CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. Provisional Application Nos. 63/416,105, filed October 14, 2022; 63/527,474, filed July 18, 2023; and 63/540,013, filed September 22, 2023, the contents of which are hereby incorporated by reference in their entirety.

BACKGROUND

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.

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.

At the same time, CO2 emission from fermentation in an ethanol plant is estimated to be 0.9 kg per each kg ethanol produced. Meanwhile, the demand for fuel ethanol is expected to decrease as the electrical car market expands and demand for gasoline declines. It is thus necessary to develop technology that can directly convert both ethanol and CO2 to other highly demanded products.

SUMMARY OF THE INVENTION

In certain aspects, provided herein are systems for the production of aviation fuel comprising: an alcohol feed [1]; an alcohol to olefins (ATO) reactor [2] comprising an ATO catalyst, said ATO reactor having an alcohol inlet and an ATO product outlet, wherein the alcohol feed [1] is coupled to the alcohol inlet; an oligomerization reactor [7] comprising an oligomerization catalyst, said oligomerization reactor having an ATO product inlet and an oligomerized product outlet, wherein the ATO product outlet on the ATO reactor is coupled to the ATO product inlet of the oligomerization reactor; a second reduction gas feed [30]; a carbon source feed [31]; an aromatic reactor [27] comprising an aromatic catalyst, said aromatic reactor having a second reduction gas inlet, a carbon source feed inlet, and an aromatic product outlet, wherein the second reduction gas feed [30] is coupled to the second reduction gas inlet, and the carbon source feed [31] is coupled to the carbon source feed inlet; and a blender [14] having an oligomerized product inlet, an aromatic product inlet, and a blended product outlet, wherein the oligomerized product outlet [8] from the oligomerization reactor [7] is coupled to the oligomerized product inlet of the blender [14], and the aromatic product outlet from the aromatic reactor [27] is coupled to the aromatic product inlet of the blender [14],

In certain embodiments, systems of the present disclosure further comprise: a first reduction gas feed [9]; an isomerization reactor [10] comprising an isomerization catalyst, said isomerization reactor having a first reduction gas inlet, an oligomerized product inlet, and an isomerized product outlet, wherein the first reduction gas feed [9] is coupled to the first reduction gas inlet ,the oligomerized product outlet on the oligomerization reactor is coupled to the oligomerized product inlet of the isomerization reactor, and the isomerized product outlet is coupled to the oligomerized product inlet of the blender;

In certain embodiments, systems of the present disclosure further comprise: a third reduction gas feed [19]; and a hydrogenation reactor [18] comprising a hydrogenation catalyst, said hydrogenation reactor having a third reduction gas feed inlet, an aromatic product inlet, and a hydrogenated product outlet, wherein the third reduction gas feed [19] is coupled to the third reduction gas feed inlet, the aromatic product outlet of the aromatic reactor [27] is coupled to the aromatic product inlet of the hydrogenation reactor; and the hydrogenated product outlet is coupled to the aromatic product inlet [15] of the blender.

In certain embodiments, systems of the present disclosure further comprise a separator [21] 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 [21] and the separated product outlet is coupled as applicable toto (a) the aromatic product inlet of the hydrogenation reactor [18] or to (b) the aromatic product inlet of the blender [14],

In further aspects, provided herein are methods for producing aviation fuel comprising: contacting an alcohol feed comprising ethanol with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising ethylene; contacting the olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising linear paraffins and/or long-chain olefins; contacting a carbon source feed and a second reduction gas with an aromatic catalyst at an aromatic temperature and an aromatic pressure to afford an aromatic product mixture comprising one or more aromatics and/or naphthenes; and blending the oligomerized product mixture and the aromatic product mixture to afford a blended product mixture.

In certain embodiments, methods of the disclosure further comprise: contacting the oligomerized product mixture and a first 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.

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 hydrogenation pressure to afford a hydrogenated product mixture comprising aromatics 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.

