Systems and methods for conversion of ethanol to fuel

Abstract

Provided herein are systems and methods for converting ethanol and carbon-containing by-product gases to mixtures of paraffins and aromatics suitable for use as aviation fuels.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 416,105, filed on October 14, 2022; U.S. Provisional Application No. 63 / 527,474, filed on July 18, 2023; and U.S. Provisional Application No. 63 / 540,013, filed on September 22, 2023, the contents of which are hereby incorporated by reference in their entirety. Background Art

[0003] As atmospheric CO2 concentrations increase, it is advantageous to develop technologies that can remove or mitigate CO2 emissions. 2 Emission-reducing transportation technologies, such as electric vehicles, have become a priority. However, the development of electric aircraft, especially commercial electric aircraft, is problematic due to the low energy density of the required batteries. Therefore, there is still a need to develop sustainable aviation fuels (SAFs), and currently available technologies will not be able to meet market needs.

[0004] Currently, jet fuel (Jet-A) is composed of normal paraffins, isoparaffins, cycloparaffins, and aromatic compounds extracted from crude oil. In order to produce SAF that can directly replace Jet-A, SAF must match the current composition of Jet-A extracted from crude oil. Current SAF production technology involves extracting SAF from vegetable oils, animal fats, and waste oils. However, SAF manufactured by such processes mainly contains paraffins, and there are not enough cycloparaffins and aromatic compounds to directly replace Jet-A extracted from crude oil. Therefore, it is necessary to produce a technology that can directly replace Jet-A extracted from crude oil.

[0005] At the same time, it is estimated that the CO produced by fermentation in ethanol plants 2 The emission is 0.9kg / kg of ethanol produced. At the same time, as the electric vehicle market expands and the demand for gasoline decreases, the demand for fuel ethanol is expected to decrease. Therefore, it is necessary to develop technologies that can directly convert both ethanol and CO2 into other high-demand products. Summary of the invention

[0006] In certain aspects, provided herein is a system for producing aviation fuel, the system comprising:

[0007] Alcohol feed [1];

[0008] An alcohol to olefins (ATO) reactor [2], the ATO reactor comprising an ATO catalyst, the ATO reactor having an alcohol inlet and an ATO product outlet, wherein the alcohol feed [1] is connected to the alcohol inlet;

[0009] an oligomerization reactor [7], the oligomerization reactor comprising an oligomerization catalyst, the 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;

[0010] A second reducing gas feed

[30] ;

[0011] Carbon source feed

[31] ;

[0012] an aromatic reactor

[27] , the aromatic reactor comprising an aromatic catalyst, the aromatic reactor having a second reducing gas inlet, a carbon source feed inlet, and an aromatic product outlet, wherein the second reducing gas feed

[30] is coupled to the second reducing gas inlet, and the carbon source feed

[31] is coupled to the carbon source feed inlet; and

[0013] A blender

[14] having an oligomerized product inlet, an aromatic product inlet and a mixed product outlet, wherein the oligomerized product outlet [8] from the oligomerization reactor [7] is connected to the oligomerized product inlet of the blender

[14] , and the aromatic product outlet from the aromatic reactor

[27] is connected to the aromatic product inlet of the blender

[14] .

[0014] In certain embodiments, the system of the present disclosure further comprises:

[0015] first reducing gas feed [9];

[0016] an isomerization reactor

[10] , the isomerization reactor comprising an isomerization catalyst, the isomerization reactor having a first reducing gas inlet, an oligomerized product inlet and an isomerized product outlet, wherein the first reducing gas feed [9] is coupled to the first reducing 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;

[0017] In certain embodiments, the system of the present disclosure further comprises:

[0018] a third reducing gas feed

[19] ; ​​and

[0019] A hydrogenation reactor

[18] , the hydrogenation reactor comprising a hydrogenation catalyst, the hydrogenation reactor having a third reducing gas feed inlet, an aromatic product inlet and a hydrogenated product outlet, wherein the third reducing gas feed

[19] is connected to the third reducing gas feed inlet, the aromatic product outlet of the aromatic reactor

[27] is connected to the aromatic product inlet of the hydrogenation reactor, and the hydrogenated product outlet is connected to the aromatic product inlet

[15] of the blender.

[0020] In certain embodiments, the system of the present disclosure further comprises 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, when applicable, to (a) the aromatic product inlet of the hydrogenation reactor

[18] or (b) the aromatic product inlet of the blender

[14] .

[0021] In a further aspect, provided herein is a method for producing aviation fuel, the method comprising:

[0022] contacting an alcohol feed comprising ethanol with an ATO catalyst at an ATO temperature and an ATO pressure to produce an olefin product mixture comprising ethylene;

[0023] contacting the olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to obtain an oligomerized product mixture comprising linear paraffins and / or long chain olefins;

[0024] contacting a carbon source feed and a second reducing gas with an aromatic catalyst at an aromatic temperature and an aromatic pressure to obtain an aromatic product mixture comprising one or more aromatic compounds and / or cycloparaffins; and

[0025] The oligomerized product mixture and the aromatic product mixture are blended to obtain a blended product mixture.

[0026] In certain embodiments, the method of the present disclosure further comprises:

[0027] The oligomerized product mixture and the first reducing gas are contacted with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising linear paraffins, branched paraffins and / or cycloparaffins, wherein the isomerized product mixture is blended with the aromatic product mixture, or when present, the hydrogenated mixture, to obtain the blended product mixture.

[0028] In certain embodiments, the methods of the present disclosure further comprise contacting the aromatic product mixture and a third reducing gas with a hydrogenation catalyst at a hydrogenation temperature and a hydrogenation pressure to obtain a hydrogenated product mixture comprising aromatic compounds and cycloparaffins, wherein the hydrogenated product mixture is mixed with the oligomerized product mixture, or when present, the isomerized product mixture, to obtain the blended product mixture. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A flow chart for producing aviation fuel, which can directly replace Jet-A refined from crude oil, is shown. The aviation fuel is composed of ethanol, CO 2 and reducing gas manufacturing.

[0030] Figure 2 An exemplary isomerization reactor

[64] is shown having a third reducing gas feed inlet [5], C 9-15 A hydrocarbon inlet

[63] and an isomerized product outlet

[65] .

[0031] Figure 3 An exemplary hydrocracking reactor is shown, the hydrocracking reactor

[69] having a fourth reducing gas feed inlet [6], a first C 16+ Hydrocarbon inlet

[61] , second C 16+ A hydrocarbon inlet

[68] and a hydrocracked product outlet

[70] . DETAILED DESCRIPTION

[0032] In certain aspects, the present disclosure provides a process for producing aviation fuel from ethanol provided directly from an ethanol production facility, which can directly replace Jet-A extracted from crude oil. It should be understood that the systems and methods of the present disclosure are particularly advantageous at production scales larger than bench-top production scales (e.g., pilot plant scales, demonstration scales, and production scales or full-scale production).

[0033] exist Figure 1 In the system shown, alcohol (e.g., ethanol) in an alcohol feed is provided to a reactor 1 into which an ATO catalyst comprising fluid catalyst particles, such as comprising crystalline zeolite or silicoaluminophosphate, is loaded. The alcohol in the alcohol feed is converted to an olefin product mixture comprising ethylene in the reactor 1. Additional ATO catalysts are further described below.

[0034] The olefin product mixture from reactor 1 is provided to an oligomerization reactor, in which an oligomerization catalyst (e.g., zeolite, such as ZSM-5) is loaded. The olefin product mixture can directly enter the oligomerization reactor from reactor 1, or can be purified in addition. Addition oligomerization catalysts are described below. The olefin product mixture is converted into a product mixture through oligomerization comprising linear paraffins and / or long-chain olefins in the oligomerization reactor.

[0035] In some embodiments, the olefin product mixture is provided to a batch reactor in which a homogeneous oligomerization catalyst is dissolved in an oligomerization solution such that the oligomerized product is insoluble or immiscible in the oligomerization solution.

[0036] The oligomerized product mixture produced by oligomerization is fed to a fixed bed hydroisomerization reactor, in which paraffin isomerization occurs. Hydrogen is added to the isomerization reactor. A catalyst (such as zeolite-supported Pd or Pt) will be loaded into the reactor. In this reactor, a portion of normal paraffins will be converted into isoparaffins. A separator can be used after the hydroisomerization reactor to separate unconverted hydrogen from the liquid product. The degree of hydroisomerization and the ratio of the obtained normal paraffins and isoparaffins can be adjusted according to the needs of the site by fine-tuning the reactor conditions (e.g., temperature, pressure) to achieve the desired product distribution.

[0037] The carbon source (such as CO 2 ) is supplied to the reactor 2 together with hydrogen or another reducing gas. After optionally combining with the recycled gas, the carbon source feed passes through the reactor 1, in which the aromatic catalyst (such as CuZnAlO x / HZSM-5、ZnCr 2 O 4 / ZSM-5、ZnAlO x / HZSM-5 or ZnZrO / HZSM-5) to convert CO 2 and hydrogen into hydrocarbons, primarily aromatic compounds. Additional suitable aromatic catalysts are described further below. The hydrocarbons produced in reactor 2 may also include cycloparaffins, so that reactor 2 provides a product mixture having a certain ratio of aromatic compounds to cycloparaffins.

[0038] The reactor effluent from the reactor 2 may optionally be fed to a separator having an aromatic product inlet, an optional 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. The recycled gas (containing unconverted CO) from the separator2 and H 2 The CO (plus CO produced in reactor 2) is optionally recycled to the carbon source feed as described above for use in reactor 2. The ratio of carbon source, reducing gas and recycled gas in the carbon source feed can be adjusted or adapted according to site needs to achieve a specific desired product mixture composition.

[0039] The effluent of reactor 2 is optionally provided to a hydrogenation reactor, wherein 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 cycloparaffins (cycloolefins and alkanes). This allows the ratio of aromatic compounds to cycloparaffins to be reduced as desired.

[0040] A separator may be used after the aromatic and / or hydrogenation reactor to separate unconverted hydrogen from the liquid product. The degree of hydrogenation and the ratio of the resulting aromatic compounds and cycloparaffins may be adjusted to achieve the desired product distribution by fine-tuning the reactor conditions (e.g., temperature, pressure) according to site needs.

