluidized bed reactor, an ebullated bed reactor, a continuously stirred tank reactor, or others. The ATA reactor may also be referred to as a methanol to aromatics (MTA) reactor. The ATA reactor includes an ATA catalyst that converts alcohols into aromatics such as benzene, toluene, xylenes, and others at elevated temperature and ambient to low pressures. The ATA temperature may be about 250 °C to about 550 °C, about 300 °C to about 500 °C, or about 450 °C to about 500 °C. In yet further embodiments, the ATA temperature is about 390 °C, about 400 °C, about 425 °C, about 430 °C, about 475 °C, or about 500 °C,

[0363] The ATA pressure may be about 100 kPa to about 515 kPa. In certain preferred embodiments, the ATA pressure is about 100 kPa. In certain embodiments, the ATA or pressure is about 200 kPa. In further embodiments, the ATA pressure is about 300 kPa. In yet - 44 -

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[0365] further embodiments, the ATA pressure is about 400 kPa. In still further embodiments, the ATA pressure is about 440 kPa. In still further embodiments, the ATA pressure is about 500 kPa. In certain embodiments, the ATA pressure is about 515 kPa.

[0366] Greater than about 50%, about 60%, about 70%, about 80%, or over about 90% of methanol may be converted to aromatics. In some embodiments, about 60% to about 80% of the methanol is converted to aromatics. In some embodiments, toluene is the preferred product of the ATA reaction.

[0367] The ATA reaction may afford a product comprising about 60% to about 70% of Ce-15 aromatics.

[0368] Conversion of Olefins to Aromatics

[0369] In certain aspects, the present disclosure provides methods for the production of aromatics comprising contacting olefins, optionally, a second reduction gas and a carbon source gas, with an aromatic catalyst to afford an aromatic product mixture.

[0370] In certain embodiments, contacting the olefin product mixture with the aromatic catalyst occurs at an aromatic temperature from about 100 °C to about 600 °C, preferably from about 100 °C to about 550 °C. The aromatic temperature may be at least about 80 °C, or at least about 100 °C, or at least about 120 °C. The aromatic temperature may be about 600 °C or less, about 550 °C or less, or about 500 °C or less. In certain embodiments, the aromatic temperature is from about 250 °C to about 600 °C.

[0371] In some embodiments, contacting the olefin product mixture with the aromatic catalyst occurs at an aromatic pressure from about 5 psi to about 3000 psi, or about 5 psi to about 1000 psi. In certain such embodiments, the aromatic pressure is about 5 psi, about 15 psi, about 50 psi, about 100 psi, about 250 psi, about 350 psi, about 450 psi, about 550 psi, about 650 psi, about 850 psi, or about 1000 psi.

[0372] In certain embodiments, contacting the olefin product mixture with an aromatic catalyst to afford an aromatic product mixture is carried out at an aromatic standard Gas Hourly Space Velocity (aromatic GHSV) of about 8000 mL / g*h to about 12000 mL / g*h., about 8750 mL / g*h to about 9250 mL / g*h, or about 8750 mL / g*h to about 9000 mL / g*h.

[0373] In certain embodiments, the aromatic product mixture comprises aromatic hydrocarbons to naphthenes in an aromaticsmaphthenes ratio, which may be controlled by - 45 -

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[0375] changes to the relative amounts of the carbon source gas, the second reduction gas, and the aromatic catalyst in concert with changes to the aromatic temperature and aromatic pressure. In certain embodiments, the aromaticsmaphthenes ratio may be further modified using a hydrogenation reactor. In certain embodiments, the ratio does not need further modification and the aromatic product mixture may be used directly in subsequent steps ( / .<?., without a subsequent hydrogenation step).

[0376] As used herein, the term “wt% polycyclic aromatics” in the aromatic product mixture is a percentage of polycyclic aromatics based on total aromatics. In certain embodiments, the aromatic product mixture comprises from about 0 wt% to about 2 wt% polycyclic aromatics. In further embodiments, the aromatic product mixture comprises from about 0.1 wt% to about 2 wt% polycyclic aromatics. In yet further embodiments, the aromatic product mixture comprises from about 0.1 wt% to about 1 wt% polycyclic aromatics. In still further embodiments, the aromatic product mixture comprises from about 1 wt% to about 2 wt% polycyclic aromatics.

[0377] In certain aspects, the systems and methods of the present disclosure involve the use of aromatic catalysts. As used herein, the term “aromatic catalyst” refers to a catalyst used for the conversion of olefins and / or carbon sources, as relevant to the compounds present in the feed stream, to aromatics, but which does not necessarily itself comprise aromatics. Use of an aromatic catalyst may also produce other hydrocarbons in a lesser amount. In certain aspects, the aromatic catalysts of the disclosure comprise: one or more aromatic metal oxides; optionally an aromatic catalyst support; and optionally one or more aromatic metal additives.

[0378] In certain embodiments, catalysts of the disclosure are described as comprising and / or being 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 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 aromatic catalysts described below, the molar ratio of oxygen relative to the total composition may vary.

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[0381] In certain embodiments, the one or more aromatic metal oxides is selected from zinc oxide, copper oxide, chromium oxide, and zirconium oxide. In further embodiments, the one or more aromatic metal additives, when present, are selected from a group IA or IIA element, palladium, platinum, and ruthenium. In yet further embodiments, the one or more aromatic metal oxides comprises a first aromatic metal oxide and a second aromatic metal oxide, wherein the first aromatic metal oxide is zinc or copper, and the second aromatic metal oxide is selected from chromium, aluminum, and zirconium.

[0382] In some embodiments, the first aromatic metal oxide and second metal oxide are present in a first metallic ratio of from about 1 : 5 to about 5 : 1. In certain embodiments, the first metallic ratio is about 1:5. In further embodiments, the first metallic ratio is about 1:4.5. In yet further embodiments, the first metallic ratio is about 1 :4. In still further embodiments, the first metallic ratio is about 1:3.5. In certain embodiments, the first metallic ratio is about 1:3. In further embodiments, the first metallic ratio is about 1:2.5. In yet further embodiments, the first metallic ratio is about 1:2. In still further embodiments, the first metallic ratio is about 1:1.5. In certain embodiments, the first metallic ratio is about 1:1. In further embodiments, the first metallic ratio is about 1.5:1. In yet further embodiments, the first metallic ratio is about 2:1. In still further embodiments, the first metallic ratio is about 2.5:1. In certain embodiments, the first metallic ratio is about 3:1. In further embodiments, the first metallic ratio is about 3.5:1. In yet further embodiments, the first metallic ratio is about 4:1. In still further embodiments, the first metallic ratio is about 4.5:1. In certain embodiments, the first metallic ratio is about 5:1.

[0383] In certain embodiments, the aromatic catalyst comprises: one or more aromatic metals; optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII aromatic metal additives; and optionally a Group IA or IIA metal promoter.

[0384] In certain embodiments, the one or more aromatic metals comprises a first aromatic metal and a second aromatic metal. In further embodiments, the first aromatic metal is zinc oxide. In yet further embodiments, the second aromatic metal is selected from zirconium, chromium, aluminum, and copper. In still further embodiments, the first aromatic metal is present in the form of an oxide, nitride, or carbide. In certain embodiments, the second aromatic metal is present in the form of an oxide, nitride, or carbide.

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[0387] In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is from about 1:10 to about 10:1. In further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:10. In yet further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1 :9. In still further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:8. In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1 :7. In further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:6. In yet further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:5. In still further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1 :4. In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1 :3. In further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:2. In yet further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1 : 1. In still further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 2:1. In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 3 : 1. In further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 4:1. In yet further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 5:1. In still further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 6: 1. In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 7: 1. In further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 8:1. In yet further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 9: 1. In still further embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 10:1.

[0388] In certain embodiments, the metal additive is selected from gallium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, and aluminum. In certain preferred embodiments, the metal additive is gallium. In further embodiments, the metal additive is chromium. In yet further embodiments, the metal additive is molybdenum. In still further embodiments, the metal additive is tungsten. In certain embodiments, the metal additive is manganese. In further embodiments, the metal additive is rhenium. In yet further embodiments, the metal additive is iron. In still further embodiments, the metal additive is ruthenium. In - 48 -

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[0390] certain embodiments, the metal additive is osmium. In further embodiments, the metal additive is cobalt. In yet further embodiments, the metal additive is rhodium. In still further embodiments, the metal additive is iridium. In certain embodiments, the metal additive is nickel. In further embodiments, the metal additive is palladium. In yet further embodiments, the metal additive is platinum. In still further embodiments, the metal additive is copper. In certain embodiments, the metal additive is silver. In further embodiments, the metal additive is gold. In further embodiments, the additive is aluminum. In certain certain preferred embodiments, the one or more aromatic catalyst metal additives is gallium.

