Method and catalyst for converting carbon dioxide to long chain hydrocarbons - Patents.com

Abstract

The present disclosure provides catalysts, reactor systems, and methods for converting carbon dioxide and hydrogen gas into paraffins, olefins, and other hydrocarbon products. Also included are methods for the utilization of mixtures of carbon dioxide, carbon monoxide, and hydrogen gas in a manner other than that of a conventional Fischer-Tropsch reactor to produce hydrocarbons.

Description

[Technical field]

[0001] The present invention relates to a process and catalyst for the conversion of carbon dioxide to long chain hydrocarbons.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 298,402, filed January 11, 2022, and U.S. Provisional Patent Application No. 63 / 409,085, filed September 22, 2022. The entire contents of each of these applications are incorporated herein by reference. [Background technology]

[0003] As atmospheric carbon dioxide concentrations increase, developing technologies to remove carbon dioxide from the air is becoming advantageous from the perspectives of social welfare, human health, and energy security. Carbon dioxide conversion technologies are 2 Combined with air capture, this has the added benefit of producing commodity chemicals on-site anywhere in the world, without the cost or risk of transportation. 2 The need to eliminate solar radiation is coupled with the increasing global use of renewable electricity generation methods such as photovoltaic cells and wind turbines. Techniques such as these use intermittent energy sources such as the sun, which sets in the evening and rises in the morning, and the wind, which blows intermittently. Thus, the supply of electricity from these sources to the grid is spiked at some times and low at other times. This presents an opportunity for technologies that can utilize electricity intermittently to produce desired products on-site.

[0004] Of the available technologies for producing chemicals from carbon dioxide, hydrogenation of carbon dioxide or carbon monoxide using renewably derived hydrogen gas from a water electrolyser or equivalent system that produces carbon-neutral hydrogen gas can be fully powered by renewable (such as solar, wind, hydroelectric, etc.) electricity. Such methods use an external energy source to convert carbon-based feedstocks (carbon dioxide or carbon monoxide) and water into hydrocarbon chemicals, which is similar to the fundamental photosynthetic process that makes life on Earth possible. For example, plants use photosynthesis to convert carbon dioxide, water, and solar energy into chemical energy by creating sugars and other complex hydrocarbons. This effectively stores energy from the sun in the chemical bonds of carbon-based compounds. This process has supported Earth's ecosystems for billions of years, balancing atmospheric carbon dioxide concentrations. Summary of the Invention [Problem to be solved by the invention]

[0005] In the last century, humans have utilized the by-products of photosynthesis, such as fossil fuels, to provide the energy necessary for modern life. This has released millions of tons of carbon dioxide into the Earth's atmosphere that was previously sequestered in fossil fuels by photosynthesis over millions of years. Scientific evidence points to this rapid increase in atmospheric carbon dioxide concentrations from anthropogenic sources being potentially catastrophic for the global climate. Thus, the development of carbon negative processes that mimic the natural processes that sequester carbon dioxide is important for the future of the Earth, and it is the purpose of this application to disclose one such invention. [Means for solving the problem]

[0006] In certain aspects, the disclosure provides a catalyst comprising copper, zinc, one or more first elements selected from iron or cobalt, oxygen, optionally aluminum, 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, wherein the one or more first elements are present in an amount of about 1 to about 50 weight % (e.g., about 1 to about 10 weight %, about 25 to about 40 weight %, about 30 to about 40 weight %, or about 35 to about 50 weight %) of the total amount of copper, zinc, the one or more first elements, the optional second elements, and the optional Group IA metals.

[0007] In certain aspects, the present disclosure provides a copper zinc aluminum (CZA) catalyst comprising copper, zinc, optionally one or more first elements selected from cobalt, iron, or nickel, oxygen, optionally aluminum, and 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, wherein the molar ratio of copper to zinc is about 1 to about 5.

[0008] In certain aspects, the present disclosure provides a catalyst comprising one or more metals, preferably the metal is iron, optionally one or more second elements selected from copper and / or zinc, optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, or palladium), and optionally a Group IA or IIA metal promoter.

[0009] In certain aspects, the present disclosure provides a catalyst composition comprising a catalyst disclosed herein and, optionally, an additional support.

[0010] In certain aspects, the present disclosure provides methods for preparing the catalysts or catalyst compositions disclosed herein, such as methods that include preparing the catalyst by co-precipitation, wet impregnation, or ball milling, or a combination thereof.

[0011] In certain aspects, the present disclosure provides a method for the preparation of a method for treating a cancer cell comprising administering to a patient a 2 , CO, or a mixture of the two to a liquid product mixture, comprising: 2 , CO, or a mixture of the two, and a reducing agent gas, at a reducing temperature and pressure, thereby providing a liquid product mixture.

[0012] In certain aspects, the present disclosure provides a catalyst comprising one or more paraffinic metal oxides, optionally a support, and optionally one or more metal additives. [Brief description of the drawings]

[0013] [Figure 1] 1 shows a gas chromatogram identifying the major individual hydrocarbon compounds, namely linear alkanes, in a hydrocarbon mixture produced by an exemplary cobalt copper zinc catalyst. [Diagram 2] 1 shows a gas chromatogram identifying the major individual hydrocarbon compounds in a hydrocarbon mixture produced by an exemplary iron copper zinc catalyst, including linear alkanes and primary olefins. [Diagram 3] 1 shows a zoomed-in gas chromatogram identifying individual hydrocarbon compounds in a hydrocarbon mixture produced by an exemplary iron-copper-zinc catalyst, including secondary olefins, aromatics, and cycloalkanes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] One of the major obstacles towards carbon dioxide sequestration is the effective utilization and catalytic conversion of carbon dioxide or carbon monoxide to useful chemicals. Plants achieve this through dehydrogenases, which utilize transition metals to catalyze the hydrogenation of carbon dioxide to carbon monoxide, formic acid, or some other component of cellulose. Artificial systems have attempted to replicate this pathway, and chemical methods for carbon dioxide conversion have been known for decades. However, many of these have impractical energy requirements for any large-scale deployment.

[0015] The Fischer-Tropsch (FT) process is one of the most widely used petrochemical processes for fuel production today to produce chemicals from carbonaceous feedstocks. First reported by Fischer and Tropsch in 1922 using alkaline iron catalysts, the FT process converts CO and H at high temperatures and pressures. 2 Nearly all modern FT processes use a mixture of aluminum oxide (Al 2 O 3 ) use commercial catalysts composed of cobalt, iron, iron carbide, or ruthenium deposited on a support. Thousands of variations of these catalysts have been produced with the ultimate goal of improving the economics of the FT process. From the perspective of catalyst development, these improved economics can come from increasing the space-time yield of the catalyst to allow for smaller, more efficient reactor designs, narrowing the distribution of hydrocarbon products, or reducing the selectivity to uneconomic by-products.

[0016] The product distribution from the FT process is characterized by CH on the surface of the FT catalyst. x Characterized by polymerization of reaction intermediates. CH x Monomers are polymerized on the surface of the FT catalyst to form C y H z It becomes an intermediate, C y H zThe intermediates are then subjected to further hydrogenation or dehydrogenation to form paraffins, olefins, and other hydrocarbon compounds. In the FT process, the active CH x and C y H z It is difficult to control the C-C coupling of species, which leads to a statistical distribution of hydrocarbon products. The distribution of hydrocarbon products in FT is predicted by the Anderson-Schulz-Flory (ASF) model and is typically referred to as the ASF distribution. The ASF model depends on the chain growth random variables, which are influenced by the nucleophilic FT catalyst, the reduction chemical potential of the active sites, the availability of the catalyst for C-C coupling, and the reaction conditions in the FT reactor.