[0041] The effluents from the hydroisomerization reactor (comprising an isomerized product mixture of n-paraffins and iso-paraffins) and the hydrogenation reactor (comprising a hydrogenated product mixture of aromatic compounds and cycloparaffins) are provided to and combined in a blender to provide a blended product comprising C 9-15 Hydrocarbons, including linear paraffins, branched paraffins, aromatic compounds and cycloparaffins. The blended product preferably contains about 10% to about 20% aromatic compounds. The ratio of the effluent and the resulting blended product composition can be adjusted on site to meet the desired product specifications.

[0042] After the blending step, the blended product can be further processed as needed to obtain a fuel that meets applicable standards (such as a jet fuel that can directly replace Jet-A refined from crude oil) because the ratio of iso-paraffins to normal paraffins and the ratio of aromatics to cycloparaffins can be controlled separately in the hydroisomerization / hydrogenation reactor, and the ratio of paraffins to aromatics can be adjusted during blending. It will be appreciated by those skilled in the art that the flexibility of this system design allows these ratios to be adjusted as needed for other uses. A particular advantage of the system and method of the present invention is that the aromatics and paraffins can be combined prior to purification, thereby significantly saving capital expenditures.

[0043] Aviation fuel production system

[0044] In some aspects, there is provided herein a system for converting a carbon source gas and a reducing gas into aviation fuel. In the present disclosure, some components of these systems are described as being "connected" to each other. It should be understood that, as used herein, the term "connection" describes components that are operationally connected to each other but do not exclude components that are referred to as being connected to each other and that have intermediate components. The connection of one component to another component can also be applied to discontinuous processes, such as allowing a reaction in one component to proceed (e.g., complete), followed by a batch process of transferring the product mixture to the next connected component.

[0045] In addition, as understood, various system components are described as "having" certain features. For example, in certain embodiments, the aromatic reactor

[27] is described as having a second reducing gas inlet

[30] , a carbon source feed inlet

[31] , and an aromatic product outlet

[28] . Such descriptions do not exclude, and specifically take into account, the presence of additional features (such as inlets, outlets, valves, control mechanisms, measuring devices, heating and / or cooling systems, etc.). In addition, in the system 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 desired. Those of ordinary skill in the art will recognize that once the key features and operating conditions of a system (such as the system described herein) are understood, the detailed design and operation of such a system will involve many choices, such as specific reagent flows, separation steps, etc. Although the present disclosure provides many specific embodiments, any appropriate combination of these design choices may also be implemented.

[0046] In addition, various systems and methods of the present disclosure reference molecules having a particular carbon number (e.g., C X–Y As will be appreciated, these carbon numbers refer to the carbon composition of the majority of the fractions, but the fractions may include additional components with carbon numbers above or below the indicated carbon numbers. Separators capable of producing these fractions are well known in the art and can be adjusted as necessary to obtain a suitable product mixture as disclosed herein or as otherwise desired by the operator. Certain components of the system are provided by Figure 1 Components shown in FIG. 1 are referenced by corresponding numbers in parentheses (ie,

[10] ).

[0047] In certain aspects, provided herein is a system for producing aviation fuel, the system comprising:

[0048] Alcohol feed [1];

[0049] an alcohol to olefins (ATO) reactor [2], the ATO reactor comprising an ATO catalyst [not shown], the 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];

[0050] an oligomerization reactor [7], the oligomerization reactor comprising an oligomerization catalyst [not shown], the 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;

[0051] A second reducing gas feed

[30] ;

[0052] Carbon source feed

[31] ;

[0053] an aromatic reactor

[27] , the aromatic reactor comprising an aromatic catalyst, the aromatic reactor having a second reducing gas inlet

[26] , a carbon source feed inlet

[26] , and an aromatic product outlet

[28] , wherein the second reducing gas feed

[30] is coupled to the second reducing gas inlet

[26] , and the carbon source feed

[31] is coupled to the carbon source feed inlet

[26] ; and

[0054] A blender

[14] having an oligomerized product inlet

[13] , an aromatic product inlet

[15] and a mixed product outlet [not shown], wherein the oligomerized product outlet [8] from the oligomerization reactor [7] is connected to the oligomerized product inlet

[13] of the blender

[14] , and the aromatic product outlet

[28] from the aromatic reactor

[27] is connected to the aromatic product inlet

[15] of the blender

[14] .

[0055] In certain embodiments, the system of the present disclosure further comprises:

[0056] first reducing gas feed [9];

[0057] an isomerization reactor

[10] , the isomerization reactor comprising an isomerization catalyst [not shown], the isomerization reactor having a first reducing gas inlet [not shown], an oligomerized product inlet [8] and an isomerized product outlet

[13] , wherein the first reducing gas feed [9] is coupled to the first reducing 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 oligomerized product inlet of the blender;

[0058] In certain embodiments, the system of the present disclosure further comprises:

[0059] a third reducing gas feed

[19] ; ​​and

[0060] A hydrogenation reactor

[18] , the hydrogenation reactor comprising a hydrogenation catalyst, the hydrogenation reactor having a third reducing gas feed inlet [not shown], an aromatic product inlet

[20] and a hydrogenated product outlet [not shown], wherein the third reducing gas feed

[19] is connected to the third reducing gas feed inlet [not shown], the aromatic product outlet

[28] of the aromatic reactor

[27] is connected to the aromatic product inlet

[20] of the hydrogenation reactor; and the hydrogenated product outlet [not shown] is connected to the aromatic product inlet

[15] of the blender.

[0061] In certain embodiments, the system of the present disclosure further comprises 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] .

[0062] In other embodiments, the alcohol feed is connected 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 connected to a CO outlet of an industrial alcohol production facility (such as a fuel ethanol plant or a biorefinery). 2 outlet. In yet further embodiments, the alcohol feed comprises alcohol produced by a renewable or sustainable process.

[0063] Aviation fuel production method

[0064] As described below, the present disclosure provides various methods for converting carbon source gas into aviation fuel. The present disclosure includes exemplary process conditions (e.g., temperature, pressure, space velocity, etc.) that provide certain advantages in the context of the systems and methods disclosed herein. However, any suitable conditions may be used, and one of ordinary skill in the art will understand how to change the conditions of any particular process described herein to obtain results, and fine-tune the product distribution as considered according to the needs of a particular application.

[0065] In a further aspect, provided herein is a method for producing aviation fuel, the method comprising:

[0066] contacting an alcohol feed comprising ethanol with an ATO catalyst at an ATO temperature and an ATO pressure to produce an olefin product mixture comprising ethylene;

[0067] contacting the olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to obtain an oligomerized product mixture comprising linear paraffins and / or long chain olefins;

[0068] contacting a carbon source feed and a second reducing gas with an aromatic catalyst at an aromatic temperature and an aromatic pressure to obtain an aromatic product mixture comprising one or more aromatic compounds and / or cycloparaffins; and

[0069] The oligomerized product mixture and the aromatic product mixture are blended to obtain a blended product mixture.

[0070] In certain embodiments, the process of the present disclosure further comprises contacting the oligomerized product mixture and a first reducing gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising linear paraffins, branched paraffins and / or cycloparaffins; wherein the isomerized product mixture is blended with the aromatic product mixture, or when present, the hydrogenated mixture, to obtain the blended product mixture.

[0071] In certain embodiments, the methods of the present disclosure further comprise contacting the aromatic product mixture and a third reducing gas with a hydrogenation catalyst at a hydrogenation temperature and a hydrogenation pressure to obtain a hydrogenated product mixture comprising aromatic compounds and cycloparaffins, wherein the hydrogenated product mixture is mixed with the oligomerized product mixture, or when present, the isomerized product mixture, to obtain the blended product mixture.

[0072] Alcohol to Alkanes

[0073] In some embodiments, the alcohol feed comprises one or more alcohols and water. In certain embodiments, the alcohol feed exists in the form of a liquid or condenses into a liquid. In some embodiments, the alcohol feed is passed into the second reactor in a gas phase. In some embodiments, the liquid alcohol and water mixture is heated to more than 100° C. so that all its components are vaporized to be introduced into the methanol to olefins reactor.

[0074] Catalysts for converting alcohols to olefins suitable for the presently disclosed systems and methods are disclosed in the following patents, each of which is incorporated by reference in its entirety: European Patent No. 0,096,996; U.S. Patents 4,499,327; 5,191,141; 5,126,308; 5,714,662; and 4,440,871.

[0075] Alcohol to olefins (ATO) reactors are typically fixed bed flow reactors, but may also be one of several other reactor types, including trickle bed reactors, fluidized bed reactors, ebullient bed reactors, continuous stirred tank reactors, and the like. The ATO reactor includes an ATO catalyst that converts methanol to olefins (such as ethylene, propylene, butene, etc.) at high temperature and ambient pressure to low pressure conditions. In certain embodiments, the ATO temperature is about 260°C to about 510°C. In other embodiments, the ATO temperature is about 315°C to about 370°C. In yet other 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 other embodiments, the ATO temperature is about 345°C. In yet other embodiments, the ATO temperature is about 355°C. In still other embodiments, the ATO temperature is about 365°C. In certain embodiments, the ATO temperature is about 370°C.

[0076] In certain embodiments, the ATO pressure is about 100 kPa to about 515 kPa. In certain preferred embodiments, the ATO pressure is about 100 kPa. In certain embodiments, the ATO pressure is about 200 kPa. In other embodiments, the ATO pressure is about 300 kPa. In yet other embodiments, the ATO pressure is about 400 kPa. In still other embodiments, the ATO pressure is about 500 kPa. In certain embodiments, the ATO pressure is about 515 kPa.

[0077] In some embodiments, 90%-100% of methanol is converted into olefins. In some embodiments, ethylene is the preferred product of the ATO reaction. In some embodiments, the reaction is carried out under ambient pressure. The resulting olefins are separated from the byproduct water and purified by distillation, membrane separation or any other technology known to those skilled in the art for separating olefins. 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.

