Method and apparatus for selective upgrading of alcohol

Abstract

A method is disclosed for utilizing carbon dioxide to produce multi-carbon products. The disclosed system and method includes reducing CO2 to produce a first product mixture including an alcohol product mixture including one or more alcohols and a paraffin product mixture including one or more paraffins, dehydrating the alcohol product mixture to form an olefin product mixture including one or more olefins, oligomerizing the olefin product mixture to form a higher olefin product mixture including unsaturated paraffins and optionally aromatic compounds, and reducing the higher olefin product mixture to form a higher hydrocarbon product mixture including unsaturated paraffins and optionally aromatic compounds. Catalyst materials and reaction conditions for each step are disclosed that optimize the yield for ethanol or jet fuel range hydrocarbons.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 189,826, filed May 18, 2021, the contents of which are incorporated by reference herein in their entirety. [Background technology]

[0002] As the concentration of carbon dioxide in the atmosphere increases, there are benefits to developing technologies that eliminate or mitigate carbon dioxide emissions. Due to the negative impacts on social welfare, human health, and energy security caused by increasing atmospheric CO2 concentrations, countries are rapidly introducing restrictions on greenhouse gas (GHG) emissions, specifically CO2. This provides additional economic incentives for companies to produce and use large-scale commodity products from CO2, rather than releasing it into the atmosphere.

[0003] The need to remove CO2 from the air is aligned with the increasing global use of renewable electricity generation methods, such as solar and wind turbines. Renewable electricity generation methods emit less greenhouse gases per kilowatt-hour than electricity generated by fossil fuels, such as coal and natural gas. Therefore, from a CO2 removal perspective, it is advantageous to use renewable electricity or other low-carbon electricity to power processes that utilize CO2. There are several chemical technologies that utilize CO2 as a reagent, but carbon dioxide hydrogenation using hydrogen gas has the potential to produce lower carbon chemicals than some of its competitors. Hydrogen can be produced from water electrolysers, which can be fully powered by renewable electricity or by other methods that produce carbon-neutral hydrogen gas, such as steam methane reforming combined with carbon sequestration. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a need for scalable processes for utilizing CO2 and converting it into products containing more than one carbon atom, such as higher alcohols or hydrocarbon fuels, because these products are generally of higher economic value than products containing fewer carbon atoms, in part due to the complexity of their manufacture. Although there are processes that convert CO2 into molecules such as carbon monoxide, methane, and methanol, there is a need for chemical processes that can upgrade these single carbon products into multi-carbon alcohols and hydrocarbons. These higher alcohols and hydrocarbons may enable economical utilization of CO2 to produce products that have lower CO2 equivalent emissions than their fossil fuel-derived counterparts. [Means for solving the problem]

[0005] In some aspects, a system for producing alcohols or hydrocarbons is provided, comprising: a CO2 reduction reactor for converting a first gas mixture comprising CO2 and a reducing gas to a first product mixture comprising an alcohol product mixture comprising one or more alcohols, and optionally a paraffin product mixture comprising one or more paraffins, the CO2 reduction reactor comprising a first catalyst; an ATO reactor for dehydrating an alcohol product mixture to an olefin product mixture comprising one or more olefins, the ATO reactor comprising a second catalyst; an oligomerization reactor for oligomerizing the olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, the oligomerization reactor comprising a third catalyst; and an olefin reduction reactor for reducing a higher olefin product mixture to a higher hydrocarbon product mixture comprising unsaturated paraffins, the olefin reduction reactor comprising a fifth catalyst Provided herein is a system comprising:

[0006] In certain embodiments, the system comprises: a separator configured to separate ethylene from the olefin product mixture; a mixing vessel for combining ethylene and water to form a third feed mixture; and an ethylene hydration reactor for hydrating ethylene to form ethanol, the ethylene hydration reactor comprising a fourth catalyst. It further comprises:

[0007] In a further embodiment, the ethylene hydration reactor is configured such that a mixture of ethylene and steam is passed through a dispersed catalyst contact and reaction zone.

[0008] In a further aspect, there is provided a method for converting CO2 to an alcohol or a hydrocarbon, comprising: CO2 as follows: an alcohol product mixture comprising one or more alcohols; and Paraffin product mixture containing one or more paraffins and reducing the first product mixture to a first product mixture comprising: the reducing step comprising contacting a first gas mixture comprising CO and a reducing gas with a first catalyst at a reduction temperature and reduction pressure; Optionally, separating the alcohol product mixture from the paraffin product mixture; dehydrating the alcohol product mixture to an olefin product mixture comprising one or more olefins, said dehydrating comprising contacting the alcohol product mixture with a second catalyst at an ATO temperature and an ATO pressure; oligomerizing the olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, said oligomerizing step comprising contacting the olefin product mixture with a third catalyst at an oligomerization temperature and pressure; and reducing the higher olefin product mixture to a higher hydrocarbon product mixture comprising unsaturated paraffins, the reducing step comprising contacting the higher olefin product mixture with a fifth catalyst at an olefin reduction temperature and an olefin reduction pressure. A method is provided herein comprising:

[0009] In certain embodiments, the method comprises the steps of: separating ethylene from the olefin product mixture; forming a third feed mixture comprising ethylene and water; hydrating ethylene in a third feed mixture, the hydrating step including contacting the third feed mixture with a fourth catalyst at an ethylene hydration temperature and an ethylene hydration pressure to produce ethanol. Further includes:

[0010] In yet a further aspect, there is provided a method for converting CO2 to ethanol, comprising: contacting a first gas mixture comprising CO and a reducing gas with a first catalyst at a reducing temperature and pressure to produce a first product mixture comprising methanol and ethanol; contacting a second feed mixture comprising methanol with a second catalyst at an MTO temperature and an MTO pressure to produce ethylene and a second product mixture comprising C3 and higher paraffins, olefins, and other hydrocarbons, wherein the MTO pressure is the ATO pressure and the MTO temperature is the ATO temperature; Optionally, contacting the second product mixture comprising C3 and higher paraffins, olefins, and other hydrocarbons with a third catalyst at a Jet-A temperature and Jet-A pressure to produce jet fuel, wherein the Jet-A pressure is an olefin reduction pressure and the Jet-A temperature is an olefin reduction temperature; contacting the third feed mixture comprising ethylene and water with a fourth catalyst at an ethylene hydration temperature and an ethylene hydration pressure to produce ethanol. A method is provided herein comprising: [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a process schematic of a system for co-producing jet fuel and ethanol. [Figure 2A] 1 is a flow diagram illustrating components and reactors for a renewable energy powered system for converting carbon dioxide and water to ethanol and propylene. [Figure 2B] 1 is a flow diagram illustrating components and reactors for a renewable energy powered system for converting carbon dioxide and water to ethanol and propylene. [Figure 2C] 1 is a flow diagram illustrating components and reactors for a renewable energy powered system for converting carbon dioxide and water to ethanol and propylene. [Diagram 3] 1 is a flow diagram illustrating components and reactors for a system for converting carbon dioxide and water to sustainable drop-in aviation fuel containing both aromatics and paraffins. [Figure 4] FIG. 1 shows a GC-FID chromatogram of the product from the modified MTO process disclosed herein, as described in Example 4. [Diagram 5] FIG. 1 shows a GC-FID chromatogram of the propylene oligomerization product liquid described in Example 5. [Figure 6] FIG. 1 shows a comparison of GC-FID chromatograms for the paraffin liquid feed and the isomerized product. [Figure 7] FIG. 1 shows a GC-FID chromatogram of ethylene hydrogenation liquid product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In certain aspects, the present disclosure provides systems and methods for converting CO2 to alcohols and hydrocarbons. In some embodiments of the present invention, CO2 is sourced from capture from a point source, optionally purified using an amine capture system or other purification system, and in others, CO2 is captured from air. In some embodiments, CO2 is used in the form of flue gas. The systems and methods of the present disclosure can be used regardless of the CO2 source.

[0013] Explanation of the whole process In certain aspects, the disclosed system and method operates by the following steps: reducing CO2 to produce a first product mixture comprising an alcohol product mixture comprising one or more alcohols and a paraffin product mixture comprising one or more paraffins, dehydrating the alcohol product mixture to form an olefin product mixture comprising one or more olefins, oligomerizing the olefin product mixture to form a higher olefin product mixture comprising unsaturated paraffins and optionally aromatic compounds, and reducing the higher olefin product mixture to form a higher hydrocarbon product mixture comprising unsaturated paraffins and optionally aromatic compounds. As will be understood by those skilled in the art, the terms "higher olefin" and "unsaturated paraffin" are synonymous and are used interchangeably herein. The first product mixture comprising both alcohol and paraffin product mixtures may be separated into its alcohol and paraffin components before subjecting the alcohol product mixture to the dehydration step, or the entire first product mixture may be treated by the dehydration step. If a separation step is performed, the alcohol product mixture may be reintroduced into the overall process or into a subsequent blending step at any suitable stage. Each reaction is carried out in a reactor suitable for that particular reaction, including the presence of a suitable catalyst. The present disclosure encompasses both overall processes (wherein the steps of the process may be carried out in any suitable order) and systems in which each reactor is operatively connected to a subsequent reactor such that the product from each step is transferred to the subsequent reactor for the subsequent reaction t.