[0017] In a typical ASF distribution, lighter hydrocarbons (smaller than pentane) are produced with high selectivity when there is a low chain growth probability. With a higher chain growth probability (approaching 1), heavier hydrocarbons with carbon numbers above 21 are expected. Current industrial FT processes that produce synthetic crude oil (syncrude) produce a broad distribution of hydrocarbon products with carbon numbers between 1 and 80. This requires significant downstream processing, including but not limited to fractionation and hydroprocessing, to produce a hydrocarbon mixture suitable for use as sustainable diesel or aviation fuel, where saturated alkanes with carbon numbers between 8 and 20 are preferred. Thus, if a specific fuel product, such as sustainable aviation fuel, is desired, the overall yield of the FT process is reduced. For example, industrial FT processes that follow the ASF model have a maximum selectivity of about 39% for products with carbon numbers between 10 and 20. It is therefore desirable to develop a gas-to-liquid process with chemical reactions that allow deviation from the ASF model.

[0018] Another process that uses synthesis gas (syngas) to produce commodity chemicals is methanol production. Catalysts made from copper with zinc oxide on an alumina scaffold, known as copper-zinc-alumina or "CZA" catalysts, are typically used to produce methanol from synthesis gas composed of carbon monoxide and hydrogen gases, a commodity chemical produced on the scale of millions of tons per year. Certain variants of CZA catalysts are also used to produce methanol from synthesis gas, a commodity chemical produced on the scale of millions of tons per year, due to their high selectivity for CO to methanol. 2 However, this high selectivity to methanol prevents the production of higher alcohols or hydrocarbons in situations where these may be desired.

[0019] In any of these processes, the key components are a catalyst that converts the carbonaceous feedstock and hydrogen gas (or hydrogen equivalent). 2 The catalyst for the conversion is specifically CO 2 However, the major challenge facing the study is that CO requires significant amounts of energy to be converted into other compounds. This reduces the stability and activity of CO. 2 This poses a significant challenge for industrial catalysis for the conversion of CO 2 Several catalysts for the thermochemical reduction of CO have been demonstrated in the academic literature, but none have been translated into industrial use due to either high cost or poor stability. Ni-based catalysts have been used primarily for the reduction of CO 2 CH 4 Co, Fe, Ru, Ir, Zn, Pd, Cu, and Rh compounds are also used to hydrogenate CO for the formation of higher hydrocarbons. 2Hydrogenation catalysts have been used in the past. Combinations of some of these elements in specific ratios in bimetallic and trimetallic catalysts have also been attempted. However, catalysts based on the low-cost metals listed above (such as Cu, Zn, Fe, Co, or Ni) (i.e., not Pt group metals such as Ru, Ir, and Rh) that are suitable for large-scale commercial deployment have not been shown to be effective in converting CO to paraffins or other hydrocarbons suitable for use as diesel or aviation fuels. 2 None have yet been demonstrated as a commercial catalyst for the hydrogenation of

[0020] This is in part because previously reported compounds do not exhibit the stability required to scale up the materials, as these catalysts break down during operation in the reactor to yield less active materials. It is also because the selectivity of the catalysts for the appropriate hydrocarbons is low, based on the distribution of carbon chain lengths produced under commercial reactor conditions. Prior to this disclosure, the lack of a stable and efficient catalyst for this process led to the development of a process that was initially based on CO (as in the Sabatier process). 2 CO or CH 4 There are no known commercial chemical processes that convert carbon dioxide into hydrocarbon products suitable for use in diesel or aviation fuels without a separate step in the chemical process to convert it into

[0021] The present disclosure relates to a method for producing a CO 2 a catalyst, optionally further comprising a metal selected from iron or cobalt, and optionally comprising a support material such as alumina, zeolite, or silica, for the conversion of CO to long chain hydrocarbons; 2 and a method of using such a catalyst for the production of hydrocarbons from ethylene glycol. As further described herein, the catalyst of the present disclosure includes a first element (Co or Fe) as the metal that promotes carbon-carbon bond formation. To date, copper-zinc family catalysts, such as copper and zinc oxide on alumina (CZA) catalysts, have been used to convert CO to multi-carbon products such as paraffins. 2Among other advantages, the modified copper zinc catalysts disclosed herein are capable of efficiently hydrogenating carbonaceous feedstocks, CO 2 , CO, or CH 4 These catalysts are used to catalyze the production of hydrocarbons from toluene at a rate faster than any other reported CZA or FT catalysts. 4 This can also suppress the formation of .beta.-reacted gases and further enable effective recycling of unreacted gases in the product gas recycle in a multi-pass gas to liquids reactor.

[0022] In certain embodiments, the present disclosure provides a catalyst comprising iron oxide, and optionally further comprising one or more additional metals selected from copper and / or zinc. In certain such embodiments, the one or more additional metals are 2 In further embodiments, the iron oxide-containing catalyst further comprises a support comprising alumina, zeolite, or silica. In certain embodiments, the iron oxide-containing catalyst further comprises a support comprising alumina, zeolite, or silica. 2 are useful for converting olefins to longer chain hydrocarbons.

[0023] As further described herein, the catalyst of the present disclosure preferably comprises a CO 2 The metal that promotes activation includes one of the additional metals (Cu and / or Zn). To date, iron family catalysts such as iron oxide catalysts have been used to convert CO to high carbon products such as paraffins. 2 It has not been demonstrated as an effective catalyst for hydrogenation.

[0024] In certain embodiments, the present disclosure provides a method for producing CO 2 and H 2The present invention provides a chemical process for producing long chain hydrocarbons from CO. The process is novel in that it produces multi-carbon species, particularly long chain alkanes having carbon numbers between 6 and 20, unlike previous CZA-based processes which only produce products having carbon numbers between 1 and about 5. Additionally, the process uses CO rather than CO. 2 The FT process differs from the FT-based process in that CO is the feedstock. 2 Increasing the concentration of CO will, as known to those skilled in the art, force the reactor to produce methane exclusively. 2 and H 2 This represents a significant step forward in gas-to-liquid chemistry by using catalysts and reaction conditions where little or no methane is produced using a feed stream composed of cobalt. In some embodiments, the present invention uses cobalt to promote C-C bond and chain growth while simultaneously reducing CH 4 Prevent the generation of

[0025] In certain embodiments, the present disclosure provides a process for the synthesis of ethanol from CO via an alcohol intermediate in a single reactor. 2 and H 2 In some embodiments, the alcohol is co-produced with the long chain hydrocarbons. In some embodiments, the alcohol co-produced with the long chain hydrocarbons is primarily methanol. In some embodiments, the alcohol is an intermediate to the long chain hydrocarbons in a chemical reaction that occurs in a single reactor. In these cases, the production of long chain hydrocarbons can be achieved by first producing the alcohol, then dehydrating the alcohol to form the combined CH x This is accomplished by producing either an intermediate or a free olefin such as ethylene or propylene. x The intermediates or free olefins are further oligomerized to produce longer chain hydrocarbons. In some embodiments, the alcohols are by-products to longer chain hydrocarbons in a chemical reaction that occurs in a single reactor.