[0391] In certain embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. In further embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium. In yet further embodiments, the metal promoter is selected from beryllium, magnesium, calcium, strontium, and barium. In still further embodiments, the metal promoter is potassium.

[0392] In certain embodiments, the aromatic catalyst is ZnCrC .

[0393] In certain embodiments, the aromatic metal is zinc; the one or more aromatic metal additives is present, and wherein the one or more aromatic metal additives is gallium; and the aromatic catalyst comprises an aromatic catalyst support, wherein the aromatic catalyst support is ZSM-5.

[0394] In certain embodiments, the aromatic catalyst comprises a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain embodiments, the zeolite is ZSM-5, MCM-49, PSH-3, PSH-3, or MCM-22. The zeolite may be ZSM-5. The ZSM-5 may have a silicon to aluminum ratio (SAR) of about 5 to about 1000, about 30 to about 1000, about 80 to about 400, about 30 to about 280, or about 80 to about 280.

[0395] The zeolite may comprise a modifier. The modifier may be Ga, Fe, Mn, Zn, P, Pt or a combination thereof. In certain embodiments, the zeolite comprises from 0 wt% to about 10 wt% of the modifier. In further embodiments, the zeolite comprises from 0.01 wt% to about 10

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[0398] wt% of the modifier, from 0.01 wt% to about 5 wt% of the modifier, from 0.01 wt% to about 3 wt% of the modifier, from 0.1 wt% to about 1.5 wt% of the modifier, or from 0.5 wt% to about 1 wt% of the modifier. In certain embodiments, the zeolite is ZSM-5 modified with Ga, Fe, Mn, Zn, P, Pt, or a combination thereof. The zeolite may be ZSM-5 modified with Zn, optionally in an amount of 0 wt% to about 10 wt% of the total catalyst composition.

[0399] Optional features of the invention relating to catalysts for conversion of carbon sources and reduction gas to aromatics described above may also constitute optional features in relation to catalysts for conversion of carbon sources to paraffins or catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, and vice versa.

[0400] The aromatic catalyst may include a binder. The binder may be any binder known for use in the art. In certain embodiments, the binder may be selected from the group consisting of: boehmite (e.g., PURAL® TH 100, PURAL® TH 80, PURAL® TH 200, PURAL® 200), silica-alumina hydrate (e.g., SIRAL® 1, SIRAL® 5, SIRAL® 10, SIRAL® 20, SIRAL® 40), aluminate, silicon, zirconium, silica, pseudoboehmite alumina (e.g., VERSAL® V-250), bentonite, or any combination thereof. The binder may be present in an amount of about 0% to about 60% by weight, or about 0% to about 40% by weight of the total catalyst composition. In certain embodiments, the binder is present in about 0.1% to about 30%, about 0.1% to about 20%, about 1% to about 30%, about 1% to about 20%, about 1% to about 15%, about 5% to about 30%, about 5% to about 20%, about 5% to about 15%, about 0.5% to about 10%, about 0.5% to about 5% by weight of the total catalyst composition. In an embodiment, the aromatic catalyst includes a silica binder in amount of about 15% to about 25%, or about 20% by weight of the total catalyst composition.

[0401] In certain embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, to aromatics. In other embodiments, aromatic catalysts of the disclosure are active in the conversion of a carbon source gas, such as CO2, and an olefin source to aromatics. The olefin source may be a hydrocarbon product mixture, such as a medium hydrocarbon product mixture comprising one or more C5-8 paraffins and / or olefins, or an olefin product mixture, such as a stream comprising one or more C5-8 olefins, to aromatics.

[0402] The feed stream through the aromatic catalyst may carbon source gas be a mixture of hydrocarbons, including, but not limited to, olefins. Accordingly, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, to - 50 -

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[0404] the specified aromatic molecule(s). Optionally, the selectivity for the aromatic catalyst refers to conversion of hydrocarbons, including, but not limited to, olefins, in the presence of a carbon gas source to the specified aromatic molecule(s). The aromatic catalyst used herein may have a selectivity for aromatics of over about 50% by weight, over about 55% by weight, over about 60% by weight, or over about 65% by weight. The aromatic catalyst may have a selectivity for aromatics of about 50% to about 90% by weight, about 55% to about 85% by weight, about 60% to about 85% by weight, or about 65% to about 80% by weight. The aromatic catalyst used herein may have a selectivity for target aromatic of about 5% to about 20% by weight, or about 7% to about 15% by weight. The aromatic catalyst used herein may have a selectivity for methane of less than about 8%, less than about 5% by weight, or less than about 4% by weight. The aromatic catalyst used herein may have a selectivity for methane of about 1% to about 8% by weight, about 2% to about 6% by weight, about 2% to about 5% by weight, or about 3% to about 4% by weight.

[0405] Catalysts for Conversion of Carbon Sources and Reduction Gas to Aromatics

[0406] In certain aspects, the systems and methods of the present disclosure involve the use of bi-functional aromatic catalysts. As used herein, the term “bi-functional aromatic catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to aromatics, but which does not necessarily itself comprise aromatics. In certain aspects, the bi-functional aromatic catalysts of the disclosure comprise: one or more aromatic metal oxides; optionally an bi-functional aromatic catalyst support; and optionally one or more aromatic metal additives. In certain embodiments, catalysts of the disclosure are described as comprising and / or being 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 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 bi-functional aromatic catalysts described below, the molar ratio of oxygen relative to the total composition may vary.

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[0408] FH13166046.1Attorney Docket No.: CSW-02925

[0409] In certain embodiments, the one or more aromatic metal oxides is selected from zinc oxide, copper oxide, chromium oxide, and zirconium oxide. In further embodiments, the one or more aromatic metal additives, when present, are selected from a group IA or IIA element, palladium, platinum, and ruthenium. In yet further embodiments, the one or more aromatic metal oxides comprises a first aromatic metal oxide and a second aromatic metal oxide, wherein the first aromatic metal oxide is zinc or copper, and the second aromatic metal oxide is selected from chromium, aluminum, and zirconium.

[0410] In some embodiments, the first aromatic metal oxide and second metal oxide are present in a first metallic ratio of from about 1 : 5 to about 5 : 1. In certain embodiments, the first metallic ratio is about 1:5. In further embodiments, the first metallic ratio is about 1:4.5. In yet further embodiments, the first metallic ratio is about 1 :4. In still further embodiments, the first metallic ratio is about 1:3.5. In certain embodiments, the first metallic ratio is about 1:3. In further embodiments, the first metallic ratio is about 1:2.5. In yet further embodiments, the first metallic ratio is about 1:2. In still further embodiments, the first metallic ratio is about 1:1.5. In certain embodiments, the first metallic ratio is about 1:1. In further embodiments, the first metallic ratio is about 1.5:1. In yet further embodiments, the first metallic ratio is about 2:1. In still further embodiments, the first metallic ratio is about 2.5:1. In certain embodiments, the first metallic ratio is about 3:1. In further embodiments, the first metallic ratio is about 3.5:1. In yet further embodiments, the first metallic ratio is about 4:1. In still further embodiments, the first metallic ratio is about 4.5:1. In certain embodiments, the first metallic ratio is about 5:1.

[0411] In certain embodiments, the bi-functional aromatic catalyst comprises: one or more metals; optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII metal additives; and optionally a Group IA or IIA metal promoter.

[0412] In certain embodiments, the one or more metals comprises a first metal and a second metal. In further embodiments, the first metal is zinc oxide. In yet further embodiments, the second metal is selected from zirconium, chromium, aluminum, and copper. In still further embodiments, the first metal is present in the form of an oxide, nitride, or carbide. In certain embodiments, the second metal is present in the form of an oxide, nitride, or carbide.