[0078] Olefin oligomerization to higher olefins and paraffins

[0079] In some embodiments, it is desirable to oligomerize olefins produced by an alcohol-to-olefin process in the presence of an oligomerization catalyst to produce a mixture of higher carbon olefins and optionally aromatic compounds. As used herein, the modifier "high carbon" with respect to hydrocarbons or olefins will refer to hydrocarbons or olefins with a carbon number higher than the precursor. Exemplary higher carbon alkenes and olefins include, but are not limited to, C 8 -C 16Hydrocarbons and / or olefins. Typical precursors may be a mixture of short chain olefins and short chain alkanes (e.g., C2-C5). In certain embodiments, these precursors are the effluent from the ATO reactor of the present disclosure, and the effluent can be used for oligomerization without further purification.

[0080] The 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 carried out in a fixed bed type reactor. In certain embodiments, the oligomerization process is carried out in a batch reactor. In certain embodiments, the oligomerization catalyst is a heterogeneous catalyst. In other embodiments, the oligomerization catalyst is a homogeneous catalyst.

[0081] In certain embodiments, the oligomerization catalyst is a zeolite. In other embodiments, the oligomerization catalyst is an aluminosilicate zeolite. In yet other embodiments, the oligomerization catalyst is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, and ZSM-35. In still other embodiments, the oligomerization catalyst is ZSM-5. In certain embodiments, the ZSM-5 is a phosphorus-modified ZSM-5. In certain preferred embodiments,

[0082] As desired, the temperature at which this oligomerization can be performed can range from about 50°C to about 500°C to tailor the degree of oligomerization based on the desired product length and distribution. In certain embodiments, the oligomerization temperature is about 50°C to about 500°C. In other embodiments, the oligomerization temperature is about 50°C. In yet other 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 other embodiments, the oligomerization temperature is about 450°C. In yet other embodiments, the oligomerization temperature is about 550°C. In still other embodiments, the oligomerization temperature is about 650°C. In certain embodiments, the oligomerization temperature is about 750°C. In other embodiments, the oligomerization temperature is about 850°C. In yet other embodiments, the oligomerization temperature is about 950°C. In still other embodiments, the oligomerization temperature is about 1000°C.

[0083] As desired, the range of pressure at which this oligomerization can be performed can be from about 0 psi (ambient pressure) to about 2000 psi, to customize 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 other embodiments, the oligomerization pressure is about 0 psi. In other 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 other embodiments, the oligomerization pressure is about 500 psi. In yet other embodiments, the oligomerization pressure is about 750 psi. In still other embodiments, the oligomerization pressure is about 1000 psi. In certain embodiments, the oligomerization pressure is about 1250 psi. In other embodiments, the oligomerization pressure is about 1500 psi. In yet other embodiments, the oligomerization pressure is about 1750 psi. In still other embodiments, the oligomerization pressure is about 2000 psi.

[0084] In certain embodiments, the higher olefin product mixture produced during the oligomerization step comprises from about 10% to about 20% by volume aromatic compounds.

[0085] As will be understood by those skilled in the art, pressure measurements in "pounds per square inch" (psi) may refer to both pressure as measured on a pressure gauge (psig), where 0 psi corresponds to atmospheric pressure, and absolute pressure (psia), where 0 psi corresponds to a complete vacuum. As used herein, the unit "psi" refers to absolute pressure (psig), unless expressly specified otherwise.

[0086] Isomerization of oligomerized products and hydrogenation of aromatic products

[0087] In certain embodiments, the method further comprises contacting the oligomerized product mixture and the first reducing gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising linear paraffins, branched paraffins and / or cycloparaffins. In certain embodiments, the methods of isomerization and hydrogenation (where applicable) are independently selected from the methods described herein. The method of isomerizing the oligomerized product can be the same as the method of hydrogenating the aromatic product mixture, or it can be different, as will be understood by those of ordinary skill in the art. In some embodiments, the method of the present disclosure does not include hydrogenating the aromatic product mixture.

[0088] In further embodiments, the isomerized product mixture comprises:

[0089] Another C 1-8 hydrocarbon;

[0090] Another C 9-15Hydrocarbons, including linear paraffins, branched paraffins, and cycloparaffins; and

[0091] Another C 16+ hydrocarbon.

[0092] In certain embodiments, the hydrogenated product mixture, when present, comprises:

[0093] Another C 1-8 hydrocarbon;

[0094] Another C 9-15 Hydrocarbons, including linear alkanes, branched alkanes, aromatics, and cycloparaffins; and

[0095] Another C 16+ hydrocarbon.

[0096] 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.

[0097] Conversion of carbon source gases into aromatic compounds

[0098] In certain aspects, the present disclosure provides a method for producing aromatic compounds, the method comprising contacting a second reducing gas and a carbon source gas with an aromatic catalyst or catalytic composition of the present disclosure to obtain an aromatic product mixture.

[0099] In certain embodiments, the second reducing gas is selected from H 2 , hydrocarbons, synthesis gas (CO / H 2 ), or selected from or derived from flare gas, waste gas or natural gas. In another embodiment, the second reducing gas is H 2 In yet another embodiment, the second reducing gas is a synthetic gas. In still another embodiment, the second reducing gas is a hydrocarbon, such as CH 4 , ethane, propane or butane. In certain embodiments, the second reducing gas is or is derived from flare gas, waste gas or natural gas. In other embodiments, the second reducing gas is CH 4 .

[0100] In some embodiments, the carbon source gas is CO 2 In another embodiment, the carbon source gas comprises CO 2 In yet further embodiments, the carbon source gas is CO. In still further embodiments, the carbon source gas comprises CO.

[0101] In certain embodiments, the molar ratio of the second reducing gas to the carbon source gas is from about 10:1 to about 1:10. In other embodiments, the molar ratio of the second reducing gas to the carbon source gas is from about 5:1 to about 0.5:1. In yet other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 5:1. In still other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 4.5:1. In certain embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 3:1. In still other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 2.5:1. In still other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 2:1. In still other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 1.5:1. In certain embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 1:1. In other embodiments, the molar ratio of the second reducing gas to the carbon source gas is about 0.5:1.

[0102] In certain embodiments, the aromatic temperature at which the second reducing gas and the carbon source gas are contacted with the aromatic catalyst is about 100°C to about 500°C, preferably 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 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.

[0103] In some embodiments, the aromatic pressure at which the second reducing gas and the carbon source gas are contacted with the aromatic catalyst is about 50 psi to about 3000 psi, preferably about 50 psi to about 1000 psi. In some 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 some preferred embodiments, the aromatic pressure is about 450 psi.

[0104] In certain embodiments, contacting the second reducing gas and the carbon source gas with the aromatic catalyst to obtain an aromatic product mixture comprising one or more aromatic compounds and / or cycloalkanes 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. In other embodiments, the aromatic GHSV is about 8750 ml / g*h to about 9250 ml / g*h. In still other embodiments, the aromatic GHSV is about 8750 ml / g*h, about 9000 ml / g*h, or about 9250 ml / g*h. In a preferred embodiment, the paraffin GHSV is about 9000 ml / g*h.

[0105] In certain embodiments, the first reducing gas comprises H 2 and CO 2 .

[0106] In certain embodiments, the aromatic product mixture comprises aromatics and cycloparaffins at a certain aromatic compound:cycloparaffin ratio, which can be controlled by changing the relative amounts of the carbon source gas, the second reducing gas, and the aromatic catalyst, and changing the aromatic temperature and the aromatic pressure. In certain embodiments, the aromatic compound:cycloparaffin ratio can be further modified using a hydrogenation reactor. In certain embodiments, the ratio does not need to be further modified, and the aromatic product mixture can be used directly in subsequent steps (i.e., without a subsequent hydrogenation step).

[0107] In certain embodiments, the crude product mixture further comprises unreacted carbon source and / or reducing gas. In other embodiments, the method further comprises separating unreacted CO from the crude product mixture. 2 and / or reducing gas to obtain a degassed crude product mixture. In yet another embodiment, the degassed crude product mixture comprises C 1-4 Hydrocarbon, C 5-8 Hydrocarbon, C 9-15 Hydrocarbons and C 16+ In still other embodiments, the separation comprises high pressure separation, low pressure separation or a combination thereof. In certain embodiments, the separation comprises high pressure separation and low pressure separation.

[0108] In certain embodiments, the method further comprises converting the unreacted CO 2 and / or the reducing gas is combined with one or more of the first reducing gas, the first carbon source gas, the second reducing gas, and the second carbon source gas. In another embodiment, the method further comprises purifying the degassed product mixture to obtain a product comprising C 9-15 A purified product mixture of hydrocarbons. In yet further embodiments, the purifying comprises a first separation and a second separation.

[0109] As used herein, the term "wt% polycyclic aromatic compounds" in an aromatic product mixture is the percentage of polycyclic aromatic compounds based on total aromatic compounds. In certain embodiments, the aromatic product mixture contains about 0 wt% to about 2 wt% polycyclic aromatic compounds. In other embodiments, the aromatic product mixture contains about 0.1 wt% to about 2 wt% polycyclic aromatic compounds. In yet other embodiments, the aromatic product mixture contains about 0.1 wt% to about 1 wt% polycyclic aromatic compounds. In still other embodiments, the aromatic product mixture contains about 1 wt% to about 2 wt% polycyclic aromatic compounds.

[0110] Catalysts for the conversion of alcohols to olefins

[0111] In certain aspects, the systems and methods of the present disclosure involve using a catalyst to convert an alcohol to a product comprising an olefin, such as converting ethanol to a mixture comprising ethylene.

[0112] In some embodiments, the alcohol to olefins (ATO) catalyst comprises fluid catalyst particles comprising crystalline zeolite or silicoaluminophosphate. In other 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 other embodiments, the ATO catalyst comprises alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite or thermally shocked gibbsite.

[0113] 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 having active sites that facilitate 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.