BRIEF DESCRIPTION OF THE DRAWINGS

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

Fig- 2 shows an exemplary isomerization reactor [64] having a third reduction gas feed inlet [5], a C9-15 hydrocarbon inlet [63], and an isomerized product outlet [65],

Fig- 3 shows an exemplary hydrocracking reactor a hydrocracking reactor [69] having a fourth reduction gas feed inlet [6] a first Ci6+ hydrocarbon inlet [61], a second Ci6+ hydrocarbon inlet [68], and a hydrocracked product outlet [70],

DETAILED DESCRIPTION OF THE INVENTION

In certain aspects, the present disclosure provides processes for the production of aviation fuel, which can be directly substituted for Jet-A derived from crude oil, from ethanol, which may be provided directly from an ethanol production facility. As will be appreciated, the systems and methods of the present disclosure are particularly advantageous at larger-than-benchtop production scales, e.g, pilot plant scale, demonstration scale, and production scale or full-scale production.

In the system shown in Fig. 1, an alcohol (e.g, ethanol) in an alcohol feed is provided to Reactor 1, where an ATO catalyst comprising e.g. fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate is loaded. The alcohol in the alcohol feed is converted in Reactor 1 to an olefin product mixture comprising ethylene. Additional ATO catalysts are further described below.

The olefin product mixture from Reactor 1 is provided to an oligomerization reactor, where an oligomerization catalyst, e.g., a zeolite, such as ZSM-5, is loaded. The olefin product mixture may be used in the oligomerization reactor directly from Reactor 1 or may be additionally purified. Addition oligomerization catalysts are described below. The olefin product mixture is converted in the oligomerization reactor to an oligomerized product mixture comprising linear paraffins and/or long-chain olefins.

In some embodiments, the olefin product mixture is provided to a batch-type reactor, where a homogeneous oligomerization catalyst is dissolved in an oligomerization solution, such that the oligomerized product is insoluble or immiscible with the oligomerization solution.

The oligomerized product mixture from the oligomerization is sent to a fixed bed hydro-isomerization reactor where paraffin isomerization occurs. Hydrogen is added to this isomerization reactor. Catalysts, such as Pd or Pt on zeolite, will be loaded into the reactor. In this reactor, a portion of the n-paraffins will be converted to iso-paraffins. Separators may be used after the hydro-isomerization reactor to separate unconverted hydrogen from the liquid product. The degree of hydro-isomerization and resultant ratios of n- and i-paraffins may be adjusted by tuning the reactor conditions (e.g., temperature, pressure) as needed on-site to achieve the desired product distribution.

A carbon source, such as CO2, is provided to Reactor 2 along with hydrogen or another reduction gas. After optional combination with recycled gases, the carbon source feed passes through Reactor 1 where an aromatic catalyst such as CuZnA10 _x /HZSM-5, ZnCnC /ZSM-S, ZnA10 _x /HZSM-5, or ZnZrO/HZSM-5 is loaded to convert CO2 and hydrogen into hydrocarbons, mainly aromatics. Additional appropriate aromatic catalysts are further described below. The hydrocarbons produced in Reactor 2 may also include naphthenes, such that Reactor 2 provides a product mixture with a ratio of aromatics to naphthenes.

The reactor effluents from Reactor 2 are optionally sent to 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 of the separator and the separated product outlet is coupled to the aromatic product inlet of the hydrogenation reactor. Recycled gases from the separator comprising unconverted CO2 and H2, plus CO generated in Reactor 2, are optionally recycled to the carbon source feed as described above for use in Reactor 2. The ratios of the carbon source, reduction gas, and recycled gases in the carbon source feed may be adjusted or adapted as needed on-site to achieve a specific desired product mixture composition.

The effluent of Reactor 2 is optionally provided to a hydrogenation reactor, where a hydrogenation catalyst such as Pd or Pt on zeolite will be loaded into the reactor. In the hydrogenation reactor, a portion of the aromatic hydrocarbons from the effluent of Reactor 2 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.

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.

The effluents from the hydro-isomerization reactor (isomerized product mixture comprising n- and i-paraffins) and the hydrogenation reactor (hydrogenated product mixture comprising aromatics and naphthenes) are provided to and combined in a blender to provide a blended product comprising C9-15 hydrocarbons including linear paraffins, branched paraffins, aromatics, and naphthenes. The blended product preferably comprises 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.