[0413] In certain embodiments, the ratio of the first metal to the second metal is from about 1:10 to about 10:1. In further embodiments, the ratio of the first metal to the second metal is - 52 -

[0414] FH13166046.1Attorney Docket No.: CSW-02925

[0415] about 1 : 10. In yet further embodiments, the ratio of the first metal to the second metal is about 1 :9. In still further embodiments, the ratio of the first metal to the second metal is about 1 :8. In certain embodiments, the ratio of the first metal to the second metal is about 1:7. In further embodiments, the ratio of the first metal to the second metal is about 1:6. In yet further embodiments, the ratio of the first metal to the second metal is about 1:5. In still further embodiments, the ratio of the first metal to the second metal is about 1:4. In certain embodiments, the ratio of the first metal to the second metal is about 1:3. In further embodiments, the ratio of the first metal to the second metal is about 1:2. In yet further embodiments, the ratio of the first metal to the second metal is about 1:1. In still further embodiments, the ratio of the first metal to the second metal is about 2:1. In certain embodiments, the ratio of the first metal to the second metal is about 3:1. In further embodiments, the ratio of the first metal to the second metal is about 4:1. In yet further embodiments, the ratio of the first metal to the second metal is about 5:1. In still further embodiments, the ratio of the first metal to the second metal is about 6:1. In certain embodiments, the ratio of the first metal to the second metal is about 7:1. In further embodiments, the ratio of the first metal to the second metal is about 8:1. In yet further embodiments, the ratio of the first metal to the second metal is about 9:1. In still further embodiments, the ratio of the first metal to the second metal is about 10:1.

[0416] In certain embodiments, the metal additive is selected from gallium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, and aluminum. In certain preferred embodiments, the metal additive is gallium. In further embodiments, the metal additive is chromium. In yet further embodiments, the metal additive is molybdenum. In still further embodiments, the metal additive is tungsten. In certain embodiments, the metal additive is manganese. In further embodiments, the metal additive is rhenium. In yet further embodiments, the metal additive is iron. In still further embodiments, the metal additive is ruthenium. In certain embodiments, the metal additive is osmium. In further embodiments, the metal additive is cobalt. In yet further embodiments, the metal additive is rhodium. In still further embodiments, the metal additive is iridium. In certain embodiments, the metal additive is nickel. In further embodiments, the metal additive is palladium. In yet further embodiments, the metal additive is platinum. In still further embodiments, the metal additive is copper. In - 53 -

[0417] FHl 3166046.1Attorney Docket No.: CSW-02925

[0418] certain embodiments, the metal additive is silver. In further embodiments, the metal additive is gold. In further embodiments, the additive is aluminum.

[0419] In certain embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. In further embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, magnesium, calcium, and cesium. In yet further embodiments, the metal promoter is selected from beryllium, magnesium, calcium, strontium, and barium. In still further embodiments, the metal promoter is potassium.

[0420] In certain embodiments, the bi-functional aromatic catalyst is ZnCrCU

[0421] In certain preferred embodiments, the aromatic metal is zinc; the one or more aromatic metal additives is present, and wherein the one or more aromatic metal additives is gallium; and

[0422] the bi-functional aromatic catalyst comprises an aromatic catalyst support, wherein the bifunctional aromatic catalyst support is ZSM-5.

[0423] In certain embodiments, the bi-functional aromatic catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, DA- 114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain preferred embodiments, the zeolite is ZSM-5.

[0424] In further embodiments, the zeolite component further comprises a modifier, preferably Ga or Zn. In yet further embodiments, the zeolite component comprises from 0 wt% to about 2 wt% of the modifier. In still further embodiments, the zeolite component comprises from 0.01 wt% to about 2 wt% of the modifier. In certain embodiments, the zeolite component comprises from 0.1 wt% to about 1.5 wt% of the modifier. In some preferred embodiments, the zeolite component comprises from 0.5 wt% to about 1 wt% of the modifier.

[0425] In certain embodiments, the bi-functional aromatic catalyst comprises from about 10 wt% to about 90 wt% of the mixed oxide component and from about 90 wt% to about 10 wt% of the zeolite component. In further embodiments, the bi-functional aromatic catalyst comprises from about 25 wt% to about 75 wt% of the mixed oxide component and from about - 54 -

[0426] FH13166046.1Attorney Docket No.: CSW-02925

[0427] 75 wt% to about 25 wt% of the zeolite component. In certain preferred embodiments, the bifunctional aromatic catalyst comprises from about 40 wt% to about 60 wt% of the mixed oxide component and from about 60 wt% to about 40 wt% of the zeolite component.

[0428] In certain embodiments, the mixed oxide component comprises:

[0429] iron;

[0430] zinc in a molar ratio of from 0 to about 0.50 relative to iron;

[0431] Na, K, Cs, Mg, Ca, or a combination thereof, in a molar ratio of from 0 to about 0.10 relative to iron;

[0432] Cu, Cr, Mn, or a combination thereof, in a molar ratio of from 0 to about 0.60 relative to iron.

[0433] In some embodiments, the bi-functional aromatic catalyst comprises K in a molar ratio of from 0 to about 0.10 relative to iron. In certain preferred embodiments, the bi-functional aromatic catalyst comprises K in a molar ratio of about 0.036 relative to iron.

[0434] In certain aspects, the bi-functional aromatic catalysts further comprise an aromatic catalyst support. The aromatic catalyst support may be any suitable material that can serve as a catalyst support.

[0435] In some embodiments, the aromatic catalyst support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the aromatic catalyst support comprises y-alumina. In certain embodiments, the aromatic catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the aromatic catalyst support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the aromatic catalyst support is an aluminum oxide that is formed in-situ as part of the paraffin catalyst. In some embodiments, the aromatic catalyst support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the aromatic catalyst support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0436] In some embodiments, the aromatic 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.

[0437] - 55 -

[0438] FH13166046.1Attorney Docket No.: CSW-02925

[0439] In some embodiments, the aromatic catalyst support is selected from SiA10x, SC -ZrCh, zirconium tungstate, tungstated-titania, and anatases (SiCh-AhCh, SiCh-TiCh). In further embodiments, the aromatic catalyst support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0440] In some embodiments, the aromatic 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), mordenite zeolites, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In certain preferred embodiments, the aromatic catalyst support is ZSM-5. 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.

[0441] In some embodiments, the aromatic catalyst support is modified with molybdenum, chlorine, and / or sulfur.

[0442] In some embodiments, the aromatic catalyst support is a mesoporous material. In some embodiments, the aromatic catalyst support has a mesopore volume from about 0.01 to about 3.0 cc / g.

[0443] In some embodiments, the aromatic catalyst support has surface area from about 10 m2 / g to about 1000 m2 / g. In some preferred embodiments, the catalytic composition comprising the aromatic catalyst support and a catalyst disclosed herein has a surface area from about 10 m2 / g to about 1000 m2 / g.

[0444] In some embodiments, the catalytic composition is in a form of particles having an average size from about 10 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 20 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 1 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 100 nm to about 500 nm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 300 nm.

[0445] - 56 -

[0446] FH13166046.1Attorney Docket No.: CSW-02925

[0447] In some embodiments, the catalytic composition comprises from about 5 wt.% to about 80 wt.% of the bi-functional aromatic catalyst. In some embodiments, the catalytic composition comprises from about 5 wt.% to about 70 wt.% of the bi-functional aromatic catalyst. In some embodiments, the catalytic composition comprises from about 20 wt.% to about 70 wt.% of the bi-functional aromatic catalyst. In some embodiments, the catalytic composition comprises from about 30 wt.% to about 70 wt.% of the bi-functional aromatic catalyst.

[0448] In some embodiments, the support is a high surface area scaffold. In some embodiments, the support comprises mesoporous silica. In some embodiments, the support comprises carbon allotropes.

[0449] In some embodiments, the bi-functional aromatic catalyst is a nanoparticle catalyst. In some embodiments, the particle sizes of the bi-functional aromatic catalyst on the surface of the scaffold are about 1 nm to 5 nm. In some embodiments, the particle sizes of the bi-functional aromatic catalyst on the surface of the scaffold are about 5 nm to 100 nm. In some embodiments, the particle sizes of the bi-functional aromatic catalyst on the surface of the scaffold are 100-500 nm. In some embodiments, the particles not subjected to agglomeration are 100-500 nm in particle size.

[0450] Optional and preferred features of the invention relating to catalysts for conversion of carbon sources and reduction gas to aromatics described above may also constitute optional or preferred features in relation to catalysts for conversion of carbon sources to paraffins or catalysts for conversion of carbon source gases and reduction gases to linear alpha olefins, and vice versa.