[0114] In some embodiments, the ATO catalyst is an ethanol dehydration catalyst. In some embodiments, the ethanol dehydration catalyst is γAl 2 O 3In some embodiments, the ethanol dehydration catalyst is a catalyst described in Zhang, M. & Yu, Y., Dehydration of Ethanol to Ethylene, Ind. Eng. Chem. Res. 2013, 52, 9505-9514 (herein referred to as Appendix A).

[0115] In certain embodiments, the ATO reactor is configured such that a suspension of vaporized ethanol and fluid catalyst particles pass upwardly through a dispersed catalyst contacting and reaction zone.

[0116] Catalysts for the conversion of olefins to paraffins

[0117] In certain aspects, the systems and methods of the present disclosure relate to the use of olefin catalysts. As used herein, the term "paraffin" refers to long chain hydrocarbons, preferably C8-C16 hydrocarbons, which can be linear, branched, cyclic or mixtures thereof. Paraffins can also be fully saturated, fully unsaturated, partially saturated, partially unsaturated or mixtures thereof.

[0118] Some aspects of the system and method disclosed herein relate to hydrogenating the product mixture through oligomerization to reduce the number of unsaturated carbon-carbon bonds and thus obtain a mixture of high carbon hydrocarbons. As understood, many catalysts can be suitable for such hydrogenation. Suitable catalysts (catalysts for hydrogenation and isomerization) used in the system and method of the present disclosure are described below.

[0119] Catalysts for converting carbon sources and reducing gases into aromatic compounds

[0120] 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 for converting a carbon source and a reducing gas into aromatic compounds, but it does not necessarily contain aromatic compounds itself. In certain aspects, the aromatic catalyst of the present disclosure comprises: one or more aromatic metal oxides; optionally an aromatic catalyst support; and optionally one or more aromatic metal additives.

[0121] In certain embodiments, the catalysts of the present disclosure are described as comprising and / or derived from a particular metal oxide or combination of metal oxides. It will be appreciated by those of ordinary skill in the art that during various catalyst preparation and activation methods known in the art, as well as in the catalyst preparation and activation methods exemplified herein, some or all of the oxygen atoms of the metal oxide may be combined with other atoms in the catalyst mixture, and / or may be removed from the catalyst mixture during the activation step (e.g., converted to CO). 2and removed). In addition, one of ordinary skill in the art will appreciate that for such catalysts (e.g., the aromatic catalysts described below), the molar ratio of oxygen relative to the total composition may vary.

[0122] In certain embodiments, the one or more aromatic metal oxides are selected from zinc oxide, copper oxide, chromium oxide and zirconium oxide. In other embodiments, the one or more aromatic metal additives (when present) are selected from Group IA or IIA elements, palladium, platinum and ruthenium. In yet other embodiments, the one or more aromatic metal oxides include 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.

[0123] In some embodiments, the first aromatic metal oxide and the second metal oxide are present in a first metal ratio of about 1:5 to about 5:1. In certain embodiments, the first metal ratio is about 1:5. In other embodiments, the first metal ratio is about 1:4.5. In still other embodiments, the first metal ratio is about 1:4. In still other embodiments, the first metal ratio is about 1:3.5. In certain embodiments, the first metal ratio is about 1:3. In other embodiments, the first metal ratio is about 1:2.5. In still other embodiments, the first metal ratio is about 1:2. In still other embodiments, the first metal ratio is about 1:1.5. In certain embodiments, the first metal ratio is about 1:1. In other embodiments, the first metal ratio is about 1.5:1. In still other embodiments, the first metal ratio is about 2:1. In still other embodiments, the first metal ratio is about 2.5:1. In certain embodiments, the first metal ratio is about 3:1. In still other embodiments, the first metal ratio is about 3.5:1. In yet further embodiments, the first metal ratio is about 4: 1. In still further embodiments, the first metal ratio is about 4.5: 1. In certain embodiments, the first metal ratio is about 5:1.

[0124] 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.

[0125] In certain embodiments, the one or more aromatic metals include a first aromatic metal and a second aromatic metal. In other embodiments, the first aromatic metal is zinc oxide. In yet other embodiments, the second aromatic metal is selected from zirconium, chromium, aluminum and copper. In still other embodiments, the first aromatic metal exists in the form of an oxide, a nitride or a carbide. In certain embodiments, the second aromatic metal exists in the form of an oxide, a nitride or a carbide.

[0126] In certain embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:10 to about 10:1. In other embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:10. In yet other embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:9. In still other 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 still other embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:6. In still other embodiments, the ratio of the first aromatic metal to the second aromatic metal is about 1:5. In still other 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 still other 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 still 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 still 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.

[0127] 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 other embodiments, the metal additive is chromium. In yet other embodiments, the metal additive is molybdenum. In still other embodiments, the metal additive is tungsten. In certain embodiments, the metal additive is manganese. In yet other embodiments, the metal additive is rhenium. In yet other embodiments, the metal additive is iron. In yet other embodiments, the metal additive is ruthenium. In certain embodiments, the metal additive is osmium. In yet other embodiments, the metal additive is cobalt. In yet other embodiments, the metal additive is rhodium.

[0128] In still further embodiments, the metal additive is iridium.In certain embodiments, the metal additive is nickel.

[0129] In other embodiments, the metal additive is palladium.In still other embodiments, the metal additive is platinum.

[0130] In still further embodiments, the metal additive is copper.In certain embodiments, the metal additive is silver.

[0131] In other embodiments, the metal additive is gold. In other embodiments, the additive is aluminum. In certain preferred embodiments, the one or more aromatic catalyst metal additives are gallium.

[0132] In certain embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. In other embodiments, the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium. In still other embodiments, the metal promoter is selected from beryllium, magnesium, calcium, strontium, and barium. In still other embodiments, the metal promoter is potassium.

[0133] In certain embodiments, the aromatic catalyst is ZnCrO 4 .

[0134] In certain preferred embodiments, the aromatic metal is zinc; the one or more aromatic metal additives are present, and wherein the one or more aromatic metal additives are gallium; and

[0135] 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, wherein the mixed oxide component comprises iron and zinc; and a zeolite component comprising a zeolite. In certain embodiments, the zeolite is selected from Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. In certain preferred embodiments, the zeolite is ZSM-5.

[0136] In other embodiments, the zeolite component further comprises a modifier, preferably Ga or Zn. In yet other embodiments, the zeolite component comprises 0wt% to about 2wt% of the modifier. In still other embodiments, the zeolite component comprises 0.01wt% to about 2wt% of the modifier. In certain embodiments, the zeolite component comprises 0.1wt% to about 1.5wt% of the modifier. In some preferred embodiments, the zeolite component comprises 0.5wt% to about 1wt% of the modifier.

[0137] In certain embodiments, the aromatic catalyst comprises about 10 wt % to about 90 wt % of the mixed oxide component and about 90 wt % to about 10 wt % of the zeolite component. In other embodiments, the aromatic catalyst comprises about 25 wt % to about 75 wt % of the mixed oxide component and about 75 wt % to about 25 wt % of the zeolite component. In certain preferred embodiments, the aromatic catalyst comprises about 40 wt % to about 60 wt % of the mixed oxide component and about 60 wt % to about 40 wt % of the zeolite component.

[0138] In certain embodiments, the mixed oxide composition comprises:

[0139] iron;

[0140] Zinc in a molar ratio relative to iron of 0 to about 0.50;

[0141] Na, K, Cs, Mg, Ca or a combination thereof in a molar ratio of 0 to about 0.10 relative to iron;

[0142] Cu, Cr, Mn or a combination thereof, in a molar ratio relative to iron of 0 to about 0.60.

[0143] In some embodiments, the aromatic catalyst comprises K in a molar ratio of 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.

[0144] In some embodiments, the aromatic catalyst support comprises one or more materials selected from the following: oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin. In some preferred embodiments, the aromatic catalyst support comprises γ-alumina. In certain embodiments, the aromatic catalyst support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide and silicon carbide. In some embodiments, the aromatic catalyst support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite and thermally shocked gibbsite. In some embodiments, the aromatic catalyst support is alumina formed in situ as part of a paraffin catalyst. In some embodiments, the aromatic catalyst support is selected from, but not limited to, MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 and TiO 2 In some embodiments, the aromatic catalyst support is selected from MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 .

[0145] In some embodiments, the aromatic catalyst support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0146] In some embodiments, the aromatic catalyst support is selected from SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2In other embodiments, the aromatic catalyst support is an aluminum-based material, such as alumina (eg, γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite.

[0147] In some embodiments, the aromatic catalyst carrier is a zeolite, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. In certain preferred embodiments, the aromatic catalyst carrier is ZSM-5. In further embodiments, the zeolite comprises a modifier, such as Zn, Ga, Fe or other transition metals. In yet further embodiments, the modifier exists in the form of isomorphous substitution in the metal or zeolite framework of the zeolite load.

[0148] In some embodiments, the aromatic catalyst support is modified with molybdenum, chlorine, and / or sulfur.

[0149] In certain preferred embodiments, the aromatic catalyst metal is zinc; the one or more aromatic metal additives are present, and wherein the one or more aromatic metal additives are gallium; and the aromatic catalyst comprises an additional support, wherein the additional support is ZSM-5.

[0150] In some embodiments, the additional support is a mesoporous material. In some embodiments, the additional support has a mesoporous volume of about 0.01 cc / g to about 3.0 cc / g.

[0151] In some embodiments, the additional carrier has a surface area of ​​about 10 m 2 / g to about 1000m 2 In some preferred embodiments, the surface area of ​​the catalytic composition disclosed herein comprising an additional support and a catalyst is about 10 m 2 / g to about 1000m 2 / g.

[0152] In some embodiments, the catalytic composition is in the form of particles having an average size of about 10 nm to about 5 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 20 nm to about 5 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 50 nm to about 1 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 100 nm to about 500 nm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 50 nm to about 300 nm.

[0153] In some embodiments, the catalytic composition comprises about 5 wt.% to about 80 wt.% of an aromatic catalyst. In some embodiments, the catalytic composition comprises about 5 wt.% to about 70 wt.% of an aromatic catalyst. In some embodiments, the catalytic composition comprises about 20 wt.% to about 70 wt.% of an aromatic catalyst. In some embodiments, the catalytic composition comprises about 30 wt.% to about 70 wt.% of an aromatic catalyst.