[0014] Those skilled in the art will also recognize that separation steps may be added at any suitable stage to either optimize the product of any step for reaction in subsequent steps or to isolate useful products. For example, in certain embodiments, the alcohol product mixture produced in the first reduction step includes ethanol. Ethanol may be isolated from the alcohol product mixture (or first product mixture) and set aside for sale or other processing. The remainder of the alcohol product mixture (or first product mixture) may then be processed through the remaining steps. Other useful products include ethylene (which may be separated after the dehydration step) and aromatics (which may be separated after the oligomerization step).

[0015] Thus, in certain embodiments, a system for producing alcohols or hydrocarbons is provided, comprising: a CO2 reduction reactor for converting CO2 to a first product mixture comprising an alcohol product mixture comprising one or more alcohols, and optionally a paraffin product mixture comprising one or more paraffins, the CO2 reduction reactor comprising a first catalyst; an ATO reactor for dehydrating an alcohol product mixture to an olefin product mixture comprising one or more olefins, the ATO reactor comprising a second catalyst; an oligomerization reactor for oligomerizing the olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, the oligomerization reactor comprising a third catalyst; and an olefin reduction reactor for reducing a higher olefin product mixture to a higher hydrocarbon product mixture comprising unsaturated paraffins, the olefin reduction reactor comprising a fifth catalyst Provided herein is a system comprising:

[0016] In a further aspect, there is provided a method for converting CO2 to an alcohol or a hydrocarbon, comprising: CO2 as follows: an alcohol product mixture comprising one or more alcohols; and Paraffin product mixture containing one or more paraffins wherein the reducing step comprises contacting a first gas mixture comprising CO and a reducing gas with a first catalyst at a reduction temperature and pressure; Optionally, separating the alcohol product mixture from the paraffin product mixture; dehydrating the alcohol product mixture to an olefin product mixture comprising one or more olefins, said dehydrating comprising contacting the alcohol product mixture with a second catalyst at an ATO temperature and an ATO pressure; oligomerizing the olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, said oligomerizing step comprising contacting the olefin product mixture with a third catalyst at an oligomerization temperature and pressure; and reducing the higher olefin product mixture to a higher hydrocarbon product mixture comprising unsaturated paraffins, the reducing step comprising contacting the higher olefin product mixture with a fifth catalyst at an olefin reduction temperature and an olefin reduction pressure. A method is provided herein comprising:

[0017] In yet a further aspect, there is provided a method for converting CO2 to ethanol, comprising: contacting a first gas mixture comprising CO and a reducing gas with a first catalyst at a reducing temperature and pressure to produce a first product mixture comprising methanol and ethanol; contacting a second feed mixture comprising methanol with a second catalyst at an MTO temperature and MTO pressure to produce a second product mixture comprising ethylene and C3 and higher paraffins, olefins and other hydrocarbons, wherein the MTO pressure is the ATO pressure and the MTO temperature is the ATO temperature; Optionally, contacting the second product mixture comprising C3 and higher paraffins, olefins, and other hydrocarbons with a third catalyst at a Jet-A temperature and Jet-A pressure to produce jet fuel, wherein the Jet-A pressure is an olefin reduction pressure and the Jet-A temperature is an olefin reduction temperature; contacting the third feed mixture comprising ethylene and water with a fourth catalyst at an ethylene hydration temperature and an ethylene hydration pressure to produce ethanol. A method is provided herein comprising:

[0018] CO2 capture In certain embodiments of the disclosed systems and methods, the utilized CO2 can be captured from ambient air, as described in International Application No. PCT / US2022 / 021469, the entire contents of which are expressly incorporated herein by reference.

[0019] In certain embodiments, the system of the present disclosure comprises an apparatus for carbon dioxide capture comprising a solution of a zinc complex in water and optionally a co-solvent, the zinc complex comprising at least one ligand coordinated to the zinc.

[0020] In certain embodiments, the method of the present disclosure comprises capturing carbon dioxide from a gas feed stream, the capturing comprising contacting the gas feed stream with a solution of a zinc complex in water and optionally a co-solvent to react the carbon dioxide and water to form a solution of hydrated carbon dioxide, where the zinc complex comprises at least one ligand coordinated to the zinc.

[0021] In certain embodiments, at least one ligand has at least κ 2 Style (κ 2 fashion) is a bidentate, tridentate, tetradentate, pentadentate, hexadentate, heptadentate or octadentate ligand coordinated to the zinc. In a further embodiment, at least one ligand is not a cyclen or porphyrin ligand.

[0022] In certain embodiments, the zinc complex has the formula: (L 1 ) n Zn(L 2 ) m (In the formula, L 1 Each of them must be at least κ 2 in a bidentate, tridentate, tetradentate, pentadentate, hexadentate, heptadentate or octadentate ligand coordinated to Zn, L 1 are each bonded to Zn through at least one donor heteroatom selected from O or N, L 1 are each mono-, di-, tri-, tetra-, penta- or hexa-anionic; L 2 are each selected from -OH or -OH2; n is 1 or 2; m is 0 or 1. has.

[0023] In a further embodiment, the zinc complex further comprises a cation and the complex has the formula: [{(L 1 ) n Zn(L 2 ) m} w ] z [A y ] x (In the formula, z is {(L 1 ) n Zn(L 2 ) m} moiety is selected from 0, -1, -2, or -3; A is a cation, x is the charge of the cation A and is selected from +1 or +2; w is an integer equal to (y x) / z, y is an integer equal to (w z) / x) has.

[0024] In yet a further embodiment, L 1 is not a cyclen ligand or a porphyrin ligand. 1 are ethylenediaminetetraacetic acid (EDTA), glutaric acid, nitrilotriacetic acid, triazacyclononane, trispyrazolylborate, terpyridine, porphine, choline, tris(2-aminoethyl)amine, triethylenetetramine, 12-crown-4, 15-crown-5, 16-crown-6, (2,2,2)cryptand, glycine, salen, 2-(pyridin-2-yl)propan-2-ol, niacin, picolinic acid, 2-acetylpyridine, iminodiacetic acid, oxalate, glutaric acid, ethylene glycol-bis(β -aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid, or ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (EDDHA), each of which is optionally substituted by one or more substituents independently selected from H, OH, amino, imine, sulfate, sulfonyl, alkyl, heteroalkyl, alkoxy, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, acetyl, carboxylate, or glycolate.

[0025] In certain embodiments, L 1 is the formula L 1A , L 1B , L 1C Or L 1D Ligands:

[0026] [ka] TIFF2024519843000002.tif66135(in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9is each independently selected at each occurrence from H, OH, amino, imine, sulfate, sulfonyl, alkyl, heteroalkyl, alkoxy, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, acetyl, carboxylate, glycolate; Y is NH, S or O; b, independently for each occurrence, is an integer from 0 to 4; c, independently for each occurrence, is an integer from 0 to 3;

[0027] [ka] is a single or double bond) It is.

[0028] In a further embodiment, L 1 teeth,

[0029] [ka] is selected from.

[0030] In yet further embodiments, the cation is selected from ammonium, sodium, potassium, calcium, or magnesium. In still further embodiments, the complex is water soluble and the complex is stable under basic conditions. In certain embodiments, the complex is stable at a pH of about 7 to about 16. In further embodiments, the complex is stable at a pH of about 8 to about 10.

[0031] In certain embodiments, the solution of the zinc complex further comprises a salt. In further embodiments, the salt is a carbonate salt. In yet further embodiments, the salt is potassium carbonate. In still further embodiments, the salt is present in the solution in an amount of about 0.001 M to about 20 M. In certain embodiments, the zinc complex is present in the solution in an amount of about 0.00001 M to about 10 M. In further embodiments, the pH of the solution is about 7 to about 16. In still further embodiments, the pH of the solution is about 8 to about 10.

[0032] In certain embodiments, the co-solvent is selected from ethanolamine, propylene carbonate, or an ionic liquid. In further embodiments, the solution of the zinc complex is homogeneous.

[0033] Hydrogenation of CO2 to alcohols and paraffins The disclosed systems and methods are particularly useful for the conversion of CO2 to paraffins and alcohols. As used herein, the term "paraffin" is used to refer to long chain hydrocarbons, preferably C8 to C16 hydrocarbons, which may be linear, branched, cyclic, or mixtures thereof. Paraffins may also be fully saturated, fully unsaturated, partially saturated, partially unsaturated, or mixtures thereof.

[0034] Any suitable catalyst for hydrogenating CO2 to alcohols can be used in the methods described herein. Exemplary catalysts for hydrogenating CO2 to alcohols suitable for the disclosed systems and methods are disclosed in the following applications: PCT Publication Nos. WO2021 / 226172, WO2021 / 262922, and WO2019 / 010095, each of which is incorporated by reference in its entirety.

[0035] In some embodiments, in a first reactor, CO2 and H2 are passed over a catalyst(s) to produce a mixture of methanol, ethanol, and other alcohols. In some embodiments, CO2 and H2 are passed over a catalyst(s) to produce substantially pure methanol (i.e., 80%, 85%, 90%, 95%, 99%, etc.). The most common catalyst for this type of process is a copper-based catalyst. Several other materials can produce a mixture of methanol and ethanol, including, but not limited to, modified CuZnAl catalysts, including Co, Fe, or Ni, zirconia-based catalysts, CoS, MoS, CoMoS, CoMoSK, NiCoMoSK, and several others.

[0036] In certain embodiments, the catalyst for hydrogenating CO2, referred to herein as the "first catalyst", comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or alloys or chemical compounds thereof. In further embodiments, the first catalyst comprises nanoparticles comprising CuZn, CuZnFeK, CuZnFeKC, CuZnFeAlK, CuZnFeNa, CuZnFeCoK, CuZnFeCoNaK, CuCoAl, CoMoSK, CuZnK, CuCoMn, RhRu, PdCuFe, Rh, or RhFeSi, optionally supported on an alumina support. In yet further embodiments, the first catalyst comprises nanoparticles comprising CoMoSK, optionally supported on an alumina support.