[0451] In certain embodiments, bi-functional aromatic catalyst of the disclosure, such as those described above, is active in the conversion of a carbon source gas, such as CO2, to aromatics, and optionally may be any aromatic catalyst disclosed for this purpose in co-assigned U.S. Patent No. 12,018,221, and in WO 2024 / 064387, the entire contents of which are incorporated by reference herein in its entirety.

[0452] Alkylation

[0453] 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 - 57 -

[0454] FH13166046.1Attorney Docket No.: CSW-02925

[0455] 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.

[0456] 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.

[0457] 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.

[0458] Catalysts for Alkylation of Aromatics

[0459] 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.

[0460] 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.

[0461] - 58 -

[0462] FH13166046.1Attorney Docket No.: CSW-02925

[0463] Catalysts for Oligomerization

[0464] In certain aspects, the systems and methods of the present disclosure involve the use of oligomerization catalysts. As used herein, the term “oligomerization catalyst” refers to a catalyst used for the oligomerization of carbon sources.

[0465] The oligomerization catalyst may be a heterogeneous acid catalyst, such as a zeolite or a molecular sieve. The oligomerization catalyst may be an amorphous or crystalline aluminosilicate molecular sieve. The oligomerization catalyst may be a zeolite. The oligomerization catalyst may be an aluminosilicate zeolite. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, beta-zeolite, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. The oligomerization catalyst may be ZSM-5, beta-zeolite, MCM-22, MCM-49, PSH-3, mordenite, SAPO-5, or a combination thereof. The oligomerization catalyst may be selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof. The oligomerization catalyst may be ZSM-5.

[0466] The weight-based space velocity is measured as the amount of reactant mass per unit catalyst mass per unit time. The range for the weight-based space velocity for the oligomerization catalyst is between about 0.1 g of reactant per g of catalyst per hour (0.1 h-1) and about 50 h-1, or between about 0.5 h-1 to about 20 h-1.

[0467] In certain embodiments, an oligo-alkylation reactor is used, and a combination of one or more alkylation catalyst and one or more oligomerization catalysts may be combined within the oligo-alkylation reactor. The one or more alkylation catalyst and the one or more oligomerization catalysts may be mixed, layered within the reactor optionally with an intermediate quench. In other embodiments, an oligo-alkylation catalyst may be used. The oligo-alkylation catalyst may be a liquid acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), an amorphous heterogeneous acid catalyst, such as tungsten / Zr oxide, a heterogeneous acid catalyst, such as a zeolite or a molecular sieve, and a combination thereof. In some embodiments, the oligo-alkylation catalyst is an amorphous or crystalline aluminosilicate molecular sieve. In other embodiments, the oligo-alkylation catalyst is selected from the group consisting of: ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM- - 59 -

[0468] FH13166046.1Attorney Docket No.: CSW-02925

[0469] 23, ZSM-12, ZSM-57, ZSM-35, zeolite beta, a faujasite, a mordenite, SAPO-5, SAPO-11, a zeolite of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof. In further embodiments, the oligo-alkylation catalyst is ZSM-5, beta-zeolite, MCM-22, MCM-49, PSH-3, mordenite zeolite, SAPO-5, or any combination thereof.

[0470] Catalysts for Hydrogenation and Isomerization

[0471] In certain aspects, the systems and methods of the present disclosure involve the use of hydrogenation catalysts and / or isomerization catalysts for isomerizing or hydrogenating percentages of the hydrocarbons produced, respectively. In certain embodiments, the hydrogenation catalysts and isomerization catalysts of the disclosure may be independently selected from the catalysts described below.

[0472] The isomerization catalyst and / or the hydrogenation catalyst of the present disclosure may be an aluminosilicate catalyst, such as a zeolite. The isomerization catalyst and / or the hydrogenation catalyst of the present disclosure may be a tungsten zirconate, phosphate, or sulfate e.g., WOx / ZrOx In further embodiments, the isomerization catalyst and / or the hydrogenation catalyst is AlCh. In yet further embodiments, the isomerization catalyst and / or the hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In still further embodiments, the isomerization catalyst and / or the hydrogenation catalyst is Pt on beta-zeolite. In certain embodiments, isomerization catalysts and / or hydrogenation catalysts of the disclosure comprise an isomerization catalyst metal, and a zeolite support. In further embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo.

[0473] In certain aspects, the isomerization catalysts further comprise an additional support. The additional support may be any suitable material that can serve as a catalyst support.

[0474] The additional support may comprise one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the additional support comprises y-alumina. In certain embodiments, the additional support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is selected from alumina - 60 -

[0475] FH13166046.1Attorney Docket No.: CSW-02925

[0476] (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the additional support is an aluminum oxide that is formed in-situ as part of the paraffin catalyst. In some embodiments, the additional support is selected from, but not limited to, MgO, AI2O3, ZrCh, SnCh, SiCh, ZnO, WO3, and TiCh. In some embodiments, the additional support is selected from MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2.

[0477] The hydrogenation catalyst support may comprise: A) one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin, such as MgO, AI2O3, ZrO2, SnO2, SiO2, ZnO, WO3, silica carbide, and TiO2; B) a carbon-based material such as activated carbon, carbon nanotubes, graphene, and graphene oxide;

[0478] C) SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2); D) an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites; or E) a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. Optionally, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals; and / or optionally the modifier is present as a zeolite-supported metal or as isomorphous substitution in the zeolite framework.

[0479] The additional support may include one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0480] The additional support may be selected from SiAlOx, SO4-ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2). In further embodiments, the additional support is an aluminum-based material such as alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites.

[0481] The additional support may be a zeolite such as Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In - 61 -

[0482] FH13166046.1Attorney Docket No.: CSW-02925

[0483] further embodiments, the zeolites comprise additional metals such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the additional metals are present as zeolite supported metals or as isomorphous substitution in the zeolite framework. The additional support may be modified with molybdenum, chlorine, and / or sulfur.

[0484] In still further embodiments, the isomerization catalyst and the hydrogenation catalyst are independently selected from Pt / ZrCh / WCh, Pt / ZrWC , Pt / SiA10x, Pt / SC -ZrCh, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiA10x, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, Ni-W / SAPO, and any combination thereof. In certain certain preferred embodiments, the isomerization catalyst is Pt / ZrCh / WCh. In other preferred embodiments, the isomerization catalyst is Pt / SAPO comprising 0.2 wt% Pt.

[0485] In certain embodiments, the isomerization metal comprises from about 0.5 wt% to about 40 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In further embodiments, the isomerization metal comprises about 0.5 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In yet further embodiments, the isomerization metal comprises about 1 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In still further embodiments, the isomerization metal comprises about 10 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In certain embodiments, the isomerization metal comprises about 20 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In further embodiments, the isomerization metal comprises about 30 wt% of the isomerization catalyst and / or the hydrogenation catalyst. In yet further embodiments, the isomerization metal comprises about 40 wt% of the isomerization catalyst and / or the hydrogenation catalyst.

[0486] In certain embodiments, when the isomerization catalyst is Pt / A12O3, the isomerization temperature is about 250 °C and the isomerization pressure is about 750 psi. In certain embodiments, when the isomerization catalyst is a zeolite-based catalyst, the isomerization temperature is about 300 °C and the isomerization pressure is about 750 psi.

[0487] Catalysts for Hydrocracking

[0488] 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.

[0489] - 62 -

[0490] FH13166046.1Attorney Docket No.: CSW-02925

[0491] 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.

[0492] In certain embodiments, the blended product, or any intermediate product, may be subjected to hydrocracking. 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.

[0493] In further embodiments, the hydrocracking catalyst comprises an hydrocracking metal, such as Pd, Pt, Ni, Co, Co-W, Ni-W, and Ni-Mo, and an additional support. The additional support may be any suitable material that can serve as a catalyst support.

[0494] In some embodiments, the hydrocracking support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten, and tin. In some preferred embodiments, the additional 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 paraffin 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.

[0495] In some embodiments, the hydrocracking support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0496] 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.,

[0497] - 63 -

[0498] FH13166046.1Attorney Docket No.: CSW-02925

[0499] y-alumina), boehmite, crystalline boehmite, pseudoboehmites, gibbsites, and thermally shocked gibbsites.

[0500] 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), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof. In further embodiments, the zeolites comprise a modifier such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the modifier is present as a zeolite supported metals or as isomorphous substitution in the zeolite framework.