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.

Systems for Aviation Fuel Production

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.

Additionally, as will be appreciated, various system components are described as “having” certain features. For example, in certain embodiments the aromatic reactor [27] is described as having a second reduction gas inlet [30], a carbon source feed inlet [31], and an aromatic product outlet [28], Such descriptions do not preclude, and specifically contemplate, the presence of additional features, such as inlets, outlets, valves, control mechanisms, measurement devices, heating and/or cooling systems, etc. Additionally, in the systems of the present disclosure, certain components are described as having one or more outlets or inlets. Such outlets and inlets may represent separate structural elements, or may be combined into a single inlet or outlet as suitable. The person of ordinary skill in the art will recognize that, once the critical features and operating conditions of systems such as those described herein are understood, the detailed design and operation of such systems involved many choices, such as specific reagent flows, separation steps, etc. While the present disclosure provides a number of specific embodiments, any suitable combination of these design choices may be made.

Further, the various systems and methods of the present disclosure 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., [10]), which correspond to components shown in Fig. 1.

In certain aspects, provided herein are systems for the production of aviation fuel comprising: an alcohol feed [1]; an alcohol to olefins (ATO) reactor [2] comprising an ATO catalyst [not shown], said ATO reactor having an alcohol inlet [not shown] and an ATO product outlet [3], wherein the alcohol feed [1] is coupled to the alcohol inlet [not shown]; an oligomerization reactor [7] comprising an oligomerization catalyst [not shown], said oligomerization reactor having an ATO product inlet [6] and an oligomerized product outlet [8], wherein the ATO product outlet [3] on the ATO reactor is coupled to the ATO product inlet [6] of the oligomerization reactor; a second reduction gas feed [30]; a carbon source feed [31]; an aromatic reactor [27] comprising an aromatic catalyst, said aromatic reactor having a second reduction gas inlet [26], a carbon source feed inlet [26], and an aromatic product outlet [28], wherein the second reduction gas feed [30] is coupled to the second reduction gas inlet [26], and the carbon source feed [31] is coupled to the carbon source feed inlet [26]; and a blender [14] having an oligomerized product inlet [13], an aromatic product inlet [15], and a blended product outlet [not shown], wherein the oligomerized product outlet [8] from the oligomerization reactor [7] is coupled to the oligomerized product inlet [13] of the blender [14], and the aromatic product outlet [28] from the aromatic reactor [27] is coupled to the aromatic product inlet [15] of the blender [14], In certain embodiments, systems of the present disclosure further comprise: a first reduction gas feed [9]; an isomerization reactor [10] comprising an isomerization catalyst [not shown], said isomerization reactor having a first reduction gas inlet [not shown], an oligomerized product inlet [8], and an isomerized product outlet [13], wherein the first reduction gas feed [9] is coupled to the first reduction gas inlet ,the oligomerized product outlet [8] on the oligomerization reactor [10] is coupled to the oligomerized product inlet [8] of the isomerization reactor, and the isomerized product outlet is coupled to the oligomerization product inlet of the blender;

In certain embodiments, systems of the present disclosure further comprise: a third reduction gas feed [19]; and a hydrogenation reactor [18] comprising a hydrogenation catalyst, said hydrogenation reactor having a third reduction gas feed inlet [not shown], an aromatic product inlet [20], and a hydrogenated product outlet [not shown], wherein the third reduction gas feed [19] is coupled to the third reduction gas feed inlet [not shown], the aromatic product outlet [28] of the aromatic reactor [27] is coupled to the aromatic product inlet [20] of the hydrogenation reactor; and the hydrogenated product outlet [not shown] is coupled to the aromatic product inlet [15] of the blender.