[0037] In certain embodiments, the first catalyst is selected from the following: molybdenum one or more first elements selected from Group V, VI, VII, VIII, IX, X, and XI metals (e.g., silver, cobalt, nickel, copper, rhodium, ruthenium, iridium, palladium, niobium, and manganese); one or more second elements selected from sulfur, carbon, oxygen, phosphorus, nitrogen and selenium, and Optionally, one or more Group IA metals Including, The molybdenum is present in an amount of 10 to 50 weight percent of the total amount of the one or more first elements, molybdenum, one or more second elements, and Group IA metal.

[0038] In certain embodiments, the one or more first elements include silver, cobalt, nickel, copper, rhodium, ruthenium, iridium, palladium, niobium, or manganese. In further embodiments, the one or more first elements include cobalt. In yet further embodiments, the one or more first elements include nickel. In yet further embodiments, the one or more first elements include silver. In certain embodiments, the one or more first elements include copper. In further embodiments, the one or more first elements include niobium. In yet further embodiments, the one or more first elements include manganese.

[0039] In certain embodiments, the first catalyst comprises one or more first elements in a molar ratio relative to molybdenum of about 0.15 to about 2. In further embodiments, the first catalyst comprises cobalt in a molar ratio relative to molybdenum of about 0.15 to about 2. In yet further embodiments, the first catalyst comprises cobalt in a molar ratio relative to molybdenum of about 0.29. In still further embodiments, the first catalyst comprises nickel in a molar ratio relative to molybdenum of about 0.15 to about 2. In certain embodiments, the first catalyst comprises nickel in a molar ratio relative to molybdenum of about 0.36. In still further embodiments, the first catalyst comprises silver in a molar ratio relative to molybdenum of about 0.15 to about 2. In still further embodiments, the first catalyst comprises silver in a molar ratio relative to molybdenum of about 1. In still further embodiments, the first catalyst comprises one or more Group IA metals.

[0040] In certain embodiments, the one or more Group IA metals include potassium. In further embodiments, the one or more Group IA metals include sodium. In yet further embodiments, the one or more Group IA metals include cesium. In still further embodiments, the first catalyst includes one or more Group IA metals in a molar ratio to molybdenum of about 0.10 to about 0.50. In certain embodiments, the first catalyst includes one or more Group IA metals in a molar ratio to molybdenum of about 0.44.

[0041] In certain embodiments, the one or more Group IA metals include potassium. In further embodiments, the first catalyst includes one or more second elements in a molar ratio to molybdenum of about 0.3 to about 3.25. In yet further embodiments, the first catalyst includes one or more second elements in a molar ratio to molybdenum of about 3 to about 3.25. In yet further embodiments, the first catalyst includes one or more second elements in a molar ratio to molybdenum of about 2.5 to about 3.25. In certain embodiments, the one or more second elements include sulfur.

[0042] In certain embodiments, the one or more second elements include carbon. In further embodiments, the first catalyst includes sulfur in a molar ratio to molybdenum of about 3.25. In yet further embodiments, the first catalyst includes silver, molybdenum, sulfur, and a Group IA metal.

[0043] In certain embodiments, the first catalyst is selected from the following: molybdenum Silver in a molar ratio of about 1 to molybdenum; Sulfur in a molar ratio of about 3 to molybdenum, and Group IA in a molar ratio of about 0.4 to molybdenum Includes.

[0044] In a further embodiment, the first catalyst comprises nickel, cobalt, molybdenum, sulfur and a Group IA metal.

[0045] In certain embodiments, the first catalyst is selected from the following: molybdenum Nickel to molybdenum in a molar ratio of about 0.36; Cobalt to molybdenum in a molar ratio of about 0.29; a molar ratio of sulfur to molybdenum of about 3.25; and Group IA in a molar ratio of about 0.44 to molybdenum Includes.

[0046] In a further embodiment, the first catalyst comprises niobium, cobalt, molybdenum, sulfur and a Group IA metal.

[0047] In certain embodiments, the first catalyst is selected from the following: Niobium to molybdenum in a molar ratio of about 0.12; Cobalt in a molar ratio of about 0.6 to molybdenum; a molar ratio of sulfur to molybdenum of about 3.25; and Group IA in a molar ratio of about 0.4 to molybdenum Includes.

[0048] In a further embodiment, the first catalyst is selected from the following: copper zinc One or more first elements selected from cobalt, nickel, or iron aluminum oxygen Optionally, one or more second elements selected from Group V, VI, VII, VIII, IX, X and XI metals (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium or palladium), and Optionally, one or more Group IA metals Including, The cobalt is present in an amount of about 10 to about 40 weight percent (e.g., about 25 to about 40 weight percent, about 30 to about 40 weight percent, or about 35 to about 40 weight percent) of the total amount of copper, zinc, cobalt, optional first element, and optional Group IA metal.

[0049] In certain embodiments, the first catalyst comprises one or more second elements. In further embodiments, the one or more first elements comprise iron. In yet further embodiments, the one or more first elements comprise nickel. In yet further embodiments, the one or more second elements comprise manganese. In certain embodiments, the one or more second elements comprise zirconium. In further embodiments, the one or more second elements comprise niobium. In yet further embodiments, the one or more second elements comprise molybdenum.

[0050] In certain embodiments, the first catalyst comprises copper in a molar ratio of about 1 to about 3 relative to the first element. In further embodiments, the first catalyst comprises copper in a molar ratio of about 2 to about 2.5 relative to the first element. In yet further embodiments, the first catalyst comprises zinc in a molar ratio of about 0.5 to about 1.5 relative to the first element. In still further embodiments, the first catalyst comprises iron in a molar ratio of about 0.5 to about 1.5 relative to the first element. In certain embodiments, the first catalyst comprises aluminum in a molar ratio of about 0.4 to about 2.1 relative to the first element. In further embodiments, the first catalyst comprises aluminum in a molar ratio of about 0.5 to about 1 relative to the first element.

[0051] In certain embodiments, the first catalyst comprises one or more Group IA metals. In further embodiments, the one or more Group IA metals comprise potassium. In yet further embodiments, the one or more Group IA metals comprise sodium. In yet further embodiments, the one or more Group IA metals comprise cesium. In certain embodiments, the first catalyst comprises one or more Group IA metals in a molar ratio to the first element of about 0.05 to about 0.5. In further embodiments, the first catalyst comprises one or more Group IA metals in a molar ratio to the first element of about 0.15.

[0052] In certain embodiments, the first catalyst comprises zinc oxide. In further embodiments, the first catalyst comprises copper oxide. In yet further embodiments, the first catalyst comprises cobalt oxide. In yet further embodiments, the first catalyst comprises alumina.

[0053] In certain embodiments, the first catalyst comprises cobalt, copper, zinc oxide, and alumina. In further embodiments, the first catalyst comprises the following: copper in a molar ratio of about 2.5 to cobalt; Zinc oxide in a molar ratio of about 1 to cobalt, and Alumina with a molar ratio of about 0.35 to cobalt Includes.

[0054] In certain embodiments, the first catalyst comprises cobalt, copper, zinc oxide, alumina, and a Group IA metal. In further embodiments, the first catalyst comprises the following: copper in a molar ratio of about 2.5 to cobalt; Zinc oxide in a molar ratio of about 1 to cobalt; a molar ratio of alumina to cobalt of about 0.35; and A Group IA metal in a molar ratio of about 0.1 to cobalt Includes.

[0055] In certain embodiments, the first catalyst comprises cobalt, iron, copper, zinc oxide, alumina, and a Group IA metal. In further embodiments, the first catalyst comprises the following: Copper in a molar ratio of about 1 to cobalt; iron in a molar ratio of about 1 to cobalt; Zinc oxide in a molar ratio of about 1 to cobalt; alumina in a molar ratio to cobalt of about 0.35; and A Group IA metal in a molar ratio of about 0.1 to cobalt Includes.

[0056] In certain embodiments, the first catalyst further comprises a support. In further embodiments, the support comprises one or more materials selected from oxides, nitrides, fluorides, or silicates of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, and tin. In yet further embodiments, the support comprises γ-alumina. In still further embodiments, the support comprises one or more carbon-based materials. In certain embodiments, the carbon-based materials are selected from activated carbon, carbon nanotubes, graphene, and graphene oxide. In further embodiments, the support is a mesoporous material. In still further embodiments, the support has a mesopore volume of about 0.01 to about 3.0 cc / g. In still further embodiments, the support has a mesopore volume of about 10 m 2 / g~about 1000m 2 / g surface area.

[0057] In certain embodiments, the first catalyst is in the form of particles having an average size of about 20 nm to about 5 μm. In further embodiments, the first catalyst is in the form of particles having an average size of about 50 nm to about 1 μm. In yet further embodiments, the first catalyst is in the form of particles having an average size of about 100 nm to about 500 nm. In yet further embodiments, the first catalyst is in the form of particles having an average size of about 50 nm to about 300 nm.

[0058] In certain embodiments, the first catalyst is embedded in a monolith, compressed into a pellet, or extruded into a form that supports the first catalyst under the reaction conditions.

[0059] In certain embodiments, the reducing gas is H2. In further embodiments, the reducing gas is a hydrocarbon, such as CH4, ethane, propane, or butane. In yet further embodiments, the reducing gas is or originates from flare gas, tail gas, or natural gas. In yet further embodiments, the reducing gas is CH4.