[0501] In some embodiments, the additional support is modified with molybdenum, chlorine, and / or sulfur.

[0502] 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.

[0503] Reduction Gases, Carbon Source Gases, and Ratios Thereo f

[0504] 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.

[0505] - 64 -

[0506] FH13166046.1Attorney Docket No.: CSW-02925

[0507] 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 the aromatic reactor.

[0508] In certain embodiments, the first reduction gas, the second reduction gas, when present, and the third 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.

[0509] In certain embodiments, the first reduction gas, the second reduction gas, and the third reduction gas is H2. In further embodiments, the first reduction gas, the second reduction gas, and the third reduction gas is synthesis gas. In yet further embodiments, the first reduction gas, the second reduction gas, and the third reduction gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In still further embodiments, the first reduction gas, the second reduction gas, and the third reduction gas is, or is derived from, flare gas, waste gas, or natural gas. In certain embodiments, the first reduction gas, the second reduction gas, and the third reduction gas is CH4.

[0510] In certain embodiments, the carbon source gas is CO2. In further embodiments, the carbon source gas comprises CO2. In yet further embodiments, the carbon source gas is CO. In still further embodiments, the carbon source gas comprises CO.

[0511] 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.

[0512] 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 carbon source gas is from about 10:1 to about 1:10, or about 10:1 to about 1:1. In further embodiments, the molar ratio of the first reduction gas to the carbon source gas is from about 5:1 to about 0.5:1, or about 4:1 to about 2:1.

[0513] - 65 -

[0514] FH13166046.1Attorney Docket No.: CSW-02925

[0515] Definitions

[0516] 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.

[0517] 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).

[0518] 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).

[0519] 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.

[0520] 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.

[0521] 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).

[0522] 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 - 66 -

[0523] FH13166046.1Attorney Docket No.: CSW-02925

[0524] 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.

[0525] 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).

[0526] 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.

[0527] 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.

[0528] EXAMPLES

[0529] 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

[0530] - 67 -

[0531] FH13166046.1Attorney Docket No.: CSW-02925

[0532] certain aspects and embodiments of the present invention, and are not intended to limit the invention.

[0533] EXAMPLE 1 : CO2 Hydrogenation to Methanol

[0534] CO2 hydrogenation was performed in a fixed bed flow reactor with approximately 9 liters of internal volume. The flow reactor was loaded with 10 kilograms of a catalyst composed of 63% by weight copper oxide, 27% by weight zinc oxide, and 10% by weight aluminum oxide and pressed into cylinders with 6 mm height and 4 mm diameter. The reactor was heated to approximately 250 °C. while 5% H2 in N2 gas flowed through the reactor at a flow rate of 40 standard liters per minute (SLPM) at a pressure of 100 psi to activate the catalyst. Water was collected at the separator down-stream from the flow reactor during this activation time. Following catalyst activation, the temperature of the reactor was maintained to 250 °C. and pressure was increased to 950 psi. H2 and CO2 mixture (3:1 mole ratio) flowed through the reactor at flow rates of 40 SLPM. The gases were reacted at the surface of the catalyst to produce approximately 0.4 liters per hour of a methanol water mixture with a density of 0.89 g / mL, corresponding to approximately 64% methanol in water, thus achieving quantitative selectivity for methanol production. Unreacted gases were recycled through the reactor by way of a recycle loop and compressor.

[0535] EXAMPLE 2: Methanol to Olefins using SAPO and Metal apos

[0536] Methanol to olefin producing ethylene, propylene, and other hydrocarbons is accomplished in a fixed bed flow reactor. The flow reactor was loaded with 10 kg of a silicoa-luminophosphate catalyst, H-SAPO-34, which is a chabazite structured material comprised of 50% by weight aluminum oxide, 30-45% by weight phosphorous oxide, and 20-5% by weight silicon oxide. The reactor was heated to a temperature of 450 °C. A feed mixture of 40% methanol and 60% water was heated to over 180 °C. to vaporize the methanol and water, then was introduced to the reactor at 50 PSI and a weight hourly space velocity of 5.0 / h. The methanol was converted to a mixture of ethylene, propylene, butenes, pentenes, other paraffins and olefins, and aromatics, with the major product being ethylene and propylene. Ethylene and propylene were separated from other products by distillation. The SAPO catalyst was regenerated after the conversion of methanol dropped below 90%. The reactor was heated to - 68 -

[0537] FH13166046.1Attorney Docket No.: CSW-02925

[0538] 650 °C. and the air was fed into reactor at 0.75 mL / min. The reactor was then cooled down to 450 °C to resume methanol-to-olefin processing.

[0539] EXAMPLE 3 : Olefin Oligomerization using Zeolites

[0540] The oligomerization process was carried out continuously by passing the C3+ olefinic feedstock through a fixed bed comprising a zeolite catalyst. The oligomerization process was performed within a temperature range of 100 °C to 225 °C. The pressure was maintained in the range of 20 to 80 bar. The weight-based space velocity refers to the amount of reactant mass per unit catalyst mass per unit time, and it was varied between 0.5 to 4 h’1. In a typical example, 2 g of H-form of PSH-3 was diluted with silicon carbide to obtain a bed volume of 8 cm3. The mixture was loaded into a down-flow stainless-steel fixed bed reactor, and 1 -hexene feedstock was processed at a temperature of 150° C, a pressure of 35 bar, and WHSV=2 h'1based on 1-hexene. The liquid product withdrawn from the pot after 24 h was analyzed by GC-FID to determine its composition. It was found that 75 %, by weight, of hexene that was charged to the reactor had been converted into dimers and trimers of hexene, of which 95%, by weight, of the oligomerization reaction products were dimers and trimers of hexene.

[0541] EXAMPLE 4: Ethylene Oligomerization using Homogenous Catalyst and SHOP

[0542] The first step in this process is the ethylene oligomerization to a mixture of even-numbered a-olefins at 80 °C to 120 °C and 70 bar to 140 bar (7 to 14 MPa) catalyzed by a nickel-phosphine complex. The generated alpha-olefin was separated from the solvent (acetonitrile) and then fractionated to feed into next process of oligomerization or hydrogenation. The catalyst was dissolved in solvent to be recycled.

[0543] EXAMPLE 5: Aromatization of C3

[0544] C3 olefin aromatization (minor amounts of C4 and C5 aromatics were present in feed) was performed in a fixed bed reactor with a ’A inch outer diameter. Each reactor tube was loaded with 2 grams of catalyst, with the rest of the volume being an inert material, such as quartz wool or silicon carbide. The reaction was performed over an acid catalyst with metal modification. Z was used as the base catalyst, with a silica to alumina ratio of 40. The metal addition ranges from 0.5-1.0 wt % of zinc, iron, gallium, or phosphorous, not excluding a - 69 -

[0545] FH13166046.1Attorney Docket No.: CSW-02925

[0546] combination of these metals. A swing bed reactor was operated at 500 °C while a partial pressure of 14 psi olefins out of total operative pressure 50 psi mixture is fed to the acid catalyst at a reactant WHSV of 8.5 hr- 1. This feed can contain an inert feed, such as N2. The gases react at the surface of the catalyst to produce approximately 7 grams of oil per hour, which is collected at a separator down-stream from the reactor.

[0547] EXAMPLE 6: Hydrogenation of iso paraffin / n-paraffins / aromatic blend

[0548] The mix stream of C2 oligomerization, C3 oligomerization and C4+ aromatization and alkylation was fed into the olefin hydrogenation in a / i in O.D. fixed bed reactor. The reactor was loaded with 4 g of catalyst, Palladium on alumina tablet, with the rest of the volume being an inert material, such as silicon carbide. The reaction was performed at 150 °C with a pressure of 100 psig, the liquid feed was under a WHSV of 3.0 h’1. The collected liquid is the pre-blend mixture of jet fuel with paraffins and aromatics.

[0549] The stream of C4+ aromatization and alkylation was fed into the aromatic hydrogenation in a / i in O.D. fixed bed reactor. The reactor was loaded with 4 g of catalyst, Palladium on alumina tablet, with the rest of the volume being an inert material, such as silicon carbide. The reaction was performed at 250 °C with a pressure of 300 psig, the liquid feed was under a WHSV of 1.0 h’1. The collected liquid is the pre-blend mixture of jet fuel with rich cycloparaffins.