[0026] In certain aspects, the present disclosure provides chemical processes for producing long chain hydrocarbons from carbonaceous feedstocks that do not follow the ASF distribution. In some embodiments, the ASF distribution deviates from traditional FT processes due to mechanistic uniqueness. In some embodiments, the present invention provides methods for producing a narrower distribution of desired hydrocarbons for diesel and aviation fuels than traditional FT processes. In some embodiments, the present invention provides methods for selectively producing linear alkanes having carbon numbers between 6 and 26. In some embodiments, the present invention provides methods for selectively producing linear alkanes having carbon numbers between 8 and 16. In some embodiments, the present invention provides methods for selectively producing hydrocarbons having carbon numbers between 6 and 30.

[0027] In certain aspects, the present disclosure provides catalysts for producing long chain hydrocarbons from carbonaceous feedstocks with distinct differences between Co-promoted and Fe-promoted catalysts. As shown in FIG. 1, Co-promoted copper zinc catalysts typically fully hydrogenate long chain hydrocarbons to produce saturated linear alkanes with various carbon numbers from 6 to 30. As shown in FIG. 2, Fe-promoted copper zinc catalysts typically partially hydrogenate long chain hydrocarbons to produce a mixture of saturated alkanes, olefins, and lesser concentrations of branched and cycloalkanes, aromatics, alcohols, and carboxylic acids. In some embodiments, the present invention uses both Co and Fe in various ratios in a catalyst composed of copper and zinc oxide to control the extent to which branching occurs or reaction intermediates are hydrogenated. In some embodiments, the ratio of Co:Fe is 100:1, 50:1, 20:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:20, 1:50, or 1:100.

[0028] In certain embodiments, the present disclosure provides a method for producing CO in a single reactor without the formation of by-products. 2 and H 2 A method for adaptive monitoring of a reactor for the continuous production of long chain hydrocarbons from CO 2 and H 2During operation of a reactor system producing long chain hydrocarbons from H, a narrow operating window of temperature, pressure, and gas composition exists that allows for the production of liquid products without gaseous by-products. The present invention provides a method for real-time monitoring of the composition of the gas recycle loop in a gas-to-liquid reactor system and adaptive adjustment of feed gas ratios and temperatures. In some embodiments, real-time monitoring of the composition of the gas recycle loop is performed using thermal conductivity detection to measure H 2 Determine the relative concentration of CO using infrared detection 2 , CO, C.H. 4 This is accomplished by a syngas analyzer that determines the relative concentrations of CH, CH2, CH3, CH4, CH5, CH6, CH7, CH8, CH9, CH10, CH11, CH12, CH13, CH24, CH35, CH45, CH55, CH66, CH7, CH8, CH9, CH11, CH12, CH13, CH14, CH15, CH26, CH35, CH45, CH55, CH66, CH7, CH8, CH15, CH16, CH17, CH28, CH18, CH29, CH36, CH45, CH55, CH66, CH7, CH8, CH10, CH11, CH12, CH13, CH24, CH35 ...25, CH35, CH45, CH55, CH66, CH7, CH8, CH10, CH11, CH12, CH13, CH24, CH25, CH35, CH45, CH55, CH66, CH7, CH8, CH10, CH11, CH12, CH13, CH24, CH25, CH35, CH4 4 Based on the detector outlet composition to avoid the formation of non-recyclable by-products such as CO 2 and H 2 Adjust the supply ratio.

[0029] catalyst In certain aspects, the disclosure provides a catalyst comprising copper, zinc, one or more first elements selected from iron or cobalt, oxygen, optionally aluminum, and 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, palladium, platinum, or nickel), and optionally one or more Group IA metals, wherein the one or more first elements are present in an amount of about 1 to about 40 weight % (e.g., about 1 to about 10 weight %, about 25 to about 40 weight %, about 30 to about 40 weight %, or about 35 to about 40 weight %) of the total amount of copper, zinc, the one or more first elements, the optional second elements, and the optional Group IA metals.

[0030] In some embodiments, the one or more first elements are about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16% by weight of the total amount of copper, zinc, the one or more first elements, the optional second element, and the optional Group IA metal. %, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, or about 40% by weight. In some embodiments, the one or more first elements are present in an amount of 1-10%, 10-20%, or 20-30%, 20-25%, 22-24%, 25-40%, 30-40%, or 35-40% by weight of the total amount of copper, zinc, the one or more first elements, the optional second element, and the optional Group IA metal.

[0031] In some embodiments, the catalyst comprises reduced copper metal nanoparticles and a cobalt embedded interconnect matrix of alumina modified zinc oxide. In some embodiments, the cobalt is present as cobalt oxide. In some embodiments, the copper is present as copper oxide. In some embodiments, the molar ratio of cobalt to copper to zinc (Co:Cu:Zn) is about 0.1-3 for cobalt, 1-4 for copper, and 0.5-1.5 for zinc. In some embodiments, the Co:Cu:Zn ratio ranges from 1-2 for cobalt, 1-3 for copper, and 0.5-1 for zinc. In some embodiments, the Co:Cu:Zn ratio is about 1:2.5:1. In some embodiments, the zinc is preferably 0.3-1 of the molar content of the copper. In some embodiments, the cobalt is preferably 0.1-1 of the molar content of the copper.

[0032] In some embodiments, the catalyst comprises reduced copper metal nanoparticles and an iron-embedded interconnect matrix of alumina modified zinc oxide. In some embodiments, the iron is present as iron oxide. In some embodiments, the copper is present as copper oxide. In some embodiments, the molar ratios of iron to copper to zinc (Fe:Cu:Zn) are about 0.05-3 for iron, 1-4 for copper, and 0.5-4 for zinc. In some embodiments, the Fe:Cu:Zn ratio ranges from 0.4-2 for iron, 1-3 for copper, and 0.5-3 for zinc. In some embodiments, the Fe:Cu:Zn ratio is about 1:2.3:2.3. In some embodiments, the zinc is preferably 0.3-1 of the molar content of the copper. In some embodiments, the iron is preferably 0.5-5 of the molar content of the copper.

[0033] In certain embodiments, the catalyst of the present disclosure comprises copper, e.g., reduced copper nanoparticles, and zinc oxide supported on an iron support. In further embodiments, the iron support is present as iron oxide. In yet further embodiments, the copper is present as copper oxide. In still further embodiments, the catalyst comprises iron, copper, and zinc in a Fe:Cu:Zn ratio that is about 0.05 to about 3 for iron, about 1 to about 3 for copper, and about 0.5 to about 3 for zinc. In certain embodiments, the Fe:Cu:Zn ratio is about 0.4 to about 3 for iron, about 0.4 to about 3 for copper, and about 0.4 to about 3 for zinc. In certain preferred embodiments, the Fe:Cu:Zn ratio is about 2.3:1:1. In certain preferred embodiments, the catalyst comprises a molar content of zinc that is about 0.3 to about 1 times the molar content of copper. In certain preferred embodiments, the catalyst comprises a molar content of iron that is about 0.5 to about 5 times the molar content of copper.

[0034] In some embodiments, the catalyst comprises one or more elements selected from group VI, VII, VIII, IX, X, or XI metals. In some embodiments, the catalyst comprises one or more second elements selected from group VI metals. In some embodiments, the catalyst comprises one or more second elements selected from group VII metals. In some embodiments, the catalyst comprises one or more second elements selected from group VIII metals. In some embodiments, the catalyst comprises one or more second elements selected from group IX metals. In some embodiments, the catalyst comprises one or more second elements selected from group X metals. In some embodiments, the catalyst comprises one or more second elements selected from group XI metals.