[0060] In certain embodiments, the molar ratio of reducing gas:CO2 in the first gas mixture is from about 10:1 to about 1:10. In further embodiments, the molar ratio of reducing gas:CO2 in the first gas mixture is from about 5:1 to about 0.5:1.

[0061] In certain embodiments, the first product mixture comprises methanol, ethanol, and n-propanol. In further embodiments, the amount of ethanol is at least 10% by weight of the total amount of the first product mixture. In still further embodiments, the molar ratio of ethanol to the total amount of methanol and n-propanol in the first product mixture (ethanol:total amount of methanol and n-propanol) is about 1:5 to about 1:10.

[0062] In certain embodiments, the amount of formic acid in the first product mixture is less than 10 ppm. In further embodiments, the amount of isopropanol in the first product mixture is less than 10 ppm.

[0063] In certain embodiments, the first catalyst is contacted with the first gas mixture for 24 hours. In further embodiments, the first catalyst is contacted with the first gas mixture for 96 hours. In yet further embodiments, the first catalyst is contacted with the first gas mixture for 168 hours. In certain embodiments, the first catalyst is reacted with the reducing gas prior to reacting with the first gas mixture.

[0064] This reactor temperature, referred to herein as the "reduction temperature", is typically 250°C, but may be as high as 600°C, or as low as 50°C. In certain embodiments, the reduction temperature is from about 100°C to about 600°C. In further embodiments, the reduction temperature is about 100°C. In yet further embodiments, the reduction temperature is about 200°C. In preferred embodiments, the reduction temperature is about 250°C. In certain embodiments, the reduction temperature is about 300°C. In further embodiments, the reduction temperature is about 400°C. In yet further embodiments, the reduction temperature is about 500°C. In yet further embodiments, the reduction temperature is about 600°C.

[0065] Such reactor pressure, referred to herein as "reduction pressure", can be between 100 psi and 3000 psi, but is typically 750 psi. In certain embodiments, the reduction pressure is from about 500 psi to about 3000 psi. In further embodiments, the reduction pressure is about 500 psi. In preferred embodiments, the reduction pressure is about 750 psi. In further embodiments, the reduction pressure is about 100 psi. In further embodiments, the reduction pressure is about 1500 psi. In further embodiments, the reduction pressure is about 2000 psi. In further embodiments, the reduction pressure is about 2500 psi. In further embodiments, the reduction pressure is about 3000 psi.

[0066] As will be appreciated by those skilled in the art, the measurement of pressure in units of "pounds per square inch" (psi) can refer to either gauge pressure (psig) (where 0 psi corresponds to atmospheric pressure) or absolute pressure (psia) (where 0 psi corresponds to a perfect vacuum). As used herein, unless expressly specified to the contrary, the unit "psi" refers to gauge pressure (psig).

[0067] After conversion of CO2 and H2 to alcohol and water, the unreacted feedstock and the alcohol and water in the gas phase are cooled in a condenser loop and separated in a gas-liquid separator. The unreacted gas is passed through a recycle loop and combined with fresh feedstock and reintroduced into the reactor. The per-pass conversion rate of the reactor is typically around 20%, but can range from 1% to 99.9%, depending on the gas hourly space velocity (GHSV) of the feed gas, catalyst reactivity, pressure and temperature.

[0068] In certain embodiments, after conversion of the CO2 to alcohol, the ethanol can be separated from the remainder of the alcohol products. Additionally, after conversion of the CO2 to alcohol, the alcohol product mixture can be separated from the paraffin product mixture.

[0069] Conversion of alcohols to olefins In some embodiments, after the production of alcohol, a typical liquid produced by the first step of the process would consist of water together with alcohol. The alcohol would consist primarily of methanol, followed by ethanol, and may have some other tertiary by-products including n-propanol. In some embodiments, the mixture contains up to 20% methanol and up to 20% ethanol. In some embodiments, the mixture contains up to 64% methanol. In some embodiments, the mixture contains up to 15% methanol and up to 3% ethanol. It is an object of the present invention to disclose the optimal liquid concentration for integrating the production of methanol from the reaction of CO2 and the reaction of methanol to olefins. The alcohol to water weight ratio is an important parameter that helps determine the olefin selectivity and activity of the methanol to olefins process.

[0070] In some embodiments, the alcohol and water mixture from the first reactor is condensed to a liquid. In some embodiments, the alcohol and water mixture from the first reactor is transferred in the vapor phase to the second reactor. In some embodiments, the liquid alcohol and water mixture is heated above 100° C. and all of its components are vaporized for introduction into the methanol and into the olefins reactor.

[0071] Catalysts for converting alcohols to olefins suitable for the disclosed systems and methods are disclosed in the following patents, each of which is incorporated by reference in its entirety: EP Patent No. 0,096,996, U.S. Pat. Nos. 4,499,327, 5,191,141, 5,126,308, 5,714,662, and 4,440,871.

[0072] The methods and systems of the present disclosure can include this conversion step being performed on either the complete first product mixture (i.e., containing both alcohols and paraffins) or on a mixture of only the alcohol product mixture.

[0073] The methanol-to-olefins reactor is typically a fixed-bed flow reactor, but may be one of several other reactor types including trickle-bed reactors, fluidized-bed reactors, ebullated-bed reactors, continuous stirred-tank reactors, etc. The methanol-to-olefins reactor contains a catalyst that converts methanol to olefins, such as ethylene, propylene, butylene, etc., at elevated temperatures and ambient to low pressures.

[0074] In some embodiments, the alcohol to olefin (ATO) or methanol to olefin (MTO) catalyst comprises a fluid catalyst particle comprising a crystalline zeolite or silicoaluminophosphate. In further embodiments, the ATO or MTO catalyst comprises SAPO-5, H-SAPO-34, ZSM-11, TNU-9, IM-5, ZSM-35, ZSM-22, ZSM-23, SSZ-13, UZM-12, UZM-9, UZM-5, RUB-13, ZSM-5, or ZSM-34.

[0075] In some embodiments, the ATO or MTO catalyst comprises a transition metal promoted silicoaluminophosphate, e.g., Ni-SAPO-34. In some embodiments, the ATO or MTO catalyst comprises KIT-6 or transition metal promoted KIT-6. In some embodiments, the ATO or MTO catalyst is an acidic catalyst with active sites that support methanol coordination and insertion to selectively produce olefins with water as a by-product. In some embodiments, nickel or other transition metals are used to promote oligomerization.

[0076] In one particular embodiment, an ATO or MTO reactor is configured such that a suspension of methanol vapor and fluid catalyst particles passes upwardly through a dispersed catalyst contact and reaction zone.

[0077] In certain embodiments, the ATO or MTO temperature is about 260°C to about 510°C. In further embodiments, the ATO or MTO temperature is about 315°C to about 370°C. In yet further embodiments, the ATO or MTO temperature is about 315°C. In preferred embodiments, the ATO or MTO temperature is about 325°C. In certain embodiments, the ATO or MTO temperature is about 335°C. In further embodiments, the ATO or MTO temperature is about 345°C. In yet further embodiments, the ATO or MTO temperature is about 355°C. In yet further embodiments, the ATO or MTO temperature is about 365°C. In certain embodiments, the ATO or MTO temperature is about 370°C.

[0078] In certain embodiments, the ATO or MTO pressure is about 100 kPa to about 515 kPa. In a preferred embodiment, the ATO or MTO pressure is about 100 kPa. In certain embodiments, the ATO or MTO pressure is about 200 kPa. In a further embodiment, the ATO or MTO pressure is about 300 kPa. In yet a further embodiment, the ATO or MTO pressure is about 400 kPa. In yet a further embodiment, the ATO or MTO pressure is about 500 kPa. In certain embodiments, the ATO or MTO pressure is about 515 kPa.

[0079] In some embodiments, 90-100% of the methanol is converted to olefins. In some embodiments, ethylene is the preferred product of the MTO or ATO reaction. In some embodiments, the reaction is carried out at ambient pressure. The remaining olefins are separated from the by-product water and purified by distillation, membrane separation, or any other technique known to those skilled in the art for separating olefins. In some embodiments, the ethylene obtained is purified to 90%. In some embodiments, the ethylene obtained is purified to 99.9%. In some embodiments, the ethylene obtained is purified to 99.99% or greater.

[0080] Ethylene Hydrate In some embodiments, the ethylene product entering the olefins reactor from the alcohol is separated and fed to an ethylene hydration reactor. The ethylene hydration reactor is typically a fixed bed flow reactor, but may be one of several other types of reactors. In the ethylene hydration reactor, ethylene is mixed with steam in a ratio of H2O:C2H4 of about 0.6, but this ratio may vary depending on the catalyst used. The steam and ethylene are heated to a temperature between 100-300°C, typically 250°C for a silica supported phosphoric acid catalyst.

[0081] In certain embodiments, the system comprises: a separator configured to separate ethylene from the olefin product mixture; a mixing vessel for combining ethylene and water to form a third feed mixture; and an ethylene hydration reactor for hydrating ethylene to form ethanol, the ethylene hydration reactor comprising a fourth catalyst. It further comprises:

[0082] In a further embodiment, the ethylene hydration reactor is configured such that a mixture of ethylene and steam is passed through a dispersed catalyst contact and reaction zone.