[0550] EXAMPLE 7: Aromatics Alkylation

[0551] The alkylation process was performed continuously passing a mixture of olefin and aromatic through a fixed bed reactor containing a zeolite catalyst. Alkylation was done at a temperature range of 100 to 225 °C, and pressure between 20 to 80 bar. The weight-based space velocity was kept between 0.5 to 4 h-1. The H-form of PSH-3 zeolite was pelletized into particle sizes of 0.25-0.4 mm. 2 g of this pelletized sample was diluted with silicon carbide to obtain a bed volume of 8 cm3. The mixture was loaded into a down-flow stainless-steel fixed bed reactor, and toluene and 1 -hexene at a mole ratio of 1 was fed at a temperature of 150 °C, a pressure of 35 bar, and WHSV=5.0 h'1based on total feed. The liquid product withdrawn from the gas-liquid separator pot after 24 h was analyzed by GC-FID to determine the reactant conversion and product selectivity. It was found that 96 %, by weight, of the - 70 -

[0552] FH13166046.1Attorney Docket No.: CSW-02925

[0553] hexene feed to the reactor was reacted with toluene and formed specifically mono-hexyl substituted toluene and di-hexyl substituted toluene, of which 85%, by weight, of the alkylation reaction products being mono-hexyl substituted toluene.

[0554] EXAMPLE 8: Mixing Jet fuel from Aromatic and Paraffin SAF

[0555] I. 160 gallons of fuel mixture made through the technology from the process described herein is mixed with 120 gallons of fuel mixture made from CO2 using the technology described in Example 5 and Example 7. Among the 160 gallons of the paraffinic jet fuel, 100 gallons are iso-paraffins, and 60 gallons are n-paraffins, ensured by controlling the hydro-isomerization conditions of paraffins. Among the 120 gallons of fuel mixture from CO2, 80 gallons are cycloparaffins, and 40 gallons are aromatics by controlling the aromatic hydrogenation conditions. Hence, this exemplary blended jet fuel has the composition of:

[0556] Linear paraffins: 21.4 v%

[0557] Branched paraffins: 35.7 v%

[0558] Cycloparaffins: 28.6 v%

[0559] Aromatics: 14.3 v%

[0560] Polycyclic aromatics < 1 v%

[0561] Indanes and Tetralins < 1 v%

[0562] II. 200 gallons of jet fuel made through the technology from the present disclosure is mixed with 200 gallons of jet fuel made from CO2 using the technology described in Example 5 and Example 7. Among the 200 gallons of the paraffinic jet fuel, 120 gallons are iso-paraffins, and 80 gallons are normal paraffins by controlling the hydro-isomerization conditions of paraffins. Among the 200 gallons of jet fuel made from CO2, 160 gallons are cycloparaffins, and 40 gallons are aromatics by controlling the aromatic hydrogenation conditions. Hence, the blended jet fuel has the composition of:

[0563] Linear paraffins: 20 v%

[0564] Branched paraffins: 30 v%

[0565] Cycloparaffins: 40 v%

[0566] Aromatics: 10 v%

[0567] Polycyclic aromatics < 1 v%

[0568] - 71 -

[0569] FH13166046.1Attorney Docket No.: CSW-02925

[0570] Indanes and Tetralins < 1 v%

[0571] INCORPORATION BY REFERENCE

[0572] 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.

[0573] EQUIVALENTS

[0574] 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.

[0575] - 72 -

[0576] FH13166046.1

Claims

WHAT IS CLAIMED1. A method for producing aviation fuel from a carbon source gas comprising:contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;contacting the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;contacting the medium olefin product mixture, the heavy olefin product mixture, or both of the medium and heavy olefin product mixtures with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;contacting the medium olefin product mixture, the heavy olefin product mixture, or both of the medium and heavy olefin product mixtures with an aromatic catalyst to afford an aromatic product mixture;blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

2. The method of claim 1, further comprising contacting a first portion of the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture.

3. The method of claim 2, further comprising blending the target alkyl arene product mixture with the paraffin product mixture and the aromatic product mixture to afford the blended fuel product mixture.

4. The method of any one of claims 1-3, further comprising contacting a second portion of the aromatic product mixture with the hydrogenation catalyst to afford cycloparaffins in the paraffin product mixture.- 73 -FH13166046.

15. The method of any one of the preceding claims, further comprising contacting at least a portion of the target alkyl arene product mixture with the hydrogenation catalyst to afford cycloparaffins in the paraffin product mixture.

6. The method of any one of the preceding claims, wherein the paraffin product mixture comprises linear paraffins, branched paraffins, and cycloparaffins.

7. The method of any one of the preceding claims, further comprising processing at least a first portion of the light olefin product mixture via ethylene oligomerization and olefin metathesis to afford long-chain olefins.

8. The method of claim 7, further comprising contacting the long-chain olefins with the hydrogenation catalyst to afford linear paraffins in the paraffin product mixture.

9. The method of any one of the preceding claims, further comprising contacting at least a second portion of the light olefin product mixture with: i) the aromatic catalyst to afford the aromatic product mixture, ii) the alkylation catalyst to afford the target alkyl arene product mixture, or iii) the aromatic catalyst and the alkylation catalyst to afford the target alkyl arene product mixture.

10. The method of any one of the preceding claims, wherein the ATO catalyst comprises alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

11. The method of any one of the preceding claims, wherein the ATO catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate.

12. The method of claim 11, wherein the fluid catalyst particles comprise SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, orZSM-34.- 74 -FH13166046.

113. The method of any one of the preceding claims, wherein the oligomerization catalyst is a zeolite or molecular sieve.

14. The method of any one of the preceding claims, wherein the oligomerization catalyst is an amorphous or crystalline aluminosilicate molecular sieve.

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

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

17. The method of claim 16, wherein the alkylation catalyst is a zeolite.

18. The method of claim 16 or 17, wherein the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g, SAPO-5, SAPO-11, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolites, DA-114, microcrystalline USY zeolite, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

19. The method of any one of the preceding claims, wherein the aromatic catalyst comprises a zeolite.

20. The method of claim 19, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49,- 75 -FHl 3166046.1MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and any combination thereof.

21. The method of claim 19 or 20, wherein the zeolite has a silicon to aluminum ratio (SAR) of about 30 to about 1000.

22. The method of any one of claims 19-21, wherein the zeolite comprises a modifier.

23. The method of claim 22, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt, or a combination thereof.

24. The method of any one of the preceding claims, wherein the reduction catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or alloys or any combination thereof.

25. The method of any one of the preceding claims, wherein the reduction catalyst comprises alloys of copper and zinc in nanoparticulate form.

26. The method of any one of the preceding claims, wherein the hydrogenation catalyst comprises an isomerization metal and a hydrogenation catalyst support.

27. The method of claim 26, wherein the hydrogenation catalyst is selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, Ni-W / SAPO, and any combination thereof.

28. The method of any one of the preceding claims, wherein the first reduction gas, and / or the second 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.- 76 -FH13166046.

129. The method of any one of the preceding claims, wherein the first reduction gas and / or the second reduction gas, when present, comprises H2.

30. The method of any one of the preceding claims, wherein the carbon source gas comprises CO2.

31. The method of any one of the preceding claims, wherein the oligomerized product mixture comprises Cs-Ci6 branched olefins.

32. The method of any one of the preceding claims, wherein the oligomerized product comprises unsaturated Cs-Ci6 hydrocarbons.

33. The method of any one of the preceding claims, wherein the paraffin product mixture comprises Cs-i6 hydrocarbons.

34. The method of any one of the preceding claims, wherein the blended fuel product mixture comprises Cs-i6 hydrocarbons.

35. The method of claim 33 or 34, wherein the Cs-i6 hydrocarbons include linear paraffins, branched paraffins, aromatics, and naphthenes.

36. The method of any one of the preceding claims, wherein the blended fuel product mixture comprises about 10% to about 20% aromatics.

37. The method of any one of the preceding claims, wherein the aromatic product mixture comprises from about 0 wt% to about 2 wt% polycyclic aromatics.

38. 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 to afford an alcohol product stream;- 77 -FH13166046.1an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;an optional second reduction gas feed;an optional second carbon source feed;an aromatic reactor comprising an aromatic catalyst, said aromatic reactor having a heavy olefin product inlet and an aromatic product outlet, and optionally also having a second reduction gas inlet, and a second carbon source feed inlet,wherein the heavy olefin product inlet is coupled to the heavy olefin product outlet of the ATO reactor; andwherein optionally the aromatic reactor may include a light olefin product inlet coupled to the heavy light product outlet of the ATO reactor;an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet,wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; anda blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.- 78 -FH13166046.