[0154] 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 a carbon allotrope.

[0155] In some embodiments, the aromatic catalyst is a nanoparticle catalyst. In some embodiments, the particle size of the aromatic catalyst on the surface of the support is about 1nm to 5nm. In some embodiments, the particle size of the aromatic catalyst on the surface of the support is about 5nm to 100nm. In some embodiments, the particle size of the aromatic catalyst on the surface of the support is 100nm to 500nm. In some embodiments, the particle size of the particles that have not been agglomerated is 100nm to 500nm.

[0156] In certain embodiments, the aromatic catalysts of the present disclosure (such as the catalysts described above) are used to generate carbon source gases (such as CO 2 ) are active in converting them into aromatic compounds.

[0157] Catalysts for hydrogenation and isomerization

[0158] In certain aspects, the systems and methods of the present disclosure involve using hydrogenation catalysts and isomerization catalysts to isomerize or hydrogenate, respectively, a percentage of the hydrocarbons produced. In certain embodiments, the hydrogenation catalysts and isomerization catalysts of the present disclosure may be independently selected from the catalysts described below.

[0159] In certain embodiments, the isomerization catalyst and / or hydrogenation catalyst of the present disclosure is an aluminosilicate catalyst, such as a zeolite. In other embodiments, the isomerization catalyst and / or hydrogenation catalyst is AlCl 3. In yet other embodiments, the isomerization catalyst and / or hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In still other embodiments, the isomerization catalyst and / or hydrogenation catalyst is Pt on β zeolite. In certain embodiments, the isomerization catalyst and / or hydrogenation catalyst of the present disclosure comprises an isomerization catalyst metal and a zeolite carrier. In other embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo.

[0160] In certain aspects, the isomerization catalyst further comprises an additional support. The additional support can be any suitable material that can be used as a catalyst support.

[0161] In some embodiments, the additional support comprises one or more materials selected from the following: oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin. In some preferred embodiments, the additional support comprises γ-alumina. In certain embodiments, the additional support is selected from carbon, silica, zeolites, alumina, zirconia, titanium oxide and silicon carbide. In some embodiments, the additional support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite and thermally shocked gibbsite. In some embodiments, the additional support is alumina formed in situ as part of the paraffin catalyst. In some embodiments, the additional support is selected from, but not limited to, MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 and TiO 2 In some embodiments, the additional support is selected from MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 .

[0162] 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.

[0163] In some embodiments, the additional support is selected from SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O3 、SiO 2 -TiO 2 In further embodiments, the additional support is an aluminum-based material such as alumina (eg, gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite.

[0164] In some embodiments, the additional carrier is a zeolite, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. In further embodiments, the zeolite comprises additional metals, such as Zn, Ga, Fe or other transition metals. In yet further embodiments, the additional metal is present in the form of isomorphous substitution in the metal or zeolite framework of the zeolite load.

[0165] In some embodiments, the additional metal is modified with molybdenum, chlorine, and / or sulfur.

[0166] In still further embodiments, the isomerization catalyst and the hydrogenation catalyst are independently selected from Pt / ZrO 2 / WO 3 、Pt / ZrWO 4 、Pt / SiAlO x 、Pt / SO 4 -ZrO 2 , Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlO x 、Ni-W / SO 4 -ZrO 2 , Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO. In certain preferred embodiments, the isomerization catalyst is Pt / ZrO 2 / WO 3 In other preferred embodiments, the isomerization catalyst is Pt / SAPO containing 0.2 wt% Pt.

[0167] In certain embodiments, the isomerization metal comprises about 0.5wt% to about 40wt% of an isomerization catalyst and / or a hydrogenation catalyst. In other embodiments, the isomerization metal comprises about 0.5wt% of an isomerization catalyst and / or a hydrogenation catalyst. In yet other embodiments, the isomerization metal comprises about 1wt% of an isomerization catalyst and / or a hydrogenation catalyst. In still other embodiments, the isomerization metal comprises about 10wt% of an isomerization catalyst and / or a hydrogenation catalyst. In certain embodiments, the isomerization metal comprises about 20wt% of an isomerization catalyst and / or a hydrogenation catalyst. In other embodiments, the isomerization metal comprises about 30wt% of an isomerization catalyst and / or a hydrogenation catalyst. In yet other embodiments, the isomerization metal comprises about 40wt% of an isomerization catalyst and / or a hydrogenation catalyst.

[0168] In certain embodiments, when the isomerization catalyst is Pt / Al2O3, 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.

[0169] Catalysts for hydrocracking

[0170] The systems and methods of the present disclosure may use any suitable hydrocracking catalyst, including catalysts known in the art. In some embodiments, catalysts similar to those described for the hydrogenation and isomerization steps (above) are also used for hydrocracking.

[0171] Any suitable hydrocracking catalyst known in the art may be used in these processes. However, the specific examples described below are intended both to illustrate the use of such catalysts and to identify catalysts that are particularly suitable for use in conjunction with other features of the systems and methods disclosed herein.

[0172] In certain embodiments, the blended product or any intermediate product may be subjected to hydrocracking. The systems and methods of the present disclosure may use any suitable hydrocracking catalyst, including catalysts known in the art. In some embodiments, catalysts similar to those described in the hydrogenation and isomerization steps (above) are also used for hydrocracking.

[0173] In other embodiments, the hydrocracking catalyst comprises a 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 may be used as a catalyst support.

[0174] In some embodiments, the hydrocracking support comprises one or more materials selected from the following: oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin. In some preferred embodiments, the additional support comprises γ-alumina. In certain embodiments, the hydrocracking support is selected from carbon, silica, zeolites, alumina, zirconia, titanium oxide and silicon carbide. In some embodiments, the hydrocracking support is selected from alumina (e.g., γ-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite and thermally shocked gibbsite. In some embodiments, the hydrocracking support is alumina formed in situ as part of a paraffin catalyst. In some embodiments, the hydrocracking support is selected from, but not limited to, MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 and TiO 2 In some embodiments, the hydrocracking support is selected from MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 .

[0175] 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.

[0176] In some embodiments, the hydrocracking support is selected from SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 In other embodiments, the hydrocracking support is an aluminum-based material, such as alumina (eg, gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite.

[0177] In some embodiments, the hydrocracking carrier is a zeolite, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolite (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite and combinations thereof. In further embodiments, the zeolite comprises a modifier, such as Zn, Ga, Fe or other transition metals. In yet further embodiments, the modifier exists in the form of isomorphous substitution in a zeolite-loaded metal or zeolite framework.

[0178] In some embodiments, the additional metal is modified with molybdenum, chlorine, and / or sulfur.

[0179] In certain embodiments, the hydrocracking metal comprises about 0.5 wt % to about 40 wt % of a hydrocracking catalyst. In other embodiments, the hydrocracking metal comprises about 0.5 wt % of a hydrocracking catalyst. In yet other embodiments, the hydrocracking metal comprises about 1 wt % of a hydrocracking catalyst. In still other embodiments, the hydrocracking metal comprises about 10 wt % of a hydrocracking catalyst. In certain embodiments, the hydrocracking metal comprises about 20 wt % of a hydrocracking catalyst. In other embodiments, the hydrocracking metal comprises about 30 wt % of a hydrocracking catalyst. In yet other embodiments, the hydrocracking metal comprises about 40 wt % of a hydrocracking catalyst.

[0180] Reducing gas, carbon source gas and their ratio

[0181] The system and method of the present disclosure can be designed to utilize any combination of suitable reducing gas and suitable carbon source gas. In certain embodiments, the carbon source gas and reducing gas can be provided to the necessary reaction vessel separately, or in certain embodiments, they can be pre-mixed (e.g., in some embodiments, the first reducing gas feed and the first carbon source gas feed can refer to the same physical characteristics, and the second reducing gas feed and the second carbon source gas feed can also refer to the same physical characteristics) to provide a single feed stream containing both the carbon source gas and the reducing gas, and the single feed stream is connected to an appropriate reactor.

[0182] Additionally, a single gas feed comprising the first reducing gas feed, the first carbon source gas feed, the second reducing gas feed, and the second carbon source gas feed may be premixed to provide a single feed stream comprising both carbon source gas and reducing gas that is coupled to the aromatic reactor.

[0183] In certain embodiments, the first reducing gas, the second reducing gas and the third reducing gas are independently selected from H2 , hydrocarbons, synthesis gas (CO / H 2 ), or selected from gases that are or are derived from flare gas, waste gas or natural gas.

[0184] In some embodiments, the first reducing gas, the second reducing gas and the third reducing gas are H 2 In another embodiment, the first reducing gas, the second reducing gas and the third reducing gas are synthetic gas. In yet another embodiment, the first reducing gas, the second reducing gas and / or the third reducing gas are hydrocarbons, such as CH 4 , ethane, propane or butane. In still other embodiments, the first reducing gas, the second reducing gas and the third reducing gas are or are derived from flare gas, waste gas or natural gas. In certain embodiments, the first reducing gas, the second reducing gas and the third reducing gas are CH 4 .

[0185] In some embodiments, the carbon source gas is CO 2 In another embodiment, the carbon source gas comprises CO 2 In yet further embodiments, the carbon source gas is CO. In still further embodiments, the carbon source gas comprises CO.

[0186] As will be appreciated by those skilled in the art, the flow rates of the carbon source gas and / or reducing gas or various product mixtures through the paraffin and / or aromatic reactors (or other portions of the disclosed systems and methods) can be adjusted as necessary to obtain the desired product output characteristics.

[0187] In addition, as will be appreciated by those skilled in the art, the carbon source gas and the reducing gas may be provided in any suitable ratio to obtain the desired product output characteristics. In certain embodiments, the molar ratio of the second reducing gas to the carbon source gas is from about 10:1 to about 1:10. In other embodiments, the molar ratio of the second reducing gas to the carbon source gas is from about 5:1 to about 0.5:1.

[0188] definition

[0189] Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings commonly understood by those of ordinary skill in the art. In general, the nomenclature used in connection with the 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 and their techniques are those well known and commonly used in the art.