In certain embodiments, systems of the present disclosure further comprise a separator [21] having an aromatic product inlet [not shown], optionally a recycle gas outlet [22], and a separated product outlet [not shown], wherein the aromatic product outlet [28] of the aromatic reactor [27] is coupled to the aromatic product inlet [not shown] of the separator [21] and the separated product outlet [not shown] is coupled to the aromatic product inlet [20] of the hydrogenation reactor [18],

In further embodiments, the alcohol feed is coupled to an alcohol outlet of an industrial alcohol production facility, such as a fuel ethanol plant or a biorefinery. In other embodiments, 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. In yet further embodiments, the alcohol feed comprises alcohol that was produced by a renewable or sustainable process. Methods for Aviation Fuel Production

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.

In further aspects, provided herein are methods for producing aviation fuel comprising: contacting an alcohol feed comprising ethanol with an ATO catalyst at an ATO temperature and an ATO pressure to afford an olefin product mixture comprising ethylene; contacting the olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to afford an oligomerized product mixture comprising linear paraffins and/or long-chain olefins; contacting a carbon source feed and a second reduction gas with an aromatic catalyst at an aromatic temperature and an aromatic pressure to afford an aromatic product mixture comprising one or more aromatics and/or naphthenes; and blending the oligomerized product mixture and the aromatic product mixture to afford a blended product mixture.

In certain embodiments, methods of the disclosure further comprise contacting the oligomerized product mixture and a first 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.

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 hydrogenation pressure to afford a hydrogenated product mixture comprising aromatics 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. Conversion of Alcohols to Paraffins

In some embodiments, the alcohol feed comprises one or more alcohols and water. In certain embodiments, the alcohol feed is present as or condensed into a liquid. In some embodiments, the alcohol feed 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 methanol to olefins reactor.

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.

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 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 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.

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.

In some embodiments, 90-100% of the methanol is converted to olefins. In some embodiments, ethylene is the preferred product of the ATO reaction. 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. In some embodiments, the resulting ethylene is purified to 90%. In some embodiments, the resulting ethylene is purified to 99.9%. In some embodiments, the resulting ethylene is purified to 99.99% or higher.

Oligomerization of Olefins to Higher Olefins and Paraffins

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.

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. In certain embodiments, the oligomerization catalyst is a heterogeneous catalyst. In other embodiments, the oligomerization catalyst is a homogeneous catalyst.

In certain embodiments, the oligomerization catalyst is a zeolite. In further embodiments, the oligomerization catalyst is an aluminosilicate zeolite. In yet further embodiments, the oligomerization catalyst is selected from ZSM-5, ZSM-11, ZSM-22, ZSM- 23, and ZSM-35. In still further embodiments, the oligomerization catalyst is ZSM-5. In certain embodiments, the ZSM-5 is phosphorus-modified ZSM-5. In certain preferred embodiments

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 500 °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. In further embodiments, the oligomerization temperature is about 450 °C. In yet further embodiments, the oligomerization temperature is about 550 °C. In still further embodiments, the oligomerization temperature is about 650 °C. In certain embodiments, the oligomerization temperature is about 750 °C. In further embodiments, the oligomerization temperature is about 850 °C. In yet further embodiments, the oligomerization temperature is about 950 °C. In still further embodiments, the oligomerization temperature is about 1000 °C.

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.

In certain embodiments, the higher olefin product mixture produced during the oligomerization step comprises from about 10% to about 20% aromatics by volume.

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).

Isomerization of Oligomerized Products and Hydrogenation of Aromatic Products

In certain embodiments, the methods further comprise contacting the oligomerized product mixture and a first reduction gas with an isomerization catalyst at an isomerization temperature and isomerization pressure to afford an isomerized product mixture comprising linear paraffins, branched paraffins, and/or naphthenes. In certain embodiments, methods of isomerizing and hydrogenating, where applicable, are independently selected from those described herein. Methods of isomerizing the oligomerized product may be identical to or may differ from methods of hydrogenating the aromatic product mixture, as will be appreciated by one of ordinary skill in the art. In some embodiments, methods of the disclosure do not comprise hydrogenating the aromatic product mixture.

In further embodiments, the isomerized product mixture comprises: additional Ci-s hydrocarbons; additional C9-15 hydrocarbons including linear paraffins, branched paraffins, and naphthenes; and additional Ci6+ hydrocarbons.