[0035] In some embodiments, the one or more second elements include manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel.

[0036] In some embodiments, the one or more second elements include nickel. In some embodiments, the one or more second elements include silver. In some embodiments, the one or more second elements include palladium. In some embodiments, the one or more second elements include niobium. In some embodiments, the one or more second elements include manganese. In some embodiments, the one or more second elements include zirconium. In some embodiments, the one or more second elements include molybdenum.

[0037] In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 2 relative to copper. In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 1.5 relative to copper. In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 1 relative to copper. In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 0.75 relative to copper. In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 0.5 relative to copper. In some embodiments, the catalyst comprises one or more second elements in a molar ratio of about 0.15 to about 0.25 relative to copper.

[0038] In some embodiments, the catalyst comprises copper in a molar ratio of about 0.5 to about 5 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 1 to about 10 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 2 to about 9 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 2.3 to about 8.4 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 2.3 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 8.4 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 1.5 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 1.0 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 0.75 to the one or more first elements. In some embodiments, the catalyst comprises copper in a molar ratio of about 0.5 to the one or more first elements.

[0039] In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.4 to about 1 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 1.5 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 1.0 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.75 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.5 relative to copper. In some embodiments, the catalyst comprises zinc in a molar ratio of about 0.4 relative to copper.

[0040] In some embodiments, the one or more second elements include niobium. In some embodiments, the one or more second elements consist of niobium. In some embodiments, the niobium is present in a molar ratio to copper of about 0.05 to about 1. In some embodiments, the niobium is present in a molar ratio to copper of about 0.2. In some embodiments, the niobium is present in a molar ratio to copper of about 0.3. In some embodiments, the niobium is present in a molar ratio to copper of about 0.1.

[0041] In some embodiments, the catalyst comprises one or more Group IA metals. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.01 to about 1.0 relative to copper. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.05 to about 0.50 relative to copper. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.20 to about 0.50 relative to copper. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.30 to about 0.50 relative to copper. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.40 to about 0.50 relative to copper. In some embodiments, the catalyst comprises one or more Group IA or IIA metals in a molar ratio of about 0.15 relative to copper.

[0042] In some embodiments, the catalyst comprises one or more Group IA metals. In some embodiments, the one or more Group IA or IIA metals comprise potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals comprise potassium, sodium, or cesium. In some embodiments, the one or more Group IA or IIA metals comprise potassium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In some embodiments, the one or more Group IA or IIA metals comprise ...

[0043] In some embodiments, the catalyst comprises potassium in a molar ratio to copper of about 0.05, about 0.09, about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35, about 0.4, about 0.45, or about 0.5, hi some embodiments, the catalyst comprises potassium in a molar ratio to copper of about 0.09.

[0044] In certain embodiments, the catalyst comprises iron in a molar ratio to copper of about 0.1 to about 10. In further embodiments, the catalyst comprises iron in a molar ratio to copper of about 0.1 to about 1. In yet further embodiments, the catalyst comprises iron in a molar ratio to copper of about 0.1 to about 0.2. In certain embodiments, the catalyst comprises iron in a molar ratio to copper of about 0.5 to about 1. In certain embodiments, the catalyst comprises iron in a molar ratio to copper selected from about 0.1, about 0.2, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, and about 10.

[0045] In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.1 to about 10. In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.1 to about 1. In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.1 to about 0.2. In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.5 to about 1. In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.1. In some embodiments, the catalyst comprises aluminum in a molar ratio to copper of about 0.2.

[0046] In some embodiments, the catalyst comprises zinc oxide.

[0047] In some embodiments, the catalyst comprises copper oxide.

[0048] In some embodiments, the catalyst comprises cobalt oxide.

[0049] In some embodiments, the catalyst comprises iron oxide.

[0050] In some embodiments, the catalyst comprises nickel oxide.

[0051] In some embodiments, the catalyst comprises alumina.

[0052] In certain embodiments, the one or more Group IA or IIA metals comprise or consist of sodium or cesium. It has been found that in the catalysts of the present disclosure, substituting sodium or cesium for potassium does not substantially affect the catalytic activity, and both sodium and cesium provide the same stability that potassium provides. This is in contrast to known synthesis gas catalysts, where the choice of potassium, sodium, or cesium greatly affects activity.

[0053] In some embodiments, the catalyst is aluminum oxide (Al 2 O 3), wherein the aluminum is present in a molar ratio relative to the copper of about 0.02 to about 3. In some embodiments, the aluminum is present in a molar ratio relative to the copper of about 0.1 to about 0.8. In some embodiments, the aluminum is present in a molar ratio relative to the copper of about 0.7. In some embodiments, the alumina is added as a support to increase the surface area of ​​the copper and zinc, or may be generated in situ as a component of the catalyst, for example, from aluminum nitrate co-precipitation with the first element, copper, and zinc precursors.

[0054] In certain embodiments, the catalyst is an iron oxide (e.g., Fe 3 O 4 , Fe 2 O 3 , and / or FeO) and copper. In further embodiments, the iron is present in a molar ratio relative to the copper of from about 0.2 to about 20. In still further embodiments, the iron is present in a molar ratio relative to the copper of from about 0.2 to about 10, from about 0.2 to about 5, from about 0.2 to about 2, from about 0.2 to about 1, from about 0.2 to about 0.5, from about 1 to about 20, from about 1 to about 10, or from about 1 to about 2. In still further embodiments, the iron is present in a molar ratio relative to the copper selected from about 1, about 2, about 5, about 10, about 15, and about 20.

[0055] In some embodiments, the catalyst includes iron oxide as a support to increase the surface area of ​​the copper and zinc, hi other embodiments, iron oxide is generated in situ as a component of the catalyst, for example, by co-precipitating iron nitrate with copper and zinc precursors.

[0056] In some embodiments, the catalyst comprises copper, zinc oxide, cobalt, and alumina. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises cobalt, copper in a molar ratio to the cobalt of about 8.4, zinc in a molar ratio to the cobalt of about 3.3, and alumina having an aluminum molar ratio to the cobalt of about 1.8. In some embodiments, the catalyst comprises copper in a molar ratio to the cobalt of about 8.4, zinc in a molar ratio to the cobalt of about 3.3, and alumina in a molar ratio to the cobalt of about 0.9.

[0057] In some embodiments, the catalyst comprises copper, zinc oxide, nickel, and alumina. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises nickel, copper in a molar ratio of about 2.5 to nickel, zinc in a molar ratio of about 1 to cobalt, and alumina having an aluminum in a molar ratio of about 0.7 to nickel. In some embodiments, the catalyst comprises copper in a molar ratio of about 2.5 to nickel, zinc oxide in a molar ratio of about 1 to nickel, and alumina in a molar ratio of about 0.35 to nickel.

[0058] In some embodiments, the catalyst comprises copper, zinc oxide, iron, and alumina. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises iron, copper in a molar ratio to iron of about 2.3, zinc in a molar ratio to iron of about 2.3, and alumina having an aluminum in a molar ratio to iron of about 0.8. In some embodiments, the catalyst comprises copper in a molar ratio to iron of about 2.3, zinc oxide in a molar ratio to iron of about 2.3, and alumina in a molar ratio to iron of about 0.4.