[0190] The methods and techniques of the present disclosure are generally performed 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 the present specification unless otherwise indicated. See, e.g., "Principles of Neural Science", McGraw-Hill Medical, New York, NY (2000); Motulsky, "Intuitive Biostatistics", Oxford University Press, Inc. (1995); Lodish et al., "Molecular Cell Biology", 4th ed., WH Freeman & Co., New York (2000); Griffiths et al., "Introduction to Genetic Analysis", 7th ed., WH Freeman & Co., New York (1999); and Gilbert et al., "Developmental Biology", 6th ed., Sinauer Associates, Inc., Sunderland, MA (2000).

[0191] Unless otherwise defined herein, chemical terms used 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, CA (1985).

[0192] All of the above and any other publications, patents, and published patent applications mentioned in this application are specifically incorporated herein by reference. In the event of a conflict, the present specification, including its specific definitions, will control.

[0193] As used herein, the term "logarithm of solubility", "LogS" or "logS" is used in the art to quantify the water solubility of a compound. The water solubility of a compound significantly affects its absorption and distribution characteristics. Low solubility is generally associated with poor absorption. The LogS value is the unit exfoliation logarithm (base 10) of the solubility measured in moles / liter.

[0194] As used herein, the term "monocyclic aromatic" refers to compounds containing only one aromatic ring, which may be substituted or unsubstituted (eg, alkylbenzenes) and may optionally be fused to non-aromatic rings (eg, tetralin and indane).

[0195] As used herein, the term "polycyclic aromatic compound" refers to a compound comprising at least two aromatic rings, which may be fused (e.g., two different rings share two adjacent ring atoms). As a non-limiting example, the term "polycyclic aromatic compound" may be used to refer to a group of compounds comprising naphthalene and / or naphthalene derivatives.

[0196] As used herein, the term "petroleum-derived" refers to compounds and compositions that are extracted from petroleum feedstocks by physical and chemical processes, but does not include compounds and compositions in which the carbon is derived from carbon dioxide or carbon monoxide, even if the carbon dioxide or carbon monoxide is produced from a petroleum feedstock (e.g., by burning petroleum).

[0197] Examples

[0198] The invention now generally described will be more readily understood by reference to the following examples, which are included merely for the purpose of illustrating certain aspects and embodiments of the invention and are not intended to limit the invention.

[0199] Example 1: For CO 2 General Procedure for the Synthesis of Aromatic Catalysts

[0200] The aromatic catalyst disclosed herein was synthesized by incipient wetness impregnation of zinc nitrate and chromium nitrate (Zn / Cr=0.5) onto a H-ZSM-5 support. The metal content of zinc and chromium was 38 wt%. The HZSM-5 support was prepared by hydrothermal reforming tetraethyl orthosilicate and aluminum nitrate (Si / Al=70) at 180°C for 48 hours. The resulting product was dried at 110°C overnight. Calcinated at 450°C for 2 hours.

[0201] Example 2: For CO 2 General procedure for conversion to aromatic compounds

[0202] By CO 2 The aromatic formation with hydrogen was carried out in a fixed bed flow reactor. 1 kg of HZSM-5 catalyst loaded with ZnCr 2 O 4 The catalyst was reduced in situ at 350 °C in a hydrogen environment for 2 h. After pretreatment, the reactor was heated to 300 °C. 75% hydrogen and 25% CO 2 The feed mixture was heated at 300 psi and 5,000 h -1The gas hourly space velocity is introduced into the reactor. 2 is converted to have a selectable carbon chain number range (C 8 -C 12 ) of a mixture of alkylated aromatic compounds.

[0203] Example 3: General procedure for the dehydration of alcohols to alkenes

[0204] The alcohol is fed into a dehydration reactor containing 1 kg of ZSM-5 zeolite catalyst. The reaction is carried out at atmospheric pressure and 280°C, and the weight hourly space velocity is 2 h-1. The alcohol feed is converted into olefins with the same carbon chain number.

[0205] Example 4: General Procedure for Oligomerization of Olefins

[0206] The collected olefins are fed into an oligomerization reactor equipped with 1 kg of ZSM-5 zeolite catalyst. The reaction is carried out at 100 psi and 300°C, and the gas hourly space velocity is 1500 h-1. The olefin feed is converted into an alpha olefin mixture with a selectable carbon chain number range between C8 and C15.

[0207] Example 5: General procedure for isomerizing paraffins

[0208] The collected paraffins were fed to an isomerization reactor equipped with 1 kg of beta zeolite catalyst supported on Pt (0.5 wt% Pt). The reaction was carried out at 750 psi and 250°C, with the molar ratio of hydrogen to hydrocarbon set at 500 and the liquid weight hourly space velocity at 1.0 h-1. The paraffin feed was converted into a mixture of saturated normal paraffins and isoparaffins with a selectable carbon chain number range between C8 and C15.

[0209] Example 6: Exemplary Procedure for Hydrogenation and Hydrodeoxygenation

[0210] Platinum (0.5 wt% Pt) impregnated on alumina and palladium on carbon (1 wt% Pd) were loaded into a hydroisomerization fixed bed reactor. The catalyst was pretreated with hydrogen at 600 psig at 100°C for 2 hours and then at 300°C for 4 hours with a GHSV of 3000. The liquid was fed at a WHSV of 1 with a liquid / hydrogen volume ratio of 50. The resulting liquid was collected to fully convert olefins and oxygenates to paraffins and obtain 10% cracked products from the process.

[0211] Example 7: General Procedure for Hydroisomerization of Paraffinic SAF

[0212] Platinum (0.2 wt% Pt) impregnated on SAPO-11 was loaded into a hydroisomerization fixed bed reactor. The catalyst was pretreated with hydrogen at 100°C for 2 hours at ambient pressure and then at 250°C for 12 hours. The liquid was fed at a WHSV of 1 with a liquid / hydrogen volume ratio of 10. The resulting liquid was collected to convert 65% of normal paraffins to isoparaffins and obtain 10% cracked products from the process.

[0213] Example 8: General Procedure for Hydrogenation of Aromatic Compounds

[0214] The collected aromatic compounds were fed into a hydrogenation reactor equipped with 1 kg of Pd on activated carbon catalyst (0.5 wt% Pd). The reaction was carried out at 500 psi and 250°C, with the molar ratio of hydrogen to hydrocarbon set at 10 and the liquid weight hourly space velocity at 1.0 h-1. The paraffin feed was converted into a mixture of aromatic compounds and cycloparaffins with an optional carbon number range between C9 and C15.

[0215] Example 9: General Procedure for Separating Target Range Hydrocarbons

[0216] At ambient pressure N 2 Under the atmosphere, 50% of the alcohol to paraffin products and 50% of CO 2 The feed mixture for producing aromatic products is introduced into a distillation system. Fractions are collected at cutoff values ​​ranging from 150°C to 275°C.

[0217] Example 10: General Procedure for Hydrocracking

[0218] The fraction collected from the separation step was fed to a hydrocracking reactor containing 1 kg of Y zeolite catalyst loaded with Pt (0.5 wt% Pt). The reaction was carried out at 750 psi, with the molar ratio of hydrogen to hydrocarbon set at 20 and a liquid weight hourly space velocity of 1.0 h -1 The fractions were converted into the selected carbon chain number range between C 8 With C 15 A mixture of saturated normal paraffins, isoparaffins, aromatic compounds and cycloparaffins.

[0219] Example 11: Blending of jet fuels produced from aromatic and paraffinic SAFs

[0220] I. 160 gallons of fuel mixture made by the techniques of the process described herein was mixed with CO 2 The 120 gallons of fuel mixture made by CO are mixed. Of the 160 gallons of paraffin jet fuel, 100 gallons are isoparaffins and 60 gallons are normal paraffins, which is ensured by controlling the hydroisomerization conditions of the paraffins. 2The fuel mixture is made with 80 gallons of cycloparaffins and 40 gallons of aromatic compounds by controlling the aromatic hydrogenation conditions. Thus, this exemplary blended jet fuel has the following composition:

[0221] Normal paraffins: 21.4v%

[0222] Isoparaffins: 35.7v%

[0223] Cycloalkanes: 28.6v%

[0224] Aromatic compounds: 14.3v%

[0225] Polycyclic aromatic compounds <1v%

[0226] Indane and tetralin < 1v%

[0227] II. 200 gallons of jet fuel made by the technology of the present disclosure was mixed with 200 gallons of jet fuel made from CO2 using the technology described in Examples 5 and 7. Of the 200 gallons of paraffin jet fuel, 120 gallons were isoparaffins and 80 gallons were normal paraffins by controlling the hydroisomerization conditions of paraffins. Of the 200 gallons of jet fuel made from CO2, 160 gallons were cycloparaffins and 40 gallons were aromatic compounds by controlling the aromatic hydrogenation conditions. Thus, the blended jet fuel had the following composition:

[0228] Normal paraffins: 20v%

[0229] Isoparaffin: 30v%

[0230] Cycloalkanes: 40v%

[0231] Aromatic compounds: 10v%

[0232] Polycyclic aromatic compounds <1v%

[0233] Indane and tetralin < 1v%

[0234] Example 12: Comparison of aviation fuel produced by the disclosed method with conventional aviation fuel

[0235] A comparison of synthetic Jet A to conventional (petroleum based) Jet A will be conducted in a turbojet engine. The two fuels will be tested sequentially using the same engine, instrumentation, and test cell. The engine will first be run on a Jet A + 5% oil blend and fed from a 2 gallon liquid dispensing tank pressurized with temporary nitrogen. The container and fuel lines will be emptied and replaced with the synthetic jet fuel + 5% oil blend, and the test will be repeated. The engine will be run at multiple speeds and will be held for 1.5 minutes at each point to achieve thermal equilibrium. The last 20 seconds of each hold will be taken as the average of the data points.

[0236] Cranking times, engine speeds, and temperatures will also be compared. After running the throttle hook to measure performance, the engine will be shut down and allowed to cool for 15 minutes. During the cool-down period, the battery will be recharged. After 15 minutes, the engine will be started and run at idle. This process will be the same for each engine to eliminate known effects on engine starting performance.