[0083] In certain embodiments, the method comprises the steps of: separating ethylene from the olefin product mixture; forming a third feed mixture comprising ethylene and water; hydrating ethylene in a third feed mixture, the hydrating step including contacting the third feed mixture with a fourth catalyst at an ethylene hydration temperature and an ethylene hydration pressure to produce ethanol. Further includes:

[0084] Ethylene hydration catalysts suitable for the disclosed systems and methods are disclosed in the following patents: U.S. Pat. Nos. 1,873,536, 3,452,106, and 4,482,767, each of which is incorporated by reference in its entirety.

[0085] Catalysts for the ethylene hydration reaction, referred to as "fourth catalysts", include, but are not limited to, silica-supported phosphoric acid, carbon-supported phosphoric acid, zeolites such as H-ZSM-5 or H-Beta, acidic polysiloxanes, polytungstic acid or metal phosphides such as germanium phosphide, titanium phosphide, tin phosphide and silicon phosphide.

[0086] In certain embodiments, the fourth catalyst is a resin-type catalyst. In further embodiments, the fourth catalyst is a sulfonated styrene-divinylbenzene copolymer resin or a silica gel supported phosphoric acid.

[0087] In some embodiments, the olefin reaction involves the C 3+ The product is used to produce larger hydrocarbons in a fixed bed flow reactor. In some embodiments, the C of alcohol is used in the olefin reaction. 3+ Ethylene is used along with the products to produce larger hydrocarbons. This reaction is carried out in a fuel synthesis reactor containing an acidic zeolite, e.g., H-ZSM-5, and unlike the alcohol to olefins process, the olefins are both heated and pressurized to temperatures of about 100°C to 400°C, preferably 250°C, and pressures of about 100 psi to 2000 psi, preferably 1000 psi. The flow rate and conversion per pass through the reactor are controlled to produce C8 to C9 olefins suitable for use as fuels. 16 Or C 10 ~C 20 Select a hydrocarbon in the range of

[0088] In certain embodiments, the ethylene hydration temperature is about 100°C to about 400°C. In further embodiments, the ethylene hydration temperature is about 100°C. In yet further embodiments, the ethylene hydration temperature is about 200°C. In preferred embodiments, the ethylene hydration temperature is about 250°C. In certain embodiments, the ethylene hydration temperature is about 300°C. In further embodiments, the ethylene hydration temperature is about 400°C.

[0089] In certain embodiments, the ethylene hydration pressure is from about 500 psi to about 1500 psi. In further embodiments, the ethylene hydration pressure is about 500 psi. In preferred embodiments, the ethylene hydration pressure is about 1000 psi. In certain embodiments, the ethylene hydration pressure is about 1500 psi.

[0090] Olefin Oligomerization In some embodiments, it is desirable to oligomerize olefins produced from an alcohol-to-olefins process or a methanol-to-olefins process in the presence of an oligomerization catalyst (referred to herein as a "third catalyst") to produce a mixture of higher olefins and optionally aromatics. As used herein, with respect to a hydrocarbon or olefin, the modifier "higher" refers to a hydrocarbon or olefin having a higher carbon number than the precursor. Exemplary higher hydrocarbons and olefins include, but are not limited to, C8-C16 hydrocarbons and / or olefins. The oligomerization process can be carried out in a fixed bed flow reactor, or any other suitable reactor type.

[0091] In certain embodiments, the third catalyst is a zeolite. In further embodiments, the third catalyst is an aluminosilicate zeolite. In yet further embodiments, the third catalyst is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-35. In a preferred embodiment, the third catalyst is ZSM-5.

[0092] The temperature at which the oligomerization can be carried out can range from about 50° C. to about 1000° C. to adjust the degree of oligomerization as needed based on the length and distribution of the desired products. In certain embodiments, the oligomerization temperature is from about 50° C. to about 1000° C. In further embodiments, the oligomerization temperature is about 50° C. In yet further embodiments, the oligomerization temperature is about 150° C. In preferred embodiments, the oligomerization temperature is about 250° C. In certain embodiments, the oligomerization temperature is about 350° C. In further embodiments, the oligomerization temperature is about 450° C. In yet further embodiments, the oligomerization temperature is about 550° C. In yet further embodiments, the oligomerization temperature is about 650° C. In certain embodiments, the oligomerization temperature is about 750° C. In further embodiments, the oligomerization temperature is about 850° C. In yet further embodiments, the oligomerization temperature is about 950° C. In yet further embodiments, the oligomerization temperature is about 1000° C.

[0093] The pressure at which this oligomerization can be carried out can range from about 0 psi to about 2000 psi to adjust the degree of oligomerization as needed based on the length and distribution of the desired products. In certain embodiments, the oligomerization pressure is from about 0 psi to about 2000 psi. In further embodiments, the oligomerization pressure is about 0 psi. In further embodiments, the oligomerization pressure is about 0 psi. In preferred embodiments, the oligomerization pressure is about 30 psi. In certain embodiments, the oligomerization pressure is about 250 psi. In further embodiments, the oligomerization pressure is about 500 psi. In yet further embodiments, the oligomerization pressure is about 750 psi. In yet further embodiments, the oligomerization pressure is about 1000 psi. In certain embodiments, the oligomerization pressure is about 1250 psi. In further embodiments, the oligomerization pressure is about 1500 psi. In yet further embodiments, the oligomerization pressure is about 1750 psi. In yet further embodiments, the oligomerization pressure is about 2000 psi.

[0094] In certain embodiments, the higher olefin product mixture produced during the oligomerization step comprises from about 10% to about 20% by volume aromatics.

[0095] Hydrogenation of higher olefins to higher hydrocarbons Certain embodiments of the systems and methods disclosed herein include hydrogenating a higher olefin product mixture to reduce the number of unsaturated carbon-carbon bonds, thereby obtaining a mixture of higher hydrocarbons. As will be appreciated, a number of catalysts may be suitable for such hydrogenation. As used herein, the term "fifth catalyst" refers to a catalyst for this hydrogenation reaction.

[0096] Furthermore, while this conversion can be carried out in any suitable reactor type, the systems and methods disclosed herein typically utilize fixed bed flow reactors. In certain embodiments, the olefin reduction reactor is configured such that a pressurized higher olefin mixture passes through a dispersed catalyst contact and reaction zone.

[0097] In certain embodiments, the fifth catalyst is an aluminosilicate catalyst. In further embodiments, the fifth catalyst is H-ZSM-5.

[0098] In certain embodiments, the olefin reduction temperature is from about 100° C. to about 400° C. In certain embodiments, the olefin reduction temperature is about 100° C. In further embodiments, the olefin reduction temperature is about 200° C. In preferred embodiments, the olefin reduction temperature is about 250° C. In certain embodiments, the olefin reduction temperature is about 300° C. In further embodiments, the olefin reduction temperature is about 400° C.

[0099] In certain embodiments, the olefin reduction pressure is from about 0 psi to about 1500 psi. In certain embodiments, the olefin reduction pressure is about 0 psi. In further embodiments, the olefin reduction pressure is about 500 psi. In a preferred embodiment, the olefin reduction pressure is about 1000 psi. In certain embodiments, the olefin reduction pressure is about 1500 psi.

[0100] Conversion of paraffin to jet fuel In some embodiments, the C3 and higher paraffins, olefins and other hydrocarbons produced by the methanol to olefins process can be converted into jet fuel.

[0101] Catalysts suitable for the disclosed systems and methods for converting olefins into heavy hydrocarbons suitable for use as jet fuels are disclosed in the following patents, each of which is incorporated by reference in its entirety: U.S. Pat. Nos. 5,210,347, 4,504,693, 4,456,781, 4,834,949, 5,177,279, and PCT Publication No. WO 2001 / 062875.

[0102] In certain aspects of the present disclosure, the apparatus may be used to blend the higher hydrocarbon product mixture, optionally with a paraffin product mixture, to produce a blended paraffin product mixture.

[0103] Furthermore, in certain aspects of the present disclosure, it may be advantageous to isomerize a portion of the linear paraffins and / or linear higher hydrocarbons to obtain an isomerized paraffin product mixture comprising linear paraffins, branched paraffins and cyclic paraffins. Such isomerization may be accomplished using any suitable catalyst, preferably a catalyst referred to herein as "sixth catalyst". In certain embodiments, the sixth catalyst is a zeolite or AlCl3. In further embodiments, the sixth catalyst is AlCl3. Furthermore, the isomerization may be performed in any suitable reactor, but is preferably performed in a continuous stirred tank reactor.

[0104] The disclosed systems and methods may also include additional equipment for fractionating the blended paraffin mixture to produce jet fuel, in certain embodiments, the jet fuel produced comprises about 10% to about 20% aromatics by volume.

[0105] definition 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 and techniques of chemistry, cell and tissue culture, molecular biology, cell and cancer biology, neurobiology, neurochemistry, virology, immunology, microbiology, pharmacology, genetics, and protein and nucleic acid chemistry described herein are well known and commonly used in the art.

[0106] The methods and techniques of the present disclosure are generally performed in accordance with conventional methods well known in the art and described in various general and more specific references cited and discussed throughout this specification, unless otherwise indicated. See, for example, "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 Edition", WH Freeman & Co., New York (2000); Griffiths et al., "Introduction to Genetic Analysis, 7th Edition", WH Freeman & Co., NY (1999); and Gilbert et al., "Developmental Biology, 6th Edition", Sinauer Associates, Inc., Sunderland, MA (2000).

[0107] Chemical terms used herein, unless otherwise defined herein, are used in accordance with conventional usage in the art as exemplified by "The McGraw-Hill Dictionary of Chemical Terms," ​​Parker S. (ed.), McGraw-Hill, San Francisco, Calif. (1985).