[0059] In some embodiments, the catalyst comprises copper, zinc oxide, cobalt, alumina, and a Group IA metal. In some embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises cobalt, copper in a molar ratio of about 8.4 to the cobalt, zinc in a molar ratio of about 3.3 to the cobalt, alumina having an aluminum in a molar ratio of about 1.8 to the cobalt, and a Group IA or IIA metal in a molar ratio of about 0.14 to the cobalt. In some embodiments, the catalyst comprises copper in a molar ratio of about 8.4 to the cobalt, zinc oxide in a molar ratio of about 3.3 to the cobalt, alumina in a molar ratio of about 0.9 to the cobalt, and a Group IA or IIA metal in a molar ratio of about 0.14 to the cobalt.

[0060] In some embodiments, the catalyst comprises copper, zinc oxide, nickel, alumina, and a Group IA metal. In some embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises nickel, copper in a molar ratio of about 2.5 to nickel, zinc in a molar ratio of about 1 to nickel, alumina having aluminum in a molar ratio of about 0.7 to nickel, and Group IA in a molar ratio of about 0.1 to nickel. In some embodiments, the catalyst comprises copper in a molar ratio of about 2.5 to nickel, zinc oxide in a molar ratio of about 1 to nickel, alumina in a molar ratio of about 0.35 to nickel, and a Group IA or IIA metal in a molar ratio of about 0.1 to nickel.

[0061] In some embodiments, the catalyst comprises copper, zinc oxide, iron, alumina, and a Group IA metal. In some embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises iron, copper in a molar ratio to iron of about 2.3, zinc in a molar ratio to iron of about 2.3, alumina having aluminum in a molar ratio to iron of about 0.4, and a Group IA or IIA metal in a molar ratio to iron of about 0.4. In some embodiments, the catalyst comprises copper in a molar ratio to iron of about 2.5, zinc oxide in a molar ratio to iron of about 1, alumina in a molar ratio to iron of about 0.35, and a Group IA or IIA metal in a molar ratio to iron of about 0.1.

[0062] In some embodiments, the catalyst includes Cu, Zn, Al, O, and an alkali metal. In certain embodiments, the catalyst includes Cu, Zn, Fe, and O. In some embodiments, the catalyst includes Cu, Zn, Ni, Al, O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Fe, Al, O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Fe, Al, O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Al, O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Nb, Al, and O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Ni, Al, and O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Mo, Al, and O, and an alkali metal. In some embodiments, the catalyst includes Cu, Zn, Co, Mo, Al, and O, and an alkali metal.

[0063] In some embodiments, the catalyst comprises Cu, Zn, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Fe, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Ni, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Fe, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Nb, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Ni, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Mo, Al, and O.

[0064] In one particular embodiment, the elemental composition of the catalytic material is Cu(ZnO)CoA / Al 2 O 3 , Cu(ZnO)CoFeA / Al 2 O 3 , Cu(ZnO)CoNbA / Al 2 O 3 , Cu(ZnO)CoNiA / Al 2 O 3 , Cu(ZnO)CoMoA / Al 2 O 3 , or Cu(ZnO)A / Fe 3 O 4 where A is an alkali metal, and further, the relative amounts of the elemental components are as described above.

[0065] In one particular embodiment, the elemental composition of the catalyst material is Cu(ZnO)Co / Al 2 O 3 , Cu(ZnO)CoFe / Al 2 O 3 , Cu(ZnO)CoNb / Al 2 O 3 , Cu(ZnO)CoNi / Al 2 O 3 , Cu(ZnO)CoMo / Al 2 O 3 , Cu(ZnO)Nb / Fe 3 O 4 where the relative amounts of the elemental components are as described above.

[0066] In some embodiments, the catalyst is one of the following exemplary catalysts: Al 2 O 3 The catalyst is selected from Cu(ZnO), Cu(ZnO)Co, Cu(ZnO)CoK, Cu(ZnO)CoFe, Cu(ZnO)Fe, Cu(ZnO)CoFeK, Cu(ZnO)FeK, Cu(ZnO)CoNi, Cu(ZnO)CoNiK, Cu(ZnO)CoNb, Cu(ZnO)CoNbK, Cu(ZnO)CoMo, and Cu(ZnO)CoMoK above, with the relative amounts of the elemental components being as described above. In certain such embodiments, the catalyst is selected from about CuO (2) (ZnO) (1) , Cu (2.5) (ZnO) (1) Co (1) , Cu (2.5) (ZnO) (1) Co (1) K (0.1) , Cu (1) (ZnO) (1) Co (1) Fe (1) , Cu (1) (ZnO) (1) Fe (1) , Cu (1) (ZnO) (1) Co (1) Fe (1) K (0.15) , Cu (1) (ZnO) (1) Fe (1) K (0.15) , Cu (2) (ZnO) (1) Co (1) Ni (1) , Cu (2) (ZnO) (1) Co (1) Ni (1) K (0.15) , Cu (2) (ZnO) (1) Co (1) Nb (1) , Cu (2) (ZnO) (1) Co (1) Nb (1) K (0.15) , Cu (2) (ZnO) (1)Co (1) Mo (1) , Cu (2) (ZnO) (1) Co (1) Mo (1) K (0.15) It is.

[0067] In a further aspect, provided herein is a catalyst for the production of paraffins, comprising: One or more metals; Optionally, one or more second elements selected from copper and zinc; and optionally, one or more Group VI, VII, VIII, IX, X, or XI metal additives; Optionally, a Group IA or IIA metal promoter is provided.

[0068] In certain embodiments, the one or more metals are selected from cobalt, iron, nickel, indium, yttrium, lanthanides, and combinations thereof. In further embodiments, the one or more metals are cobalt. In yet further embodiments, the one or more metals are iron. In yet further embodiments, the one or more metals are a combination of iron and cobalt.

[0069] In certain embodiments, the one or more metals are present in the form of an oxide, nitride, or carbide. In further embodiments, the one or more second elements are copper. In yet further embodiments, the one or more second elements are zinc. In still further embodiments, the one or more second elements are copper and zinc. In certain embodiments, the one or more second elements are present in the form of an oxide, nitride, or carbide.

[0070] In certain embodiments, the one or more Group VI, VII, VIII, IX, X, or XI metal additives, when present, are selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel. In further embodiments, the Group IA or IIA metal promoter, when present, is a Group IA element. In yet further embodiments, the Group IA or IIA metal promoter, when present, is lithium, sodium, potassium, or cesium. In still further embodiments, the one or more second elements are present in an amount of about 0.5 to about 40 weight percent of the total amount of the one or more metals, the second element, the optional one or more Group VI, VII, VIII, IX, X, or XI metal additives, and the optional Group IA or IIA metal promoter.

[0071] In certain aspects, the systems and methods of the present disclosure involve the use of a hydrogenation catalyst and an isomerization catalyst to isomerize or hydrogenate a portion of the produced hydrocarbons, respectively. In certain embodiments, the hydrogenation catalyst and the isomerization catalyst of the present disclosure may be independently selected from the catalysts described below.

[0072] In certain embodiments, the isomerization catalyst and / or hydrogenation catalyst of the present disclosure is an aluminosilicate catalyst, such as a zeolite. In further embodiments, the isomerization catalyst and / or hydrogenation catalyst is an aluminosilicate catalyst, such as a zeolite. 3 In still further embodiments, the isomerization catalyst and / or hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In still further 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 support. In further embodiments, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo. In still further embodiments, the zeolite support is SiAlO x , S.O. 4 -ZrO 2 , Y-type zeolite, β-zeolite, ZSM5, ZSM22, SAPO11, SAPO31, SAPO41, and TiO 2In yet a further embodiment, the isomerization catalyst and the hydrogenation catalyst are independently selected from 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.