[0237] Incorporated by Reference

[0238] All publications and patents mentioned herein are hereby incorporated by reference in their entirety to the same extent as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In the event of a conflict, the present application, including any definitions herein, will control.

[0239] Equivalent

[0240] Although specific embodiments of the present invention have been discussed, the above description is illustrative rather than restrictive. After reading this specification and the following claims, many variations of the present invention will become apparent to those skilled in the art. The full scope of the present invention should be determined by reference to the full scope of the claims and their equivalents and the specification and these variations.

Claims

1. A system for producing aviation fuel, the system comprising: Alcohol feed; an alcohol to olefins (ATO) reactor, the ATO reactor comprising an ATO catalyst, the ATO reactor having an alcohol inlet and an ATO product outlet, wherein the alcohol feed is coupled to the alcohol inlet; an oligomerization reactor comprising an oligomerization catalyst, the 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 reducing gas feed; Carbon source feed; an aromatic reactor comprising an aromatic catalyst, the aromatic reactor having a second reducing gas inlet, a carbon source feed inlet, and an aromatic product outlet, wherein the second reducing gas feed is coupled to the second reducing gas inlet, and the carbon source feed is coupled to the carbon source feed inlet; A blender having an oligomerized product inlet, an aromatic product inlet and a mixed product outlet, wherein the oligomerized product outlet from the oligomerization reactor is coupled to the oligomerized product inlet of the blender, and the aromatic product outlet from the aromatic reactor is coupled to the aromatic product inlet of the blender.

2. The system of claim 1, further comprising: a first reducing gas feed; an isomerization reactor comprising an isomerization catalyst, the isomerization reactor having a first reducing gas inlet, an oligomerized product inlet, and an isomerized product outlet, wherein the first reducing gas feed is coupled to the first reducing 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; 3. The system according to claim 1 or 2, further comprising: a third reducing gas feed; and A hydrogenation reactor comprising a hydrogenation catalyst, the hydrogenation reactor having a third reducing gas feed inlet, an aromatic product inlet and a hydrogenated product outlet, wherein the third reducing gas feed is connected to the third reducing gas feed inlet, the aromatic product outlet of the aromatic reactor is connected to the aromatic product inlet of the hydrogenation reactor, and the hydrogenated product outlet is connected to the aromatic product inlet of the blender.

4. The system according to any one of claims 1 to 3, further comprising 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 connected to the aromatic product inlet of the separator, and the separated product outlet is connected to the aromatic product inlet of the hydrogenation reactor.

5. The system of claim 4, wherein the recycle gas outlet, when present, is coupled to the first reducing gas feed, the second reducing gas feed, and / or the carbon source feed.

6. The system according to any one of claims 1 to 5, wherein the ATO reactor is a fixed bed reactor.

7. The system according to any one of claims 1 to 6, wherein the ATO catalyst comprises an active Al 2 O 3 .

8. The system of any one of claims 1 to 7, wherein the ATO catalyst comprises alumina (eg, gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, or thermally shocked gibbsite.

9. The system of any one of claims 1 to 8, wherein the ATO reactor is a fluidized bed reactor and the ATO catalyst comprises fluid catalyst particles comprising crystalline zeolite or silicoaluminophosphate.

10. The system of claim 9, 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, or ZSM-34.

11. The system of any one of claims 9 or 10, wherein the ATO reactor is configured such that a suspension of vaporized alcohol and the fluid catalyst particles pass upwardly through a dispersed catalyst contact and reaction zone.

12. The system of any one of claims 1 to 11, wherein the oligomerization catalyst is a zeolite.

13. The system of any one of claims 1 to 12, wherein the oligomerization catalyst is an aluminosilicate zeolite.

14. The system of any one of claims 1 to 13, wherein the oligomerization catalyst is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, ZSM-23, and ZSM-35.

15. The system of any one of claims 1 to 14, wherein the oligomerization catalyst is ZSM-5.

16. The system of claim 15, wherein the ZSM-5 is phosphorus-modified ZSM-5.

17. The system of any one of claims 1 to 16, wherein the isomerization catalyst comprises an isomerization metal, such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and an isomerization catalyst support.

18. The system of claim 17, wherein the isomerization catalyst comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the isomerization catalyst support is modified with molybdenum, chlorine and / or sulfur.

19. The system of claim 17 or 18, wherein the isomerization catalyst is selected from Pt / ZrO 2 / WO 3 、Pt / ZrWO 4 , Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO.

20. The system of any one of claims 17 to 19, wherein the isomerization catalyst is Pt / ZrO 2 / WO 3 .

21. The system of any one of claims 17 to 20, wherein the isomerization catalyst is Pt / SAPO comprising 0.2 wt% Pt.

22. The system of any one of claims 1 to 21, wherein 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.

23. The system of any one of claims 1 to 22, wherein the aromatic catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising a zeolite.

24. The system of claim 23, wherein the zeolite is ZSM-5.

25. The system of claim 23 or 24, wherein the zeolite component further comprises a modifier, such as Ga or Zn.

26. The system of claim 25, wherein the zeolite component comprises 0 wt% to about 2 wt% of the modifier.

27. The system of claim 25 or 26, wherein the zeolite component comprises 0.01 wt% to about 2 wt% of the modifier.

28. The system of any one of claims 25 to 27, wherein the zeolite component comprises 0.1 wt% to about 1.5 wt% of the modifier.

29. The system of any one of claims 25 to 28, wherein the zeolite component comprises 0.5 wt% to about 1 wt% of the modifier.

30. The system of any one of claims 23 to 29, wherein 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.

31. The system of any one of claims 23 to 30, wherein 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.

32. The system of any one of claims 23 to 31, wherein 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.

33. The system of claims 23 to 32, wherein the mixed oxide component comprises: iron; Zinc in a molar ratio relative to iron of 0 to about 0.50; Na, K, Cs, Mg, Ca or a combination thereof in a molar ratio of 0 to about 0.10 relative to iron; Cu, Cr, Mn or a combination thereof, in a molar ratio relative to iron of 0 to about 0.

60.

34. The system of claim 33, wherein the aromatic catalyst comprises K in a molar ratio relative to iron of 0 to about 0.

10.

35. The system of claim 33 or 34, wherein the aromatic catalyst comprises K in a molar ratio relative to iron of about 0.

036.

36. A system according to any one of claims 22 to 35, in: The one or more aromatic metals include a first aromatic metal and a second aromatic metal; The first aromatic metal is zinc; and The second aromatic metal is selected from the group consisting of zirconium, chromium, aluminum and copper.

37. The system of any one of claims 1 to 36, wherein the aromatic catalyst comprises an aromatic catalyst support.

38. The system of claim 37, wherein the aromatic catalyst support comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the aromatic catalyst support is modified with molybdenum, chlorine and / or sulfur.

39. The system of claim 38, wherein the aromatic catalyst support is ZSM-5 40. The system of any one of claims 22 to 39, wherein the one or more aromatic metal additives, when present, are selected from gallium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, and aluminum.

41. The system of any one of claims 22 to 40, wherein the one or more aromatic metal additives are present, and wherein the one or more aromatic metal additives are gallium.

42. The system of any one of claims 22 to 41, wherein the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium.

43. The system of claims 36 to 42, wherein the first aromatic metal and the second aromatic metal are present in a first metal ratio of about 1:5 to about 5:

1.

44. A system according to any one of claims 22 to 43, in: The aromatic metal is zinc; The one or more aromatic metal additives are present, and wherein the one or more aromatic metal additives are gallium; and The aromatic catalyst comprises an aromatic catalyst support, wherein the aromatic catalyst support is ZSM-5.

45. The system of any one of claims 1 to 44, wherein the hydrogenation catalyst comprises an isomerization metal, such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and a hydrogenation catalyst support.

46. ​​The system of claim 45, wherein the hydrogenation catalyst support comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the hydrogenation catalyst support is modified with molybdenum, chlorine and / or sulfur.

47. The system of claim 45 or 46, wherein the hydrogenation catalyst is selected from Pt / ZrO 2 / WO 3 、Pt / ZrWO 4 , Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO.

48. The system of any one of claims 45 to 47, wherein the hydrogenation catalyst is Pt / ZrO 2 / WO 3 .

49. The system of any one of claims 45 to 48, wherein the isomerization catalyst is Pt / SAPO comprising 0.2 wt% Pt.

50. The system of any one of claims 1 to 49, wherein (a) the alcohol feed is coupled to an alcohol outlet of an industrial alcohol production facility, such as a fuel ethanol plant or a biorefinery; or (b) the carbon source feed is coupled to a CO outlet of an industrial alcohol production facility, such as a fuel ethanol plant or a biorefinery. 2 exit.

51. A method for producing aviation fuel, the method comprising: contacting an alcohol feed comprising ethanol with an ATO catalyst at an ATO temperature and an ATO pressure to produce an olefin product mixture comprising ethylene; contacting the olefin product mixture with an oligomerization catalyst at an oligomerization temperature and an oligomerization pressure to obtain an oligomerized product mixture comprising linear paraffins and / or long chain olefins; contacting the carbon source gas and the second reducing gas with an aromatic catalyst to obtain an aromatic product mixture comprising one or more aromatic compounds and / or cycloparaffins; The oligomerized product mixture is blended with the aromatic product mixture to obtain a blended product mixture.

52. The method of claim 51, wherein the ATO catalyst comprises alumina (eg, gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, or thermally shocked gibbsite.

53. The method of claim 51 or 52, wherein the ATO catalyst comprises fluid catalyst particles comprising crystalline zeolite or silicoaluminophosphate.

54. The method of claim 53, 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, or ZSM-34.

55. The process of any one of claims 51 to 54, wherein the oligomerization catalyst is a zeolite.

56. The process of any one of claims 51 to 55, wherein the oligomerization catalyst is an aluminosilicate zeolite.

57. The process of any one of claims 51 to 56, wherein the oligomerization catalyst is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-35.