In certain embodiments, the hydrogenated product mixture, when present, comprises: additional Ci-s hydrocarbons; additional C9-15 hydrocarbons including linear paraffins, branched paraffins, aromatics, and naphthenes; and additional Ci6+ hydrocarbons.

In certain embodiments, the isomerization temperature is from about 50 °C to about 450 °C. In further embodiments, the isomerization pressure is from about 50 psi to about 1000 psi.

Conversion of Carbon Source Gases to Aromatics

In certain aspects, the present disclosure provides methods for the production of aromatics comprising contacting a second reduction gas and a carbon source gas with an aromatic catalyst or a catalytic composition of the disclosure to afford an aromatic product mixture.

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

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.

In certain embodiments, the molar ratio of the second reduction gas to the carbon source gas is from about 10: 1 to about 1 : 10. In further embodiments, the molar ratio of the second reduction gas to the carbon source gas is from about 5: 1 to about 0.5: 1. In yet further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 5: 1. In still further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 4.5: 1. In certain embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 3 : 1. In further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 2.5: 1. In yet further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 2: 1. In still further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 1.5: 1. In certain embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 1 : 1. In further embodiments, the molar ratio of the second reduction gas to the carbon source gas is about 0.5: 1.

In certain embodiments, contacting the second reduction gas and the carbon source gas with the aromatic catalyst occurs at an aromatic temperature from about 100 °C to about 500 °C, preferably from about 100 °C to about 450 °C. The aromatic temperature may be at least 80 °C, or at least 100 °C, or at least 120 °C. The aromatic temperature may be 550 °C or less, or 500 °C or less, or preferably 450 °C or less. In certain embodiments, the aromatic temperature is from about 250 °C to about 350 °C. In some such embodiments, the aromatic temperature is about 250 °C, about 275 °C, about 300 °C, about 325 °C, or about 350 °C. In certain preferred embodiments, the aromatic temperature is about 300 °C.

In some embodiments, contacting the second reduction gas and the carbon source gas with the aromatic catalyst occurs at an aromatic pressure is from about 50 psi to about 3000 psi, preferably from about 50 psi to about 1000 psi. In certain such embodiments, the aromatic pressure is about 50 psi, about 150 psi, about 250 psi, about 350 psi, about 450 psi, about 550 psi, about 650 psi, about 750 psi, about 850 psi, about 950 psi, or about 1000 psi. In certain preferred embodiments, the aromatic pressure is about 450 psi.

In certain embodiments, contacting a second reduction gas and a carbon source gas with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and/or cyclic paraffins is carried out at an aromatic standard Gas Hourly Space Velocity (aromatic GHSV) of from about 8000 mL/g*h to about 12000 mL/g*h. In further embodiments, the aromatic GHSV is from about 8750 mL/g*h to about 9250 mL/g*h. In still further embodiments, the aromatic GHSV is about 8750 mL/g*h, about 9000 mL/g*h, or about 9250 mL/g*h. In preferred embodiments, the paraffin GHSV is about 9000 mL/g*h.

In certain embodiments, the first reduction gas comprises H2 and CO2.

In certain embodiments, the aromatic product mixture comprises aromatic hydrocarbons to naphthenes in an aromaticsmaphthenes ratio, which may be controlled by 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 (z.e., without a subsequent hydrogenation step).

In certain embodiments, the crude product mixture further comprises unreacted carbon source and/or reduction gas. In further embodiments, the method further comprises separating the unreacted CO2 and/or reduction gas from the crude product mixture to afford a degassed crude product mixture. In yet further embodiments, the degassed crude product mixture comprises C1.4 hydrocarbons, C5-8 hydrocarbons, C9-15 hydrocarbons, and Ci6+ hydrocarbons. In still further embodiments, said 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.

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. In further embodiments, the methods further comprise purifying the degassed product mixture to afford a purified product mixture comprising C9-15 hydrocarbons. In yet further embodiments, said purifying comprises a first separation and a second separation.

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.

Catalysts for Conversion of Alcohols to Olefins

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. 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 yet further embodiments, the ATO catalyst comprises alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseudo boehmites, gibbsites, or thermally shocked gibbsites.