[0073] In certain embodiments, the isomerization metal comprises about 0.5% to about 40% by weight of the isomerization catalyst and / or hydrogenation catalyst. In further embodiments, the isomerization metal comprises about 0.5% by weight of the isomerization catalyst and / or hydrogenation catalyst. In yet further embodiments, the isomerization metal comprises about 1% by weight of the isomerization catalyst and / or hydrogenation catalyst. In still further embodiments, the isomerization metal comprises about 10% by weight of the isomerization catalyst and / or hydrogenation catalyst. In certain embodiments, the isomerization metal comprises about 20% by weight of the isomerization catalyst and / or hydrogenation catalyst. In further embodiments, the isomerization metal comprises about 30% by weight of the isomerization catalyst and / or hydrogenation catalyst. In still further embodiments, the isomerization metal comprises about 40% by weight of the isomerization catalyst and / or hydrogenation catalyst.

[0074] In one particular embodiment, the isomerization catalyst is Pt / Al 2 O 3 When the isomerization catalyst is a zeolite-based catalyst, the isomerization temperature is about 250° C. and the isomerization pressure is about 750 psi. In one particular embodiment, when the isomerization catalyst is a zeolite-based catalyst, the isomerization temperature is about 300° C. and the isomerization pressure is about 750 psi.

[0075] catalyst composition In certain embodiments, the present disclosure provides a catalyst composition comprising one or more of the catalysts disclosed herein and an additional support. The additional support can be any suitable material capable of serving as a catalyst support.

[0076] In some embodiments, the additional support comprises one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, and tin. In further embodiments, the additional support comprises one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron, 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, zirconium oxide, titanium oxide, and silica carbide. In certain embodiments, the additional support is selected from carbon, silica, zeolites, alumina, iron oxide, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is aluminum oxide formed in situ as part of the catalyst. In some embodiments, the additional support may be any of a variety of materials, including, but not limited to, Al 2 O 3 , ZrO 2 , SnO 2 , SiO 2 , ZnO, and TiO 2 In some embodiments, the additional support is selected from Al 2 O 3 , ZrO 2 , SnO 2 , SiO 2 , ZnO, and TiO 2 In some embodiments, the additional support is selected from Al 2 O 3 , ZrO 2 , SnO 2 , SiO 2 , ZnO, Fe 2 O 3 , Fe 3 O 4 , FeO, and TiO 2 is selected from.

[0077] In some embodiments, the additional support comprises one or more carbon-based materials, hi some embodiments, the carbon-based materials are selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0078] In some embodiments, the additional support is a mesoporous material, hi some embodiments, the additional support has a mesopore volume of about 0.01 to about 3.0 cc / g.

[0079] In some embodiments, the additional support is about 10 m 2 / g~about 1000m 2 In some preferred embodiments, the catalyst composition comprising the additional support and the catalyst disclosed herein has a surface area of ​​about 10 m 2 / g~about 1000m 2 / g surface area.

[0080] In some embodiments, the catalyst composition is in the form of particles having an average size of about 10 nm to about 5 μm. In some embodiments, the catalyst composition is in the form of particles having an average size of about 20 nm to about 5 μm. In some embodiments, the catalyst composition is in the form of particles having an average size of about 50 nm to about 1 μm. In some embodiments, the catalyst composition is in the form of particles having an average size of about 100 nm to about 500 nm. In some embodiments, the catalyst composition is in the form of particles having an average size of about 50 nm to about 300 nm.

[0081] In some embodiments, the catalyst composition comprises from about 5% to about 80% by weight of catalyst. In some embodiments, the catalyst composition comprises from about 5% to about 70% by weight of catalyst. In some embodiments, the catalyst composition comprises from about 20% to about 70% by weight of catalyst. In some embodiments, the catalyst composition comprises from about 30% to about 70% by weight of catalyst.

[0082] 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.

[0083] In some embodiments, the catalyst is a nanoparticle catalyst. In some embodiments, the particle size of the catalyst on the surface of the scaffold is about 1 nm to 5 nm. In some embodiments, the particle size of the catalyst on the surface of the scaffold is about 5 nm to 100 nm. In some embodiments, the particle size of the catalyst on the surface of the scaffold is 100 to 500 nm. In some embodiments, the particles that do not undergo agglomeration have a particle size of 100 to 500 nm.

[0084] Method of preparation The catalysts and catalyst compositions of the present disclosure may be prepared by any suitable method. In certain aspects, the present disclosure provides methods for preparing the catalysts or catalyst compositions disclosed herein, including preparing the catalyst by co-precipitation, wet impregnation, or ball milling.

[0085] In some embodiments, the method comprises: (a) providing a first solution comprising a source of cobalt, copper, zinc, aluminum, a base, and water; (b) heating the first solution at a first temperature for a first period of time, thereby producing a first reaction mixture; (c) heating the first reaction mixture at a second temperature for a second period of time to remove water, thereby producing a solid precursor; (d) heating the solid precursor to a third temperature for a third period of time, thereby isolating the catalyst.

[0086] In some embodiments, the method comprises: (a) providing a second solution comprising a source of cobalt, copper, zinc, iron, and water; (b) providing a third solution comprising a base; (c) heating the third solution at a third temperature for a third period of time; (d) adding alumina to the third solution, thereby forming a second reaction mixture; (e) adding a second solution to the second reaction mixture at a fourth temperature for a fourth period of time, thereby producing a third reaction mixture; (f) heating the third reaction mixture at a fifth temperature for a fifth period of time, thereby producing a solid precursor; (g) isolating the solid precursor; (h) contacting the solid precursor with a solution containing a Group IA metal, thereby producing a catalyst precursor; (i) heating the catalyst precursor to a sixth temperature for a sixth period of time, thereby isolating the catalyst.

[0087] In some embodiments, the method includes the steps of: providing a first solution comprising a cobalt source, a copper source, a zinc source, and an aluminum source; combining the first solution with a basic precipitant, such as a carbonate salt, to increase the pH of the metal salt-containing solution, thereby precipitating solid particles; and drying and calcining the solid particles to form a solid catalyst.

[0088] In certain embodiments, the base comprises a carbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium, while in other embodiments, the base comprises a bicarbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium.

[0089] In some embodiments, the method includes the steps of providing a first solution comprising a cobalt source and introducing the first solution via incipient wetness or wet impregnation into a prefabricated copper-zinc alumina material followed by drying and calcination to form a solid catalyst.

[0090] In some embodiments, the method includes the following steps: mixing a cobalt source and a support in a mill jar to provide a first mixture; ball milling the first mixture for between 2 hours and 2 weeks to provide a first precipitate; filtering and heating the first precipitate to a first temperature to provide a ball milled cobalt source; The method includes mixing the ball milled cobalt source with sources of copper and zinc and an alumina source to provide a second mixture, and isolating a solid material from the second mixture.

[0091] In some embodiments, the method further comprises combining the solid material with a source of one or more Group IA metals. In some embodiments, the method further comprises pressing the solid material into pellets. In some embodiments, the method further comprises pressing the solid material into pellets prior to introduction into the flow reactor.

[0092] Hydrogenation Method In certain embodiments, the present disclosure provides a process for the production of carbonaceous feedstocks, i.e., CO 2 to a liquid product mixture comprising: 2 and a reducing agent gas at a reduction temperature and pressure, thereby providing a liquid product mixture.