[0108] All of the above, as well as any other publications, patents and published patent applications referenced in this application, are specifically incorporated herein by reference. In case of conflict, the present specification, including its specific definitions, will control.

[0109] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes cases where said event or circumstance occurs as well as cases where it does not occur. For example, "optionally substituted alkyl" refers to both alkyl being optionally substituted and alkyl being unsubstituted.

[0110] It is understood that the substituents and substitution patterns on the compounds of the present invention can be selected by those skilled in the art to provide chemically stable compounds that can be easily synthesized from readily available starting materials by techniques known in the art and the methods described below. When a substituent is itself substituted with more than one group, it is understood that these multiple groups can be present on the same carbon or on different carbons as long as a stable structure is provided.

[0111] As used herein, the term "optionally substituted" refers to the replacement of 1-6 hydrogen radicals in a given structure with a specific substituent radical, including but not limited to: hydroxyl, hydroxyalkyl, alkoxy, halogen, alkyl, nitro, silyl, acyl, acyloxy, aryl, cycloalkyl, heterocyclyl, amino, aminoalkyl, cyano, haloalkyl, haloalkoxy, -OCO-CH2-O-alkyl, -OP(O)(O-alkyl)2, or -CH2-OP(O)(O-alkyl). Preferably, "optionally substituted" refers to the replacement of 1-4 hydrogen radicals in a given structure with the above substituents. More preferably, 1-3 hydrogen radicals are replaced by the above substituents. It is understood that the substituents may be further substituted.

[0112] As used herein, the term "alkyl" refers to any alkyl group including, but not limited to, C1 to C 10 Straight chain alkyl group or C1-C 10 It refers to saturated aliphatic groups, including branched alkyl groups. Preferably, the "alkyl" group refers to a C1-C6 straight chain alkyl group or a C1-C6 branched chain alkyl group. Most preferably, the "alkyl" group refers to a C1-C4 straight chain alkyl group or a C1-C4 branched chain alkyl group. Examples of "alkyl" include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, 1-pentyl, 2-pentyl, 3-pentyl, neo-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, 1-octyl, 2-octyl, 3-octyl, or 4-octyl. The "alkyl" group may be optionally substituted.

[0113] The term "acyl" is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)-, preferably alkylC(O)-.

[0114] The term "acylamino" is art-recognized and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula hydrocarbylC(O)NH-.

[0115] The term "acyloxy" is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)O-, preferably alkylC(O)O-.

[0116] The term "alkoxy" refers to an alkyl group having an oxygen attached thereto. Representative alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy, and the like.

[0117] The term "alkoxyalkyl" refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl.

[0118] The term "alkyl" refers to saturated aliphatic groups, including straight chain alkyl groups, branched chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups. In preferred embodiments, a straight chain or branched chain alkyl group has 30 or fewer carbon atoms in its backbone (e.g., 0.01 to 0.01 carbon atoms for straight chain). 1~30 , for branched chains, C 3~30 ), more preferably having 20 or fewer carbon atoms.

[0119] Furthermore, the term "alkyl," as used throughout the specification, examples, and claims, is intended to include both unsubstituted and substituted alkyl groups, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone, and includes haloalkyl groups, such as trifluoromethyl and 2,2,2-trifluoroethyl.

[0120] The term “C x~y " or "C x ~C y" when used in conjunction with a chemical moiety, such as acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy, is intended to include groups containing x to y carbons in the chain. CO alkyl denotes hydrogen, the group is in a terminal position, if internal, it is a bond. 1~6 An alkyl group, for example, contains 1 to 6 carbon atoms in the chain.

[0121] The term "alkylamino," as used herein, refers to an amino group substituted with at least one alkyl group.

[0122] The term "alkylthio," as used herein, refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-.

[0123] The term "amide" as used herein refers to the group

[0124] [ka] Refers to, R 9 and R 10 each independently represents a hydrogen or a hydrocarbyl group, or R 9 and R 10 together with the N atom to which they are attached complete a heterocycle having 4 to 8 atoms in the ring structure.

[0125] The terms "amine" and "amino" are art-recognized and refer to both unsubstituted and substituted amines and their salts, e.g.,

[0126] [ka] "The term '" refers to a part that can be expressed by R 9 , R 10 and R 10' each independently represents a hydrogen or a hydrocarbyl group, or R 9and R 10 together with the N atom to which they are attached complete a heterocycle having 4 to 8 atoms in the ring structure.

[0127] The term "aminoalkyl," as used herein, refers to an alkyl group substituted with an amino group.

[0128] The term "aralkyl," as used herein, refers to an alkyl group substituted with an aryl group.

[0129] The term "aryl" as used herein includes substituted or unsubstituted monocyclic aromatic groups in which each atom of the ring is carbon. Preferably, the ring is a 5- to 7-membered ring, more preferably a 6-membered ring. The term "aryl" also includes polycyclic ring systems having two or more cyclic rings (cyclic rings), where two or more carbons are common to two connected rings, and at least one of the rings is aromatic, for example, the other cyclic ring can be cycloalkyl, cycloalkenyl, cycloalkynyls, aryl, heteroaryl and / or heterocyclyl. Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like.

[0130] The term "carbamate" is art-recognized and refers to a group

[0131] [ka] Refers to, R 9 and R 10 independently represent hydrogen or a hydrocarbyl group.

[0132] The term "carbocyclylalkyl," as used herein, refers to an alkyl group substituted with a carbocycle group.

[0133] The term "carbocycle" includes 5-7 membered monocyclic rings and 8-12 membered bicyclic rings. Each ring of a bicyclic carbocycle can be selected from saturated, unsaturated, and aromatic rings. Carbocycles include bicyclic molecules in which one, two, or three or more atoms are shared between the two rings. The term "fused carbocycle" refers to a bicyclic carbocycle in which each ring shares two adjacent atoms with the other ring. Each ring of a fused carbocycle can be selected from saturated, unsaturated, and aromatic rings. In an exemplary embodiment, an aromatic ring, such as phenyl, may be fused to a saturated or unsaturated ring, such as cyclohexane, cyclopentane, or cyclohexene. Any combination of saturated, unsaturated, and aromatic bicyclic rings is included in the definition of carbocycle, as long as valence permits. Exemplary "carbocycles" include cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]oct-3-ene, naphthalene, and adamantane. Exemplary fused carbocycles include decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4,5,6,7-tetrahydro-1H-indene, and bicyclo[4.1.0]hept-3-ene. A "carbocycle" may be substituted at any one or more positions capable of bearing a hydrogen atom.

[0134] The term "carbocyclylalkyl," as used herein, refers to an alkyl group substituted with a carbocycle group.

[0135] The term "carbonate" is art-recognized and refers to the group -OCO2-.

[0136] The term "carboxy," as used herein, refers to a group represented by the formula -CO2H.

[0137] The term "ester" as used herein refers to the group -C(O)OR 9 R 9 represents a hydrocarbyl group.

[0138] The term "ether" as used herein refers to a hydrocarbyl group that is linked to another hydrocarbyl group via oxygen. Thus, the ether substituent of a hydrocarbyl group may be hydrocarbyl-O-. Ethers may be either symmetrical or asymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include "alkoxyalkyl" groups, which can be represented by the general formula alkyl-O-alkyl.

[0139] The terms "halo" and "halogen" as used herein mean halogens and include chloro, fluoro, bromo and iodo.

[0140] The terms "hetaralkyl" and "heteroaralkyl," as used herein, refer to an alkyl group substituted with a hetaryl group.

[0141] The terms "heteroaryl" and "hetaryl" include substituted or unsubstituted aromatic monocyclic ring structures, preferably 5-7 membered rings, more preferably 5-6 membered rings, which ring structures contain at least one heteroatom, preferably 1-4 heteroatoms, more preferably 1 or 2 heteroatoms. The terms "heteroaryl" and "hetaryl" also include polycyclic ring systems having two or more cyclic rings, where two or more carbons are common to two bonded rings, and at least one of the rings is heteroaromatic, for example, the other cyclic ring can be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, and / or heterocyclyl. Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine.

[0142] The term "heteroatom" as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen and sulfur.

[0143] The term "heterocyclylalkyl," as used herein, refers to an alkyl group substituted with a heterocycle group.

[0144] The terms "heterocyclyl", "heterocycle" and "heterocyclic" refer to substituted or unsubstituted non-aromatic ring structures, preferably 3-10 membered rings, more preferably 3-7 membered rings, which ring structures contain at least one heteroatom, preferably 1-4 heteroatoms, more preferably 1 or 2 heteroatoms. The terms "heterocyclyl" and "heterocyclic" also include polycyclic ring systems having two or more cyclic rings, where two or more carbons are common to two bonded rings, and at least one of the rings is heterocyclic, e.g., the other cyclic ring can be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl and / or heterocyclyl. Heterocyclyl groups include, for example, piperidine, piperazine, pyrrolidine, morpholine, lactones, lactams, and the like.

[0145] The term "hydrocarbyl" as used herein refers to a group bonded via a carbon atom, as described above, that does not have =O or =S substituents, and typically has at least one carbon-hydrogen bond and a predominantly carbon backbone, but may optionally contain heteroatoms. Thus, groups such as methyl, ethoxyethyl, 2-pyridyl, and even trifluoromethyl are considered hydrocarbyl for the purposes of this application, while substituents such as acetyl (which has =O substituents on the linking carbon) and ethoxy (which is linked via oxygen, not carbon) are not considered hydrocarbyl. Hydrocarbyl groups include, but are not limited to, aryl, heteroaryl, carbocyclic, heterocyclic, alkyl, alkenyl, alkynyl, and combinations thereof.