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.

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).

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.

Catalysts for Conversion of Olefins to Paraffins

In certain aspects, the systems and methods of the present disclosure involve the use of olefin catalysts. As used herein, the term “paraffin” is used to refer to long-chain hydrocarbons, preferably C8-C16 hydrocarbons, which may be linear, branched, cyclic, or a mixture thereof. Paraffins may also be fully saturated, fully unsaturated, partially saturated, partially unsaturated, or a mixture thereof.

Certain aspects of the systems and method disclosed herein involve hydrogenation of the oligomerized product mixture to reduce the number of unsaturated carbon-carbon bonds, and thereby afford a mixture of higher hydrocarbons. As will be appreciated, many catalysts may be suitable for such a hydrogenation. Suitable catalysts for use in systems and methods of the disclosure are described below (Catalysts for Hydrogenation and Isomerization). Catalysts for Conversion of Carbon Sources and Reduction Gas to Aromatics

In certain aspects, the systems and methods of the present disclosure involve the use of aromatic catalysts. As used herein, the term “aromatic catalyst” refers to a catalyst used for the conversion of carbon sources and reduction gases to aromatics, but which does not necessarily itself comprise aromatics. 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.

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.

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.

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.

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.

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.

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.

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 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.

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.

In certain embodiments, the aromatic catalyst is ZnCrC .

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 the aromatic catalyst comprises an aromatic catalyst support, wherein the aromatic catalyst support is ZSM-5.

In certain embodiments, the 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, SAP031, SAP041), 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.

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.

In certain embodiments, the 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 aromatic catalyst comprises from about 25 wt% to about 75 wt% of the mixed oxide component and from about 75 wt% to about 25 wt% of the zeolite component. In certain preferred embodiments, the 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.

In certain embodiments, the mixed oxide component comprises: iron; zinc in a molar ratio of from 0 to about 0.50 relative to iron;

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

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

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

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.

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.

In some embodiments, the aromatic catalyst support is selected from SiA10 _x , SO4- ZrO2, zirconium tungstate, tungstated-titania, and anatases (SiO2-AhO3, SiO2-TiO2). 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.

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 metals or as isomorphous substitution in the zeolite framework.

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

In certain certain preferred embodiments, the aromatic catalyst 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 additional support, wherein the additional support is ZSM-5.

In some embodiments, the additional support is a mesoporous material. In some embodiments, the additional support has a mesopore volume from about 0.01 to about 3.0 cc/g.

In some embodiments, the additional support has surface area from about 10 m ² /g to about 1000 m ² /g. In some preferred embodiments, the catalytic composition comprising the additional support and a catalyst disclosed herein has a surface area from about 10 m ² /g to about 1000 m ² /g. 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.

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

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.

In some embodiments, the aromatic catalyst is a nanoparticle catalyst. In some embodiments, the particle sizes of the aromatic catalyst on the surface of the scaffold are about 1 nm to 5 nm. In some embodiments, the particle sizes of the aromatic catalyst on the surface of the scaffold are about 5 nm to 100 nm. In some embodiments, the particle sizes of the 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.

In certain embodiments, aromatic catalysts of the disclosure, such as those described above, are active in the conversion of a carbon source gas, such as CO2, to aromatics.

Catalysts for Hydrogenation and Isomerization

In certain aspects, the systems and methods of the present disclosure involve the use of hydrogenation catalysts and 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.

In certain embodiments, the isomerization catalysts and/or the hydrogenation catalysts of the present disclosure are aluminosilicate catalysts, such as zeolites. 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.

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.

In some embodiments, the additional 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 additional support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is selected from alumina (e.g., y-alumina), boehmite, crystalline boehmite, pseuodboehmites, gibbsites, and thermally shocked gibbsites. In some embodiments, the additional support is an aluminum oxide that is formed in-situ as part of the 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.

In some embodiments, the additional 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.

In some embodiments, the additional support is selected from SiA10 _x , 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.

In some embodiments, the additional support is a zeolite such as 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 combinations thereof. In further embodiments, the zeolites comprise additional metals such as Zn, Ga, Fe, or other transition metals. In yet further embodiments, the additional metals are present as zeolite supported metals or as isomorphous substitution in the zeolite framework.