[0093] In some embodiments, the reducing agent gas is H 2 In some embodiments, the reducing agent gas is CH 4 , ethane, propane, or butane. In a preferred embodiment, the hydrocarbon is CH 4 In certain such embodiments, CH 4 is a component of a gas mixture that may also contain other hydrocarbons such as ethane, propane, or butane. For example, CH 4 The gas mixture used to supply may be (or may be derived from) flare gas, waste gas, natural gas, or the like.

[0094] In some embodiments, the feed mixture further comprises CO. In some embodiments, the feed mixture comprises less than 25% CO, less than 20% CO, less than 15% CO, less than 10% CO, less than 5% CO, or less than 1% CO. In some embodiments, the feed mixture is substantially free of CO.

[0095] In some embodiments, the reduction temperature is from about 100 to about 600° C. In some embodiments, the reduction temperature is from about 275 to about 350° C. In some embodiments, the reduction temperature is about 275° C. In some embodiments, the reduction temperature is about 300° C.

[0096] In some embodiments, the reduction pressure is from about 50 to about 3000 psi. In some embodiments, the reduction pressure is from about 900 to about 1100 psi. In some embodiments, the reduction pressure is about 1000 psi.

[0097] In some embodiments, the CO 2 In some embodiments, the partial pressure of CO in the feed mixture is about 20 to about 1500 psi. 2 The partial pressure of CO in the feed mixture is about 200 to about 800 psi, about 200 to about 600 psi, about 200 to about 400 psi, or about 300 to about 400 psi. 2 The partial pressure of CO in the feed mixture is about 200 psi, about 250 psi, about 300 psi, about 350 psi, about 400 psi, about 450 psi, about 500 psi, about 550 psi, about 600 psi, about 650 psi, about 700 psi, about 750 psi, about 800 psi, about 850 psi, about 900 psi, about 950 psi, or about 1000 psi. 2 The partial pressure of is approximately 330 psi.

[0098] In some embodiments, the reducing agent gas in the feed mixture is CO 2 In some embodiments, the ratio of reducing agent gas:CO in the feed mixture is about 10:1 to about 1:10.2 In some embodiments, the ratio of reducing agent gas:CO in the feed mixture is about 5:1 to about 0.5:1. 2 In some embodiments, the ratio of reducing agent gas:CO in the feed mixture is about 4:1 to about 1:1. 2 The ratio is about 3:1.

[0099] In some embodiments, the liquid product mixture comprises methanol. In some embodiments, the liquid product mixture comprises methanol, ethanol, and n-propanol. In some embodiments, the liquid product mixture comprises methanol, ethanol, acetic acid, and n-propanol. In some embodiments, the amount of ethanol and higher alcohols is at least 10% by weight of the total amount. In some embodiments, the amount of ethanol and higher alcohols is at least 7% by weight of the total amount of the liquid product mixture. In some embodiments, the amount of ethanol and higher alcohols is at least 5% by weight of the total amount of the liquid product mixture. In some embodiments, the amount of ethanol and higher alcohols is at least 2% by weight of the total amount of the liquid product mixture. In some embodiments, the molar ratio of ethanol and higher alcohols to the total amount of methanol and n-propanol in the liquid product mixture is from about 1:5 to about 1:10. In some embodiments, the amount of formic acid in the liquid product mixture is less than 10 ppm. In some embodiments, the amount of isopropanol in the liquid product mixture is less than 10 ppm.

[0100] In some embodiments, the liquid product mixture comprises a hydrocarbon. In some embodiments, the liquid product mixture comprises a paraffin. As used herein, the term "paraffin" refers to a hydrocarbon that is preferably straight chained, but may include branched hydrocarbons. Exemplary paraffins have carbon numbers from 6 to 20, preferably 9 to 16.

[0101] For the processes described herein, the term "liquid product mixture" refers to products that are liquid at atmospheric pressure and temperature.

[0102] In some embodiments, the liquid product mixture comprises paraffins, olefins, and other hydrocarbons. In some embodiments, the amount of paraffins is at least 50 wt.% of the total amount of the liquid product mixture. In some embodiments, the amount of paraffins is at least 10 wt.% of the total amount of the liquid product mixture. In some embodiments, the amount of paraffins is at least 5 wt.% of the total amount of the liquid product mixture. In some embodiments, the amount of paraffins is at least 2 wt.% of the total amount of the liquid product mixture. In some embodiments, the molar ratio of paraffins to the total amount of carbon-containing products in the liquid product mixture is from about 1:2 to about 1:10. In some embodiments, the amount of formic acid in the liquid product mixture is less than 1,000 ppm. In some embodiments, the amount of isopropanol in the liquid product mixture is less than 1,000 ppm.

[0103] The objective of the present invention is to provide high gas product recyclability using low GHSV (gas hourly space velocity) and avoid certain by-products such as formaldehyde or methane. In some embodiments, the method does not produce C1 alkanes or aldehydes such as formaldehyde or methane. In some embodiments, the method produces less than about 0.5% by weight of formaldehyde or methane. In some embodiments, the method produces less than about 0.05% by weight of formaldehyde or methane. In some embodiments, the method produces less than about 50 ppm of formaldehyde or methane. In some embodiments, the method produces less than 5 ppm of formaldehyde or methane.

[0104] In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 10. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 100. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 500. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 1,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 2,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 5,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 10,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 20,000 or greater.

[0105] In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 20,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 10,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 5,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 2,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 1,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 500. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is about 10 to about 100.

[0106] In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 10. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 100. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 500. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 1,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 2,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 5,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 10,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is less than about 20,000.

[0107] In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 100. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 500. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 1,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 2,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 5,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 10,000. In some embodiments, the GHSV of the reactive gas and recycle gas introduced into the reactor is 20,000.

[0108] In some embodiments, the method comprises contacting the catalyst with the feed mixture for at least 8,000 hours. In some embodiments, the method comprises contacting the catalyst with the feed mixture for at least 96 hours. In some embodiments, the method comprises contacting the catalyst with the feed mixture for at least 24 hours.

[0109] In certain embodiments, the methods of the present disclosure further include contacting the liquid product mixture and the first reducing gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerization product mixture comprising normal paraffins, branched paraffins, and / or naphthenes.

[0110] In a further embodiment, the isomerization product mixture comprises: Additional C 1-8 Hydrocarbons, Additional C including normal paraffins, branched paraffins, and naphthenes 9-15 Hydrocarbons, Additional C 16+ and hydrocarbons.

[0111] In some embodiments, the numbers used to describe and claim certain embodiments of the present disclosure are modified in some instances by the term "about". In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the present invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as practicable. The numerical values ​​presented in some embodiments of the present invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0112] In certain embodiments, the term "about" means within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2, 1%, 0.5%, or 0.05% of a given value or range. EXAMPLES

[0113] Having now generally described the invention, it will be more readily understood by reference to the following examples, which are included solely for the purpose of illustrating certain aspects and embodiments of the invention and are not intended to limit the invention.