139. The system of claim 38, wherein the hydrogenation reactor further comprises an aromatic product inlet coupled to the aromatic reactor.

40. The system of claim 38 or 39, wherein the hydrogenation reactor further comprises a target alkyl arene product inlet coupled to the alkylation reactor.

41. The system of any one of claims 38-40, further comprising ethylene oligomerization to afford a long-chain olefin product;wherein the system is configured to direct the long-chain olefin product to the hydrogenation reactor.

42. The system of claim 41, wherein the ethylene oligomerization is a shell higher olefin process system having a light olefin product inlet and a long-chain olefin product outlet; and the hydrogenation reactor comprises a long-chain olefin product inlet coupled to the long-chain olefin product outlet.

43. The system of any one of claims 38-42, further comprisinga separator having an aromatic product inlet, optionally a recycle gas outlet, and a separated product outlet, wherein the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the separator and the separated product outlet is coupled to the aromatic product inlet of the hydrogenation reactor.

44. The system of claim 43, wherein the recycle gas outlet, when present, is coupled to the first reduction gas feed, the second reduction gas feed, and / or the first carbon source gas feed.

45. The system of any one of claims 38-44, wherein the ATO reactor is a fixed-bed reactor.

46. The system of any one of claims 38-45, wherein the ATO catalyst comprises activated AI2O3.- 79 -FHl 3166046.

147. The system of any one of claims 38-46, wherein the ATO catalyst comprises alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

48. The system of any one of claims 38-44, wherein the ATO reactor is a fluidized bed reactor and the ATO catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate.

49. The system of claim 48, wherein the fluid catalyst particles comprise SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, orZSM-34.

50. The system of any one of claims 38-49, wherein the oligomerization catalyst is a zeolite.

51. The system of any one of claims 38-50, wherein the oligomerization catalyst is selected from MCM-22, MCM-49, PSH-3, ZSM-5, ZSM-11, ZSM-22, ZSM-23, and ZSM-35.

52. The system of any one of claims 38-51, wherein the alkylation catalyst is an acid, such as HF, SPA (solid phosphoric acid), a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), tungsten, platinum, or a zeolite.

53. The system of claim 52, wherein the alkylation catalyst is a zeolite.

54. The system of claim 53, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e g., SAPO-5, SAPO-11, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolites, DA-114, microcrystalline USY zeolite, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.- 80 -FHl 3166046.

155. The system of any one of claims 38-54, wherein the aromatic catalyst comprises a zeolite.

56. The system of claim 55, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), L zeolite (LTL), mordenite zeolites, MCM-49, MCM-22, PSH-3, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and any combination thereof.

57. The system of claim 55 or 56, wherein the zeolite has a silicon to aluminum ratio (SAR) of about 30 to about 1000.

58. The system of any one of claims 55-57, wherein the zeolite comprises a modifier.

59. The system of claim 58, wherein the modifier is selected from Ga, Fe, Mn, Zn, P, Pt, or a combination thereof.

60. The system of any one of claims 38-59, wherein the reduction catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, alloys thereof, or any combination thereof.

61. The system of any one of claims 38-60, wherein the hydrogenation catalyst comprises an isomerization metal, and a hydrogenation catalyst support.

62. The system of claim 61, wherein the hydrogenation catalyst is selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, Ni-W / SAPO, and any combination thereof.

63. A method for producing aviation fuel from a carbon source gas comprising:contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;- 81 -FH13166046.1contacting a first portion of the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;contacting the medium olefin product mixture and the heavy olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;contacting a second portion of the alcohol product stream with an ATA catalyst at an ATA temperature and an ATA pressure to afford an aromatic product mixture;blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

64. A method for producing aviation fuel from a carbon source gas comprising:contacting a reduction gas and the carbon source gas with a reduction catalyst to afford an alcohol product stream comprising methanol;contacting the alcohol product stream with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising a light olefin product mixture, a medium olefin product mixture and a heavy olefin product mixture;contacting the medium olefin product mixture and the heavy olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising branched olefins;contacting the oligomerized product mixture with a hydrogenation catalyst to afford a paraffin product mixture;contacting a second reduction gas and a second carbon source gas with a bi-functional aromatic catalyst to afford an aromatic product mixture;blending the paraffin product mixture with the aromatic product mixture to afford a blended fuel product mixture.

65. The method of claim 63 or 64, further comprising contacting a first portion of the aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture.- 82 -FH13166046.

166. The method of claim 65, further comprising blending the target alkyl arene product mixture with the paraffin product mixture and the aromatic product mixture to afford the blended fuel product mixture.

67. The method of any one of claims 63-66, further comprising contacting a portion of the aromatic product mixture with the hydrogenation catalyst to afford cycloparaffins in the paraffin product mixture.

68. The method of any one of claims 63-67, further comprising contacting at least a portion of the target alkyl arene product mixture with the hydrogenation catalyst to afford cycloparaffins in the paraffin product mixture.

69. The method of any one of claims 63-68, wherein the paraffin product mixture comprises linear paraffins, branched paraffins, and cycloparaffins.

70. The method of any one of claims 63-69, further comprising processing at least a first portion of the light olefin product mixture via ethylene oligomerization and olefin metathesis to afford long-chain olefins.

71. The method of claim 70, further comprising contacting the long-chain olefins with the hydrogenation catalyst to afford linear paraffins in the paraffin product mixture.

72. The method of any one of claims 65-71, further comprising contacting at least a second portion of the light olefin product mixture with the alkylation catalyst to afford the target alkyl arene product mixture.

73. The method of any one of claims 63-72, wherein the oligomerized product mixture comprises Cs-Ci6 branched olefins.

74. The method of any one of claims 63-73, wherein the oligomerized product comprises unsaturated Cs-Ci6 hydrocarbons.- 83 -FH13166046.

175. The method of any one of claims 63-74, wherein the paraffin product mixture comprises Cs-i6 hydrocarbons.

76. The method of any one of claims 63-75, wherein the blended fuel product mixture comprises Cs-i6 hydrocarbons.

77. The method of claim 75 or 76, wherein the Cs-i6 hydrocarbons include linear paraffins, branched paraffins, aromatics, and naphthenes.

78. The method of any one of claims 63-77, wherein the blended fuel product mixture comprises about 10% to about 20% aromatics.

79. The method of any one of claims 63-78, wherein the aromatic product mixture comprises from about 0 wt% to about 2 wt% polycyclic aromatics.

80. The method of any one of claims 63-79, wherein the ATO catalyst comprises alumina, boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

81. The method of any one of claims 63-80, wherein the ATO catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate.

82. The method of claim 81, wherein the fluid catalyst particles comprise SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, orZSM-34.

83. The method of any one of claims 63-82, wherein the oligomerization catalyst is a zeolite or molecular sieve.

84. The method of any one of claims 63-82, wherein the oligomerization catalyst is an amorphous or crystalline aluminosilicate molecular sieve.- 84 -FH13166046.

185. The method of any one of claims 63-82, wherein the oligomerization catalyst comprises a zeolite selected from ZSM-5, ZSM-11, ZSM-22, Theta-1, ZSM-23, ZSM-12, ZSM-57, ZSM-35, beta-zeolite, faujasites, mordenite zeolite, SAPO-5, SAPO-11, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, or a combination thereof.

86. The method of any one of claims 63-85, wherein the alkylation catalyst is an acid, such as HF, solid phosphoric acid, a Friedel -Crafts alkylation catalyst (e.g., HF / AlCh), tungsten, platinum, or a zeolite.

87. The method of claim 86, wherein the alkylation catalyst is a zeolite.

88. The method of claim 85 or 86, wherein the zeolite is selected from Y-type zeolites, beta-zeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g, SAPO-5, SAPO-11, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolites, DA-114, microcrystalline USY zeolite, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

89. The method of any one of claims 63-88, wherein the reduction catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, alloys thereof, or any combination thereof.

90. The method of any one of claims 63-89, wherein the reduction catalyst comprises alloys of copper and zinc in nanoparticulate form.