58. The process of any one of claims 51 to 57, wherein the oligomerization catalyst is ZSM-5.

59. The method of claim 58, wherein the ZSM-5 is phosphorus-modified ZSM-5.

60. The process of any one of claims 51 to 59, wherein 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.

61. The method of claim 60, wherein the aromatic catalyst comprises a mixed oxide component comprising iron and zinc; and a zeolite component comprising a zeolite.

62. The method of claim 61, wherein the zeolite is ZSM-5.

63. The method according to 61 or 62, wherein the zeolite component further comprises a modifier, such as Ga or Zn.

64. The method of any one of claims 61 to 63, wherein the zeolite component comprises 0 wt% to about 2 wt% of the modifier.

65. The method of any one of claims 61 to 64, wherein the zeolite component comprises 0.01 wt% to about 2 wt% of the modifier.

66. A process according to any one of claims 61 to 65, wherein the zeolite component comprises from 0.1 wt% to about 1.5 wt% of the modifier.

67. The method of any one of claims 61 to 66, wherein the zeolite component comprises 0.5 wt% to about 1 wt% of the modifier.

68. The method of any one of claims 61 to 67, wherein 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.

69. The method of any one of claims 61 to 68, wherein 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.

70. The method of any one of claims 61 to 69, wherein 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.

71. The method of claims 61 to 70, wherein the mixed oxide component comprises: iron; Zinc in a molar ratio relative to iron of 0 to about 0.50; Na, K, Cs, Mg, Ca or a combination thereof in a molar ratio of 0 to about 0.10 relative to iron; Cu, Cr, Mn or a combination thereof, in a molar ratio relative to iron of 0 to about 0.

60.

72. The system of claim 71, wherein the aromatic catalyst comprises K in a molar ratio relative to iron of 0 to about 0.

10.

73. The system of claim 71 or 72, wherein the aromatic catalyst comprises K in a molar ratio relative to iron of about 0.

036.

74. The method according to any one of claims 60 to 73, in: The one or more aromatic metals include a first aromatic metal and a second aromatic metal; The first aromatic metal is zinc; and The second aromatic metal is selected from zirconium, chromium, aluminum and copper, optionally in the form of an oxide.

75. The method of any one of claims 51 to 74, wherein the aromatic catalyst comprises an aromatic catalyst support.

76. The method of claim 75, wherein the aromatic catalyst support comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the aromatic catalyst support is modified with molybdenum, chlorine and / or sulfur.

77. The method of claim 75 or 76, wherein the aromatic catalyst support is ZSM-5.

78. The method of any one of claims 60 to 77, wherein the one or more aromatic metal additives, when present, are selected from gallium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold and aluminum.

79. The method of any one of claims 60 to 5078, wherein the metal promoter is selected from lithium, sodium, potassium, rubidium, cesium, magnesium and calcium.

80. The method of claims 74 to 79, wherein the first aromatic metal and the second aromatic metal are present in a first metal ratio of about 1:5 to about 5:

1.

81. The method according to claim 60, in: The aromatic metal is zinc; The aromatic metal additive is gallium; and The aromatic catalyst comprises an aromatic catalyst support, wherein the aromatic catalyst support is ZSM-5.

82. The process of any one of claims 51 to 81, further comprising contacting the oligomerized product mixture and a first reducing gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising linear paraffins, branched paraffins and / or cycloparaffins, wherein the isomerized product mixture is blended with the aromatic product mixture to obtain the blended product mixture.

83. The method of claim 82, wherein the isomerization catalyst comprises an isomerization metal, such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and an isomerization catalyst support.

84. The method of claim 83, wherein the isomerization catalyst support comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the isomerization catalyst support is modified with molybdenum, chlorine and / or sulfur.

85. The process according to any one of claims 82 to 84, wherein the isomerization catalyst is selected from Pt / ZrO 2 / WO 3 、Pt / ZrWO 4 , Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO.

86. The process of any one of claims 82 to 585, wherein the isomerization catalyst is Pt / ZrO 2 / WO 3 .

87. The process of any one of claims 51 to 86, further comprising contacting the aromatic product mixture and a third reducing gas with a hydrogenation catalyst at a hydrogenation temperature and a hydrogenation pressure to obtain a hydrogenated product mixture comprising cycloparaffins, aromatic compounds, and cycloparaffins, wherein the hydrogenated product mixture is mixed with the oligomerized product mixture, or when present, the isomerized product mixture, to obtain the blended product mixture.

88. The method of claim 87, wherein the hydrogenation catalyst comprises an isomerization metal such as Pd, Pt, Ni-Co, Ni-W, and Ni-Mo, and a hydrogenation catalyst support.

89. The method of claim 88, wherein the hydrogenation catalyst support comprises: A) one or more materials selected from the group consisting of oxides, nitrides, fluorides, silicates or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, tungsten and tin, such as MgO, Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 、ZnO、WO 3 , SiC and TiO 2 ; B) Carbon-based materials, such as activated carbon, carbon nanotubes, graphene, and graphene oxide; C)SiAlO x 、SO 4 -ZrO 2 , zirconium tungstate, tungstenized titanium dioxide and anatase (SiO 2 -Al 2 O 3 、SiO 2 -TiO 2 ); D) aluminum-based materials, such as alumina (e.g., gamma-alumina), boehmite, crystalline boehmite, pseudoboehmite, gibbsite, and thermally shocked gibbsite; or E) zeolites, such as Y-type zeolite, beta zeolite, ZSM-type zeolite (e.g., ZSM-5, HZSM-5, ZSM-12, ZSM-22, ZSM-57), SAPO-type zeolites (e.g., SAPO11, SAPO31, SAPO41), mordenite, MCM-49, MCM-22, DA-114, microcrystalline USY zeolite, microcrystalline USY zeolite, and combinations thereof, Optionally wherein the zeolite comprises a modifier such as Zn, Ga, Fe or other transition metals; and Optionally wherein the modifier is present as a zeolite-supported metal or isomorphously substituted in the zeolite framework; Optionally wherein the hydrogenation catalyst support is modified with molybdenum, chlorine and / or sulfur.

90. The method according to claim 60 or 61, wherein the hydrogenation catalyst is selected from Pt / ZrO 2 / WO 3 、Pt / ZrWO 4 , Pt / SiAlOx, Pt / SO4-ZrO2, Pt / ZSM5, Pt / ZSM22, Pt / SAPO, Ni-W / SiAlOx, Ni-W / SO4-ZrO2, Ni-W / ZSM5, Ni-W / ZSM22 and Ni-W / SAPO.

91. The method of any one of claims 87 to 90, wherein the hydrogenation catalyst is Pt / ZrO 2 / WO 3 .

92. The method according to any one of claims 82 to 91, wherein the first reducing gas, the second reducing gas and / or the third reducing gas are independently selected from H 2 , hydrocarbons, synthesis gas (CO / H 2 ), or selected from gases that are or are derived from flare gas, waste gas or natural gas.

93. The method according to any one of claims 82 to 92, wherein the first reducing gas, the second reducing gas and / or the third reducing gas are H 2 .

94. The method of any one of claims 82 to 92, wherein the first reducing gas, the second reducing gas and / or the third reducing gas is a forming gas.

95. The method according to any one of claims 82 to 92, wherein the first reducing gas, the second reducing gas and / or the third reducing gas are hydrocarbons such as CH 4 , ethane, propane or butane.

96. The method of any one of claims 82 to 692, wherein the first reducing gas, the second reducing gas and / or the third reducing gas is or is derived from a flare gas, an exhaust gas or a natural gas.

97. The method according to any one of claims 82 to 92, wherein the first reducing gas, the second reducing gas and the third reducing gas are CH 4 .

98. The method of any one of claims 51 to 97, wherein the carbon source gas comprises CO 2 .

99. The method of any one of claims 51 to 98, wherein the carbon source gas comprises CO.

100. The process of any one of claims 51 to 99, wherein the oligomerization temperature is from about 50°C to about 1000°C.

101. The process of any one of claims 51 to 100, wherein the oligomerization temperature is about 250°C.

102. The process of any one of claims 51 to 101, wherein the oligomerization pressure is from about 0 psi to about 2000 psi.

103. The method of any one of claims 51 to 102, wherein the oligomerization pressure is about 30 psi.

104. The process of any one of claims 82 to 103, wherein the isomerization temperature is from about 50°C to about 450°C.

105. The process of any one of claims 82 to 104, wherein the isomerization pressure is from about 50 psi to about 1000 psi.

106. The process of any one of claims 87 to 105, wherein the hydrogenation temperature is from about 50°C to about 450°C.

107. The method of any one of claims 87 to 106, wherein the hydrogenation pressure is from about 50 psi to about 1000 psi.

108. The process of any one of claims 51 to 107, wherein the oligomerized product mixture comprises unsaturated paraffins.

109. The method of claim 108, wherein the unsaturated paraffin comprises C 8 -C 16 Hydrocarbons and / or olefins.

110. The process of any one of claims 82 to 109, wherein the isomerized product mixture comprises C 9-15 Hydrocarbons, including linear alkanes, branched alkanes and cycloalkanes.

111. The process of any one of claims 87 to 110, wherein the hydrogenated product mixture comprises C 9-15 Hydrocarbons, including linear alkanes, branched alkanes, aromatics and cycloparaffins.

112. The method of any one of claims 51 to 111, wherein the blended product comprises C 9-15 Hydrocarbons, including linear alkanes, branched alkanes, cycloalkanes and aromatic compounds.

113. The method of claims 51 to 112, wherein the mixed product comprises from about 10% to about 20% aromatic compounds.

114. The method of any one of claims 51 to 113, wherein the aromatic product mixture comprises from about 0 wt% to about 2 wt% polycyclic aromatic compounds.

115. The method of claim 114, wherein the aromatic product mixture comprises from about 0.1 wt% to about 2 wt% polycyclic aromatic compounds.

116. The method of claim 115, wherein the aromatic product mixture comprises from about 0.1 wt% to about 1 wt% polycyclic aromatic compounds.

117. The method of claim 114, wherein the aromatic product mixture comprises from about 1 wt% to about 2 wt% polycyclic aromatic compounds.

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