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

In still further embodiments, the isomerization catalyst and the hydrogenation catalyst are independently selected from Pt/ZrCh/WCh, Pt/ZrWC , Pt/SiA10 _x , Pt/SC -ZrCh, Pt/ZSM5, Pt/ZSM22, Pt/SAPO, Ni-W/SiA10x, Ni-W/SO ₄ -ZrO ₂ , Ni-W/ZSM5, Ni-W/ZSM22, and Ni- W/SAPO. In certain certain preferred embodiments, the isomerization catalyst is Pt/ZrCb/WOs. In other preferred embodiments, the isomerization catalyst is Pt/SAPO comprising 0.2 wt% Pt.

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.

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.

Catalysts for 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. 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.

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.

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.

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

In some embodiments, the hydrocrackingsupport 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.

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

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

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.

Reduction Gases, Carbon Source Gases, and Ratios Thereo f

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.

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

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.

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.

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.

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 second reduction gas to the carbon source gas is from about 10: 1 to about 1 : 10. In further embodiments, the molar ratio of the second reduction gas to the carbon source gas is from about 5: 1 to about 0.5: 1.

Definitions

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.

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).

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

All of the above, and any other publications, patents and published patent applications referred to in this application are specifically incorporated by reference herein. In case of conflict, the present specification, including its specific definitions, will control.

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.

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).

The term “polycyclic aromatic(s)” as used herein refers to compounds comprising at least two aromatic rings, which may be fused (e.g., two distinct rings sharing two adjacent ring atoms). As a non-limiting example, the term “polycyclic aromatics” may be used to refer to a group of compounds comprising naphthalene and/or naphthalene derivatives.

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).

EXAMPLES

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

Example 1 : General procedure for CCb-to-aromatic catalyst synthesis

An aromatic catalyst of the disclosure is synthesized via incipient wetness impregnation of zinc nitrate and chromium nitrate (Zn/Cr = 0.5) onto the H-ZSM-5 support. The metal content of zinc and chromium is 38 wt%. The HZSM-5 support is made through hydrothermal reformation of tetraethyl orthosilicate and aluminum nitrate (Si/Al = 70) at 180 °C for 48 hours. The resulting product was dried overnight at 110 °C. Calcination was performed at 450 °C for 2 hours.

Example 2: General procedure for conversion of CO2 to aromatics

Aromatic formation from CO2 and hydrogen is carried out in a fixed bed flow reactor. The flow reactor is loaded with 1 kg of ZnCnCU on HZSM-5 catalyst. The catalyst is reduced in situ in a hydrogen environment at 350 °C for 2 hours. The reactor is heated to 300 °C after pretreatment. A feed mixture of 75% hydrogen and 25% CO2 is introduced to the reactor at 300 psi and a gas hourly space velocity of 5,000 h’ ¹ . The CO2 is converted into a mixture of alkylated aromatics with a selective range of carbon chain numbers (Cs-Cu).

Example 3: General procedure for dehydration of alcohols to olefins

The alcohols are fed into a dehydration reactor loaded with 1kg of ZSM-5 zeolite catalyst. The reaction is carried out at atmospheric pressure and 280 °C, and weight hourly space velocity of 2 h-1. The alcohols feed is converted to olefins with the same carbon chain number.

Example 4: General procedure for oligomerization of olefins

The collected olefins are fed into an oligomerization reactor loaded with 1kg of ZSM- 5 zeolite catalyst. The reaction is carried out at 100 psi and 300 °C, and gas hourly space velocity of 1500 h-1. The olefins feed is converted to a mixture of a-olefins with a selective range of carbon chain number between C8 and Cl 5.

Example 5: General procedure for isomerization of paraffins The collected paraffins are fed into an isomerization reactor loaded with 1 kg of Pt on beta-zeolite catalyst (0.5 wt% Pt). The reaction is carried out at 750 psi and 250 °C, with a mole ratio of hydrogen over hydrocarbons set at 500, and a liquid weight hourly space velocity of 1.0 h-1. The paraffins feed is converted into a mixture of saturated n-paraffin and iso-paraffin with a selective range of carbon chain number between C8 and Cl 5.