[0146] The term "hydroxyalkyl," as used herein, refers to an alkyl group substituted with a hydroxy group.

[0147] The term "lower" when used in conjunction with chemical moieties such as acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy, is intended to include groups in which there are 10 or fewer atoms, preferably 6 or fewer atoms, in the substituent. "Lower alkyl" refers, for example, to alkyl groups containing 10 or fewer, preferably 6 or fewer carbon atoms. In certain embodiments, the acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy substituents as defined herein are lower acyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy, respectively, whether they appear alone or in combination with other substituents, such as those recited in hydroxyalkyl and aralkyl (where, for example, when counting the carbon atoms in an alkyl substituent, the atoms in an aryl group are not counted).

[0148] The terms "polycyclyl", "polycycle" and "polycyclic" refer to two or more rings (e.g., cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl and / or heterocyclyl) in which two or more atoms are common to two connected rings, e.g., the rings are "fused rings". Each of the rings of a polycycle can be substituted or unsubstituted. In certain embodiments, each ring of a polycycle contains 3 to 10, preferably 5 to 7, atoms in the ring.

[0149] The term "sulfate" is art-recognized and refers to the group -OSO3H or a pharma- ceutically acceptable salt thereof.

[0150] The term "sulfonamide" is art-recognized and can be represented by the general formula

[0151] [ka] " refers to a group represented by R 9 and R 10 independently represent hydrogen or hydrocarbyl.

[0152] The term "sulfoxide" is art-recognized and refers to the group --S(O)--.

[0153] The term "sulfonate" is art-recognized and refers to the group SO3H, or a pharma- ceutically acceptable salt thereof.

[0154] The term "sulfone" is art-recognized and refers to the group -S(O)2-.

[0155] The term "substituted" refers to a moiety having a substituent replacing a hydrogen on one or more carbons of the backbone. It is understood that "substituted" or "substituted by" includes the implicit assumption that such substitution is subject to the permissible valences of the atom and substituent being substituted, and that the substitution results in a stable compound that does not undergo transformation, e.g., spontaneously, by, e.g., rearrangement, cyclization, elimination, and the like. As used herein, the term "substituted" is intended to include all of the permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this invention, heteroatoms, e.g., nitrogen, can have hydrogen substituents and / or any permissible substituent of organic compounds described herein that satisfies the valence of the heteroatom. The substituents may include any of the substituents described herein, for example, halogen, hydroxyl, carbonyl (e.g., carboxyl, alkoxycarbonyl, formyl, or acyl), thiocarbonyl (e.g., thioester, thioacetate, or thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino, amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain may themselves be substituted, if appropriate.

[0156] The term "thioalkyl," as used herein, refers to an alkyl group substituted with a thiol group.

[0157] The term "thioester" as used herein refers to the group -C(O)SR 9 Or -SC(O)R 9 Refers to, R 9 represents hydrocarbyl.

[0158] The term "thioether" as used herein is equivalent to an ether, where the oxygen is replaced by a sulfur.

[0159] The term "urea" is art-recognized and has the general formula

[0160] [ka] It can be expressed by R 9 and R 10 independently represent hydrogen or hydrocarbyl.

[0161] The term "modulate" as used herein includes inhibiting or suppressing a function or activity (eg, cell proliferation), as well as enhancing a function or activity.

[0162] The terms "logarithm of solubility", "LogS" or "logS" as used herein are used in the art to quantify the aqueous solubility of a compound. The aqueous solubility of a compound significantly affects its absorption and distribution characteristics. Low solubility is often accompanied by poor absorption. LogS values ​​are the unit-free logarithm (base 10) of the solubility measured in mol / liter.

[0163] As used herein, the term "hydrated carbon dioxide" includes all reaction products resulting from the reaction of carbon dioxide gas with water in the presence of a catalyst, including, but not limited to, carbonic acid, carbonate salts and / or ions, and bicarbonate salts and / or ions.

[0164] [Example] Having generally described the invention, the invention will be more readily understood by reference to the following examples, which are included merely for purposes of illustration of certain specific aspects and embodiments of the invention and are not intended to limit the invention.

[0165] [Example 1] Conversion of CO2 and H2 to methanol in a fixed-bed flow reactor CO2 hydrogenation was carried out in a fixed-bed flow reactor with an internal volume of approximately 9 liters. Ten kilograms of catalyst consisting of 63 wt% copper oxide, 27 wt% zinc oxide, and 10 wt% aluminum oxide were loaded into the flow reactor and compressed into a cylinder with a height of 6 mm and a diameter of 4 mm. To activate the catalyst, the reactor was heated to approximately 300°C while H2 gas was flowed through the reactor at a flow rate of 30 standard liters per minute (SLPM) and a pressure of 100 psi. During this activation period, water was collected in a separator downstream of the flow reactor. After catalyst activation, the temperature of the reactor was reduced to 250°C and the pressure was increased to 750 psi. H2 and CO2 were flowed through the reactor at flow rates of 30 SLPM and 10 SLPM, respectively. The gases were reacted on the surface of the catalyst to produce approximately 0.4 liters per hour of methanol-water mixture with a density of 0.89 g / mL, which corresponds to approximately 64% methanol in water, thus achieving quantitative selectivity for methanol production. Unreacted gases were recycled from the reactor by a recycle loop and compressor to improve the yield of methanol production.

[0166] [Example 2] General Procedure for the Conversion of Methanol to Olefins The dehydration of methanol to produce ethylene, propylene and other hydrocarbons is carried out in a fixed bed flow reactor. 10 kg of silicoaluminophosphate catalyst H-SAPO-34, a chabazite structured material consisting of 50 wt. % aluminum oxide, 30-45 wt. % phosphorus oxide and 20-5 wt. % silicon oxide, is loaded into the flow reactor. The reactor is heated to a temperature of 450°C. A feed mixture consisting of 40% methanol and 60% water is heated to above 180°C to produce methanol and water as steam, which is then pumped at 50 PSI and a weight hourly space velocity of 5.0 h -1 Methanol is converted to a mixture of ethylene, propylene, butenes, pentenes, paraffins, olefins and aromatics, with the major product being ethylene which is separated from the other products by distillation.

[0167] [Example 3] General Procedure for the Conversion of Olefins to Jet Fuel A mixture of C3 and higher paraffins, olefins, and other hydrocarbons is converted to jet fuel in a fixed bed flow reactor. The mixture of C3 and higher hydrocarbon feed is the product of a methanol to olefins system and ethylene is removed by distillation. 10 kg of aluminosilicate catalyst H-ZSM-5, consisting of aluminum oxide and silicon oxide with a silica to alumina ratio of approximately 70:1, is loaded into the flow reactor. The reactor is heated to approximately 250°C. The mixture of C3 and higher hydrocarbons is pressurized to approximately 30-1000 psi and introduced into the reactor. The flow rate of the C3 and higher hydrocarbon feed is controlled to obtain a mixture of C8-C 16 A conversion rate of approximately 50 wt.% is achieved per pass through the reactor to a mixture of hydrocarbons. C8-C 16 The hydrocarbons are distilled to remove the heavy fraction of paraffin wax, resulting in a hydrocarbon liquid that has an energy density of approximately 11.3 kWh / L, making it particularly suitable as a jet fuel.

[0168] [Example 4] Olefin formation by methanol to olefins process A 1-inch diameter flow reactor was loaded with 15 g of H-SAPO-34 catalyst pelletized into a cylinder with a diameter of 7.6 mm and a thickness of 2.5 mm. Nitrogen was fed to the reactor at 0.1 SLPM. The system was flushed with N2 for 15 minutes, after which the furnace was slowly heated to 450 °C. A liquid mixture taken directly from the CO2 hydrogenation reactor containing 40% methanol and 60% water was fed to the preheated zone at 180 °C at 2.5 mL / min to produce a vapor of methanol and water. The vapor was then pumped at 50 PSI and a weight hourly space velocity of 5.0 h -1 The resulting gas mixture, containing mainly ethylene, propylene, and some other alkanes and olefins, was collected after the gas-liquid separator and analyzed by GC-TCD. The liquid output, containing water and unreacted methanol, was collected from the gas-liquid separator and analyzed by GC-FID.

[0169] After the methanol conversion dropped below 90%, the SAPO catalyst was regenerated. The reactor was heated to 650° C. and DI water was fed to the reactor at 0.75 mL / min for 40 minutes. The reactor was then cooled to 450° C. and the methanol-to-olefins process was resumed.

[0170] [Table 1]

[0171] FIG. 4 shows a GC-FID chromatogram of the products from the MTO process disclosed herein.

[0172] [Example 5] Aromatic formation from propylene oligomerization. Propylene was fed to a fixed bed flow reactor (having a diameter of 2 mm and a length of 10 mm) containing 20 g of ZSM-5 catalyst. Alumina was used as an inert and was packed into the reactor. Propylene was fed to the reactor at 2.5 SCFH (1.2 SLPM) and 30 PSI for 10 minutes, after which the reactor was slowly heated to 250°C. Propylene was fed at 2.5 SCFH (1.2 SLPM) for 1 hour, and 100 mL of golden yellow liquid was collected. The resulting liquid was collected from the gas-liquid separator and analyzed by GC-FID.

[0173] FIG. 5 shows a GC-FID chromatogram of the propylene oligomerization product liquid.