[0114] Example 1: Elemental composition of an exemplary cobalt copper zinc alumina catalyst. [Table 1]

[0115] Example 2: Synthesis of an exemplary cobalt copper zinc alumina catalyst by a combination of coprecipitation and wet impregnation. A first solution containing zinc nitrate (1 molar equivalent), copper nitrate (3 molar equivalents), aluminum nitrate (1.4 molar equivalents) and a second solution containing sodium carbonate (9.7 molar equivalents) are combined in a reactor. The resulting mixture is rapidly stirred and heated at 70-90 °C for 2 hours, then filtered. The resulting solid material is dried under air at 110 °C for 12 hours, the resulting solid material is crushed, heated in air at a heating rate of 2 °C / min to 350 °C, and calcined at 350 °C for 6 hours. After calcination, the resulting power is then further ground in a mortar and pestle. The powder is pelletized and mixed with Co(NO) dissolved in water. 3 ) 2 6H 2 A liquid consisting of O (8 wt% Co in aqueous solution) is added to the pelletized catalyst by incipient wetness impregnation and heated to yield a cobalt copper zinc alumina catalyst (CCZA).

[0116] Example 3: Synthesis of exemplary iron catalysts by co-precipitation and wet impregnation A first solution of ferric nitrate (1 molar equivalent) and a basic solution containing sodium carbonate (1.2 molar equivalents) are combined in a reactor at about 60° C. The resulting mixture is rapidly stirred and heated at 70° C.-90° C. for 2 hours, then filtered and dried. The resulting solid material is dried under air at 110° C. for 12 hours, the resulting solid material is crushed, heated in air at a heating rate of 2° C. / min to 350° C., and calcined at 350° C. for 6 hours. After calcination, the resulting powder is further ground with a mortar and pestle.

[0117] Example 4: Elemental composition of exemplary iron copper zinc catalysts with and without alumina. [Table 2] [Table 3]

[0118] Example 5: CO in the presence of an exemplary cobalt copper zinc catalyst 2 reduction. CO in the presence of CCZA 2 The reduction was carried out over a period of 14 days under the following conditions: 3:1 H 2 :CO 2 ratio; GHSV is about 2000 hours -1 Was; CO per pass 2 Conversion rate of about 30%; Temperature 270℃; Pressure 1000psi.

[0119] The composition of the liquid product fraction obtained from the reaction is shown in Table 1. [Table 4]

[0120] Example 6: CO to Hydrocarbons Using Iron-Cu-Zinc Catalyst 2 Catalytic reduction of CO in the presence of FCZK 2 The reduction was carried out over a period of 14 days under the following conditions: 3:1 H 2 :CO 2 ratio; GHSV is 5000 hours -1 Was; CO per pass 2 Conversion rate of about 20%; Temperature 270℃; Pressure 1000psi.

[0121] The composition of the liquid product fraction obtained from the reaction is shown in Table 2. [Table 5]

[0122] Example 7: General procedure for hydroisomerization of paraffins Paraffins are fed to an isomerization reactor loaded with hydroisomerization catalyst (Pt on β-zeolite, 0.5 wt% Pt). The reaction is run at 750 psi and 250° C. for 1.0 hour with the hydrogen / hydrocarbon molar ratio set at 500. -1 The liquid weight hourly space velocity is C 8 -C 15 is converted to a mixture of saturated n-paraffins and iso-paraffins having a selected range of carbon chain numbers.

[0123] Incorporation by Reference All publications and patents mentioned herein are herein incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control.

[0124] Equivalent While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those of ordinary skill 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. A catalyst for the production of a product mixture containing long chain hydrocarbons, comprising: one or more metals selected from cobalt, iron, nickel, indium, yttrium, lanthanides, and combinations thereof; one or more second elements selected from copper, zinc, and combinations thereof; optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives; and a Group IA or IIA metal promoter.

2. 10. The catalyst of claim 1, wherein the one or more metals is cobalt.

3. 10. The catalyst of claim 1, wherein the one or more metals is iron.

4. 10. The catalyst of claim 1, wherein the one or more metals are present in the form of an oxide, nitride, or carbide.

5. The catalyst of claim 1 , wherein the one or more second elements is copper.

6. The catalyst of claim 1 , wherein the one or more second elements is zinc.

7. 10. The catalyst of claim 1, wherein the one or more second elements is a combination of copper and zinc.

8. 10. The catalyst of claim 1, wherein the one or more second elements are present in the form of an oxide, nitride, or carbide.

9. 2. The catalyst of claim 1, wherein the one or more Group VI, VII, VIII, IX, X, or XI metal additives, if present, are selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel.

10. 10. The catalyst of claim 1, wherein the Group IA or IIA metal promoter is a Group IA element.

11. 10. The catalyst of claim 1, wherein the Group IA or IIA metal promoter is lithium, sodium, potassium, or cesium.

12. 10. The catalyst of claim 1, wherein the one or more secondary elements are present in an amount of about 0.5 to about 40 weight percent of the total amount of the one or more metals, the one or more secondary elements, the optional one or more Group VI, VII, VIII, IX, X, or XI metal additives, and the Group IA or IIA metal promoter.

13. A catalyst composition comprising the catalyst of claim 1 and an additional support.

14. 14. The composition of claim 13, wherein the additional support comprises one or more materials selected from oxides, nitrides, fluorides, silicates, or carbides of elements selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron, and tin.

15. The additional support is Al ２ O ３ , ZrO ２ , SnO ２ , SiO ２ , ZnO, TiO ２ , Fe ２ O ３ , Fe ３ O ４ , FeO, or combinations thereof.

16. The composition of claim 13, wherein the composition is in the form of particles having an average size of about 10 nm to about 5 μm.

17. A method for producing the catalyst of claim 1.

18. CO ２ and a method for converting a first reducing gas into long chain hydrocarbons, comprising: ２ and contacting a feed mixture comprising said reducing gas with the catalyst of claim 1 at a reducing temperature and pressure to produce said product mixture comprising long chain hydrocarbons.

19. 20. The method of claim 18, wherein the conversion is carried out in a single reactor.

20. 20. The method of claim 18, wherein the product mixture comprises less than about 0.5 wt.% formaldehyde or methane.

21. 20. The method of claim 18, wherein the product mixture comprises a gaseous product mixture and a liquid product mixture.

22. 22. The method of claim 21, wherein the liquid product mixture comprises an aqueous liquid product mixture and a non-aqueous liquid product mixture.

23. 23. The method of claim 22, wherein the non-aqueous liquid product mixture comprises paraffins, olefins, and other hydrocarbons.

24. 23. The method of claim 22, wherein the non-aqueous liquid product mixture comprises normal alkanes having a carbon number of from 6 to 26.

25. 23. The method of claim 22, wherein the non-aqueous liquid product mixture comprises linear alkanes having a carbon number of from 8 to 16.

26. 23. The method of claim 22, wherein the non-aqueous liquid product mixture comprises hydrocarbons having a carbon number of from 6 to 30.

27. 23. The method of claim 22, wherein the non-aqueous liquid product mixture consists essentially of hydrocarbons having a carbon number of from 6 to 30.

28. 22. The method of claim 21, wherein the amount of paraffin is at least 50% by weight of the liquid product mixture.

29. The reducing agent gas is H ２ 19. The method of claim 18, wherein:

30. The method comprises: monitoring the product mixture; capturing unreacted and partially reacted components from the feed mixture to produce a recycled gas mixture; combining the recycled gas mixture with the feed mixture; 20. The method of claim 18, further comprising: adapting the ratio of the recycled gas mixture to the feed mixture.

31. 20. The process of claim 18, further comprising contacting the product mixture and isomerized gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising normal paraffins, branched paraffins, and / or naphthenes.

32. The method of claim 18, wherein the catalyst does not contain zeolite.

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