Example 6: Exemplary procedure for hydrogenation and hydrodeoxygenation

Platinum impregnated on alumina (0.5 wt% Pt) and palladium on carbon (1 wt% Pd) was loaded into a hydroisomerization fixed bed reactor. The catalyst was pretreated with hydrogen at 600 psig at 100 °C for 2 hours and then 300 °C for 4 hours with a GHSV of 3000. The liquid was fed in with a WHSV of 1, with a liquid/hydrogen volume ratio of 50. The resulting liquid was collected to give full conversion of olefins and oxygenate to paraffins and 10% cracking products from the process.

Example 7: Exemplary Procedure for hydro-isomerization of paraffinic SAF

Platinum impregnated on SAPO-11 (0.2 wt% Pt) was loaded into a hydro-isomerization fixed bed reactor. The catalyst was pretreated with hydrogen at ambient pressure at 100 °C for 2 hours and then 250 °C for 12 hours. The liquid was fed in with a WHSV of 1, with a liquid/hydrogen volume ratio of 10. The resulting liquid was collected to give 65% conversion of normal paraffins to iso-paraffins and 10% cracking products from the process.

Example 8: General procedure for hydrogenation of aromatics

The collected aromatics are fed into a hydrogenation reactor loaded with 1 kg of Pd on activated carbon catalyst (0.5 wt% Pd). The reaction is carried out at 500 psi and 250 °C, with a mole ratio of hydrogen over hydrocarbons set atlO, and a liquid weight hourly space velocity of 1.0 h-1. The paraffins feed is converted into a mixture of aromatics and cycloparaffin with a selective range of carbon number between C9 and Cl 5.

Example 9: General procedure for separation of target range hydrocarbons

A feed mixture of 50% alcohol-to-paraffins products and 50% CCh-to-aromatic products is introduced into a distillation system under ambient pressure N2 atmosphere. The fraction cut of 150 °C - 275 °C is collected. Example 10: General Procedure for Hydrocracking

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

Example 11 : Mixing Jet fuel from Aromatic and Paraffin SAF

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 cyclo-paraffins, and 40 gallons are aromatics by controlling the aromatic hydrogenation conditions. Hence, this exemplary blended jet fuel has the composition of: n-paraffins: 21.4 v% iso-paraffins: 35.7 v% Cyclo-paraffins: 28.6 v% Aromatics: 14.3 v%

Polycyclic aromatics < 1 v%

Indanes and Tetralins < 1 v%

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 cyclo-paraffins, and 40 gallons are aromatics by controlling the aromatic hydrogenation conditions. Hence, the blended jet fuel has the composition of: n-paraffins: 20 v% iso-paraffins: 30 v% Cyclo-paraffins: 40 v% Aromatics: 10 v% Polycyclic aromatics < 1 v%

Indanes and Tetralins < 1 v%

Example 12: Comparison of Aviation Fuel Produced by the Disclosed Methods with Traditional Aviation Fuel

A comparison of Synthetic Jet A with traditional (petroleum-based) Jet A will be carried out in a turbojet engine. The two fuels will be tested consecutively using the same engine, instrumentation and test cell. The engine will first be run on Jet A + 5% oil mix and will be fed from a temporary nitrogen pressured 2 gallon liquid dispensing tank. The container and fuel lines will be drained and replaced with the synthetic jet fuel + 5% oil mix and the test will be repeated. The engine will be run at multiple speeds and will be held at each point for 1.5 minutes to reach thermal equilibrium. The last 20 seconds of each hold will be averaged as data points.

Start time, engine speed, and temperature will also be compared. After running a throttle hook to measure performance the engine will be shut down and allowed to cool for 15 minutes. During the cooling period the battery will be recharged. After the 15 minutes the engine will be started and brought to idle. This process will be the same for each engine to eliminate known impacts on engine start performance.

INCORPORATION BY REFERENCE

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

EQUIVALENTS

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.