91. The method of any one of claims 63-90, wherein the hydrogenation catalyst comprises an isomerization metal, such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and a hydrogenation catalyst support.- 85 -FH13166046.

192. The method of claim 91, wherein the hydrogenation catalyst is selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, Ni-W / SAPO, and any combination thereof.

93. The method of any one of claims 63-92, wherein the first reduction gas, and / or the second 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.

94. The method of any one of claims 63-93, wherein the first reduction gas and / or the second reduction gas, when present, comprises H2.

95. The method of any one of claims 63-94, wherein the carbon source gas comprises CO2.

96. The method of any one of claims 64-95, wherein the bi-functional aromatic catalyst comprises:one or more aromatic metals;optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII aromatic metal additives; andoptionally a Group IA or IIA metal promoter.

97. The method of any one of claims 64-96, wherein the bi-functional aromatic catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising a zeolite.

98. The method of claim 97, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and any combination thereof.- 86 -FH13166046.

199. The method of claim 98, wherein the zeolite is ZSM-5.

100. The system of claim 98 or 99, wherein the zeolite component further comprises a modifier, such as Ga or Zn.

101. The method of any one of claims 63, 65-100, wherein the ATA catalyst comprises an optionally metal-modified molecular sieve.

102. The method of claim 101, wherein the ATA catalyst comprises ZSM-5 and at least one metal from Groups 8-14 of the Periodic Table.

103. 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 to afford an alcohol product stream;an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;optionally a second reduction gas feed;optionally a second carbon source feed;an aromatic reactor having an aromatic product outlet,- 87 -FH13166046.1wherein (i) when the aromatic reactor is loaded with an ATA catalyst, the aromatic reactor comprises an ATA inlet coupled to the alcohol product stream;(ii) when the aromatic reactor is loaded with an aromatic catalyst, the aromatic reactor comprises a heavy olefin product inlet coupled to the heavy olefin product outlet on the ATO reactor; or(iii) when the aromatic reactor is loaded with a bi-functional catalyst, the aromatic reactor comprises a second reduction gas inlet, and a second carbon source feed inlet; and optionally an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet, wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; anda blender having a paraffin product inlet, an aromatic product inlet, and optionally a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and when present, the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

104. 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 to afford an alcohol product stream;an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the - 88 -FH13166046.1oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;a second reduction gas feed;a second carbon source feed;an aromatic reactor comprising a bi-functional aromatic catalyst, said aromatic reactor having an aromatic product outlet, a second reduction gas inlet, and a second carbon source feed inlet, wherein the second reduction gas feed is coupled to the second reduction gas feed inlet, and the second carbon source feed is coupled to the second carbon source feed inlet; andan alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet, wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; anda blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

105. 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 to afford an alcohol product stream;an alcohol to olefins (ATO) reactor comprising an ATO catalyst, said ATO reactor having an alcohol inlet and a light olefin product outlet, a medium olefin product outlet, and a heavy olefin product outlet, wherein the alcohol product stream is coupled to the alcohol inlet;an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium olefin product inlet and an oligomerized product outlet, wherein the medium olefin product outlet on the ATO reactor is coupled to the medium olefin product inlet of the oligomerization reactor;- 89 -FH13166046.1a hydrogenation reactor comprising a hydrogenation catalyst, said hydrogenation reactor having an oligomerization product inlet and a paraffin product outlet, wherein the oligomerization product outlet on the oligomerization reactor is coupled to the oligomerization product inlet of the hydrogenation reactor;an aromatic reactor comprising an ATA catalyst, said ATA reactor having an ATA inlet and an aromatic product outlet, wherein the alcohol product stream is coupled to the ATA inlet;an alkylation reactor comprising an alkylation catalyst, said alkylation reactor having an aromatic product inlet and a target alkyl arene outlet,wherein the aromatic product inlet is coupled to the aromatic product outlet of the aromatic reactor; anda blender having a paraffin product inlet, an aromatic product inlet, and a target alkyl arene product inlet and a fuel product outlet, wherein the paraffin product outlet of the hydrogenation reactor is coupled to the paraffin product inlet of the blender; the aromatic product outlet of the aromatic reactor is coupled to the aromatic product inlet of the blender; and the target alkyl arene product outlet of the alkylation reactor is coupled to the target alkyl arene product inlet of the blender.

106. The system of any one of claims 103-105, wherein the hydrogenation reactor further comprises an aromatic product inlet coupled to the aromatic reactor.

107. The system of any one of claims 103-106, wherein the hydrogenation reactor further comprises a target alkyl arene product inlet coupled to the alkylation reactor.

108. The system of any one of claims 38, 103, 104 or 105, further comprising one or more additional hydrogenation reactors.

109. The system of claim 108, wherein the system comprises a first additional hydrogenation reactor comprising an aromatic product inlet coupled to the aromatic reactor, and a second additional hydrogenation reactor comprising a target alkyl arene product inlet coupled to the alkylation reactor.- 90 -FH13166046.1110. The system of any one of claims 103-109, further comprising ethylene oligomerization coupled to the light olefin product outlet on the ATO reactor to afford a long-chain olefin product;wherein the system is configured to direct the long-chain olefin product to the hydrogenation reactor.

111. The system of claim 110, wherein the ethylene oligomerization is a shell higher olefin process system having a light olefin product inlet and a long-chain olefin product outlet; and the hydrogenation reactor comprises a long-chain olefin product inlet coupled to the long-chain olefin product outlet.

112. The system of any one of claims 103-111, wherein the ATO reactor is a fixed-bed reactor.

113. The system of any one of claims 103-112, wherein the ATO catalyst comprises activated AI2O3.

114. The system of any one of claims 103-113, wherein the ATO catalyst comprises alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

115. The system of any one of claims 103-111, wherein the ATO reactor is a fluidized bed reactor and the ATO catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate.

116. The system of claim 115, wherein the fluid catalyst particles comprise SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, orZSM-34.

117. The system of any one of claims 103-116, wherein the oligomerization catalyst is a zeolite.- 91 -FH13166046.1118. The system of claim 117, wherein the oligomerization catalyst is selected from MCM-22, MCM-49, PSH-3, ZSM-5, ZSM-11, ZSM-22, ZSM-23, and ZSM-35.

119. The system of any one of claims 103-118, wherein the alkylation catalyst is an acid, solid phosphoric acid, a Friedel -Crafts alkylation catalyst (e.g., HF / AICI3), tungsten, platinum, or a zeolite.

120. The system of claim 119, wherein the alkylation catalyst is a zeolite.

121. The system of claim 120, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, ZSM-11, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e g., SAPO-5, SAPO-11, SAPO-31, SAPO-41), L zeolite (LTL), mordenite zeolites, DA-114, microcrystalline USY zeolite, zeolites of the MWW structural type, such as MCM-22, MCM-36, MCM-49, PSH-3, and MCM-56, and any combination thereof.

122. The system of any one of claims 103-121, wherein the reduction catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or alloys or any combination thereof.

123. The system of any one of claims 103-122, wherein the hydrogenation catalyst comprises an isomerization metal, such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and a hydrogenation catalyst support.

124. The system of claim 123, wherein the hydrogenation catalyst is selected from Pt / ZrO2 / WO3, Pt / ZrWO4, Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22, Ni-W / SAPO, and any combination thereof.

125. The system of any one of claims 103-124, wherein the aromatic reactor is a fluidized-bed reactor.- 92 -FH13166046.1126. The system of any one of claims 103, 104 or 106-125, wherein the bi-functional aromatic catalyst comprises:one or more aromatic metals;optionally one or more Group VI, VII, VIII, IX, X, XI, or XIII aromatic metal additives; andoptionally a Group IA or IIA metal promoter.

127. The system of any one of claims 103, 104 or 106-125, wherein the bi-functional aromatic catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising a zeolite.

128. The system of claim 127, wherein the zeolite is selected from Y-type zeolites, betazeolites, ZSM-type zeolites (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite zeolites, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and any combination thereof.

129. The system of claim 128, wherein the zeolite is ZSM-5.

130. The system of any one of claims 127-129, wherein the zeolite component further comprises a modifier, such as Ga or Zn.

131. The system of any one of claims 103 or 105-125, wherein the ATA catalyst comprises an optionally metal-modified molecular sieve.

132. The system of claim 131, wherein the ATA catalyst comprises ZSM-5 and at least one metal from Groups 8-14 of the Periodic Table.- 93 -FH13166046.1

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