[0174] [Example 6] Iso-paraffin formation from paraffin isomerization A 600 mL continuous stirred tank reactor was charged with 10 g AlCl3 and 50 mL paraffins containing 98% linear n-paraffins from C7 to C28. The reactor was sealed and flushed with H2 at 100 PSI three times to remove residual air. The system was then pressurized with H2 at 500 PSI and heated to 150°C with vigorous stirring for 6 hours. The reactor was then cooled to room temperature and the pressure was released. The resulting light yellow liquid was then collected and analyzed by GC-FID. 19% of the n-paraffins underwent isomerization to give iso-paraffin and cyclo-paraffin isomers.

[0175] FIG. 6 shows a comparison of the GC-FID chromatograms for the paraffin liquid feed and the isomerized product.

[0176] [Example 7] Ethanol production from ethylene hydration. A 1 inch diameter fixed bed reactor was charged with 15 g of catalyst containing phosphate treated silica. Alumina was used as an inert and was packed into the remaining part of the reactor. The system was sealed and flushed with N2 for 20 minutes, after which ethylene was fed at 150 PSI. The reactor was then slowly heated to 250°C. Water was fed to the reactor by a high pressure syringe pump to maintain a steam / ethylene ratio of 2. The liquid was collected from the liquid gas separator and analyzed by GC-FID to determine the amount of ethanol formed.

[0177] FIG. 7 shows the GC-FID chromatogram of the ethylene hydrogenation liquid product.

[0178] Incorporation by Reference All publications and patents mentioned herein are 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 case of conflict, the present application, including any definitions herein, will control.

[0179] Equal Form While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Numerous variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims that follow. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

Claims

1. CO 2 A method for converting CO 2 and a reducing gas, contacting a first gas mixture with a first catalyst to produce a first product mixture comprising methanol; A second feed mixture comprising methanol is contacted with a second catalyst to produce ethylene, as well as C 3 and producing a second product mixture comprising higher paraffins, olefins and other hydrocarbons; and contacting the third feed mixture comprising ethylene and water with a fourth catalyst to produce ethanol. A method comprising:

2. The first catalyst comprises: molybdenum one or more first elements selected from Group V, VI, VII, VIII, IX, X, and XI metals; and one or more second elements selected from sulfur, carbon, oxygen, phosphorus, nitrogen and selenium Optionally, one or more Group IA metals Including, the molybdenum is present in an amount of 10 to 50 weight percent of the total amount of the one or more first elements, molybdenum, one or more second elements, and Group IA metal; The method of claim 1.

3. The method of claim 2, wherein the one or more first elements include silver, cobalt, nickel, copper, rhodium, ruthenium, iridium, palladium, niobium or manganese, or the one or more first elements include cobalt.

4. The first catalyst comprises silver, molybdenum, sulfur and a Group IA metal, or the first catalyst comprises nickel, cobalt, molybdenum, sulfur and a Group IA metal; or the first catalyst comprises niobium, cobalt, molybdenum, sulfur and a Group IA metal; The method of claim 3.

5. The method of claim 1, wherein the first catalyst is: copper, zinc, one or more first elements selected from cobalt, nickel, or iron; Aluminum, and oxygen Optionally, one or more second elements selected from Group V, VI, VII, VIII, IX, X, or XI metals; and Optionally, one or more Group IA metals 2. The method of claim 1, comprising:

6. The first catalyst comprises cobalt, copper, zinc, oxygen, and alumina; or 6. The method of claim 5, wherein the first catalyst comprises cobalt, copper, zinc, oxygen, alumina, and a Group IA metal.

7. The method of claim 1, wherein the first catalyst comprises copper, zinc, oxygen, and aluminum.

8. The method of claim 1, wherein the reducing gas is H 2 or a hydrocarbon.

9. The method of claim 1, wherein the first catalyst comprises a metal selected from the group consisting of platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, and any combination thereof; the second catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof; The fourth catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof; The method of claim 1.

10. The method of claim 1, wherein the second catalyst is selected from the group consisting of 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, ZSM-34, and any combination thereof; the fourth catalyst is selected from the group consisting of 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, ZSM-34, and any combination thereof; The method according to claim 1 or 9.

11. The method of claim 10, further comprising contacting the second product mixture, comprising C3 and higher paraffins, olefins and other hydrocarbons, with a third catalyst to produce jet fuel; the third catalyst is a zeolite; The method of claim 1.

12. The method of claim 10, wherein the first catalyst comprises CuZn.

13. A system for producing alcohol, comprising: a CO2 reduction reactor for converting a first gas mixture comprising CO2 and a reducing gas to a first product mixture comprising an alcohol product mixture, the CO2 reduction reactor comprising a first catalyst; an ATO reactor for dehydrating an alcohol product mixture into a second product mixture comprising one or more olefins, the ATO reactor comprising a second catalyst; a separator configured to separate ethylene from the second product mixture; and an ethylene hydration reactor for hydrating ethylene to form ethanol, the ethylene hydration reactor optionally comprising a fourth catalyst. A system comprising:

14. The system of claim 13, wherein the first catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or an alloy or compound thereof.

15. The system of claim 13, wherein the first catalyst comprises nanoparticles comprising CuZn, CuZnFeK, CuZnFeKC, CuZnFeAlK, CuZnFeNa, CuZnFeCoK, CuZnFeCoNaK, CuCoAl, CoMoSK, CuZnK, CuCoMn, RhRu, PdCuFe, Rh or RhFeSi, optionally supported on an alumina support.

16. The method of claim 1, wherein the first catalyst is: copper zinc one or more first elements selected from cobalt, nickel, or iron; Aluminum, and oxygen The system of claim 13, comprising:

17. The system of claim 14, wherein the first catalyst comprises cobalt, copper, zinc, oxygen, and alumina.

18. The system of claim 13, wherein the first catalyst comprises copper, zinc, oxygen, and alumina.

19. The system of claim 13, wherein the reducing gas is H 2 or a hydrocarbon.

20. The system of claim 13, wherein the first catalyst comprises CuZn.

21. The method of claim 20, wherein the first catalyst comprises a metal selected from the group consisting of platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, and any combination thereof; the second catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof; The fourth catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof; The system of claim 13.

22. The method of claim 21, wherein the second catalyst is selected from the group consisting of 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, ZSM-34, and any combination thereof; the fourth catalyst is selected from the group consisting of 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, ZSM-34, and any combination thereof; 22. The system of claim 21.

23. The system of claim 13, wherein the second catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof.

24. The system of claim 13, wherein the fourth catalyst is selected from the group consisting of crystalline zeolites, silicoaluminophosphates, and any combination thereof.

25. An oligomerization reactor for oligomerizing an olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, the oligomerization reactor further comprising a third catalyst; the third catalyst is a zeolite; 22. The system of claim 21.

26. An oligomerization reactor for oligomerizing an olefin product mixture to a higher olefin product mixture comprising unsaturated paraffins and optionally aromatics, the oligomerization reactor further comprising a third catalyst; the third catalyst is a zeolite; The system of claim 13.

27. A method for converting CO2 to jet fuel, comprising: contacting a first gas mixture comprising CO2 and a reducing gas with a first catalyst at a reducing temperature and pressure to produce a first product mixture and a paraffinic product mixture comprising one or more paraffins, the first product mixture comprising methanol; contacting the first product mixture comprising methanol with a second catalyst to produce a second product mixture comprising ethylene and C3, higher paraffins, and olefins; oligomerizing the second product mixture into a higher hydrocarbon product mixture comprising unsaturated paraffins and aromatics, the oligomerizing step comprising contacting the second product mixture with a third catalyst; and Blending the higher hydrocarbon product mixture and the paraffin product mixture to produce jet fuel. A method comprising:

28. The method of claim 27, wherein the step of blending the higher hydrocarbon product mixture and the paraffin product mixture produces a blended paraffin product mixture, and the method further comprises the step of fractionating the blended paraffin product mixture to produce jet fuel.

29. The method of claim 27, further comprising the step of isomerizing a proportion of the blended paraffin product mixture to obtain an isomerized paraffin product mixture comprising linear paraffins, branched paraffins and cyclic paraffins, said isomerization comprising the step of contacting the blended paraffin product mixture with a sixth catalyst.

30. The method of claim 29, wherein the sixth catalyst is a zeolite.

31. The method of claim 30, wherein the zeolite is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof.

32. The method of claim 27, wherein the jet fuel contains about 10% by volume to about 20% by volume of aromatic compounds.

33. The method of claim 27, wherein the third catalyst is a zeolite.

34. The method of claim 33, wherein the zeolite is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and any combination thereof.

35. The method of claim 27, wherein the second catalyst comprises fluid catalyst particles comprising a crystalline zeolite or a silicoaluminophosphate.

36. The method of claim 35, 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.

37. The method of claim 27, wherein the first catalyst comprises platinum, palladium, copper, cobalt, zinc, selenium, rhodium, iron, molybdenum, sulfur, oxygen, or an alloy or compound thereof.

38. The method of claim 27, wherein the first catalyst comprises nanoparticles comprising CuZn, CuZnFeK, CuZnFeKC, CuZnFeAlK, CuZnFeNa, CuZnFeCoK, CuZnFeCoNaK, CuCoAl, CoMoSK, CuZnK, CuCoMn, RhRu, PdCuFe, Rh or RhFeSi, optionally supported on an alumina support.

39. The method of claim 27, further comprising the step of hydrogenating the higher hydrocarbon product mixture or the olefins prior to blending.

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