Process and catalyst for conversion of carbon dioxide to long chain hydrocarbons

Abstract

The present invention relates to processes and catalysts for converting carbon dioxide to long chain hydrocarbons. The present disclosure provides catalysts, reactor systems, and methods for converting carbon dioxide and hydrogen to paraffins, olefins, and other hydrocarbon products. Also included is a process for producing hydrocarbons using a mixture of carbon dioxide, carbon monoxide, and hydrogen in a manner different from that of a conventional Fischer-Tropsch reactor.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

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

[0003] As atmospheric CO2 concentrations increase, developing technologies to remove CO2 from the air is becoming advantageous from the perspectives of societal welfare, human health, and energy security. CO2 conversion technologies have the added benefit of producing commodity chemicals on-site anywhere on Earth, making them more attractive for use with CO2. 2 When combined with air capture, there are no transportation costs or hazardous risks. Removing CO from the air 2 The demand for electricity is coupled with the increasing global use of renewable electricity generation methods such as solar photovoltaics and wind turbines. Technologies like 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. Therefore, the power supply from these sources to the grid will surge at certain times and be low at other times. This provides an opportunity for technologies that can intermittently utilize electricity to produce desired products on site.

[0004] Among the technologies that can be used to produce chemicals from carbon dioxide, the hydrogenation of carbon dioxide or carbon monoxide using hydrogen from a renewable source of water electrolyzers can be powered entirely by renewable (solar, wind, hydroelectric, etc.) electricity. Such methods use external energy to convert carbon-based feedstocks (carbon dioxide or carbon monoxide) and water into hydrocarbon chemicals; this is similar to the basic photosynthesis process that enables life on our planet. For example, plants use photosynthesis to convert carbon dioxide, water, and solar energy into chemical energy by producing sugars and other complex hydrocarbons. This effectively stores energy from the sun in the chemical bonds of carbon-based compounds. For billions of years, this process has supported the Earth's ecosystems and balanced the concentration of carbon dioxide in the atmosphere.

[0005] Over the last century, humans have utilized byproducts of photosynthesis, such as fossil fuels, to provide the energy needed for modern life. This has released millions of tons of carbon dioxide into the Earth's atmosphere, which had previously been sequestered in fossil fuels through photosynthesis over the course of millions of years. Scientific evidence indicates that this rapid increase in atmospheric carbon dioxide concentrations from anthropogenic sources is potentially catastrophic for the global climate. Therefore, the development of carbon-negative processes that mimic natural processes to sequester carbon dioxide is critical to the future of the Earth, and the purpose of this application is to disclose such an invention. Summary of the invention

[0006] In certain aspects, the present disclosure provides a catalyst comprising: copper; zinc; one or more first elements, the one or more first elements selected from iron or cobalt; oxygen; optionally, aluminum; one or more second elements, the one or more second elements selected from Group V, Group VI, Group VII, Group VIII, Group IX, Group X, and Group XI metals (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, or palladium); and optionally, one or more Group IA metals, and wherein the one or more first elements are present in an amount of about 1 wt.% to about 50 wt.% (e.g., about 1 wt.% to about 10 wt.%, about 25 wt.% to about 40 wt.%, about 30 wt.% to about 40 wt.%, or about 35 wt.% to about 50 wt.%) based on the total amount of the copper, the zinc, the first element, the optional second element, and the optional Group IA metal.

[0007] In certain aspects, the present disclosure provides a zinc-aluminum-copper (CZA) catalyst comprising: copper; zinc; optionally, one or more first elements selected from iron, cobalt, iron or nickel; oxygen; optionally, aluminum; optionally one or more second elements selected from Group V, Group VI, Group VII, Group VIII, Group IX, Group X and Group 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 wherein the metal is iron; optionally one or more second elements, the one or more second elements being selected from copper and / or zinc; optionally, one or more Group VI, Group VII, Group VIII, Group IX, Group X or Group XI metal additives (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium or palladium); and optionally, a Group IA or Group IIA metal promoter.

[0009] In certain aspects, the present disclosure provides catalytic compositions comprising the catalysts disclosed herein and optionally an additional support.

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

[0011] In certain aspects, the present disclosure provides methods for making CO 2A method for reducing CO, CO or a mixture of the two to a liquid product mixture, the method comprising contacting a catalyst or other catalytic composition disclosed herein with a feed mixture at a reducing temperature and a reducing pressure, thereby providing the liquid product mixture, the feed mixture comprising CO 2 , CO or a mixture of both and a reducing agent gas.

[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 A gas chromatogram is shown identifying the major individual hydrocarbon compounds in the hydrocarbon mixture, namely, linear alkanes, produced by an exemplary cobalt copper zinc catalyst.

[0014] Figure 2 A gas chromatogram is shown identifying the hydrocarbon mixture produced by an exemplary iron-copper-zinc catalyst, including major individual hydrocarbon compounds among linear alkanes and primary olefins.

[0015] Figure 3 Shown is an enlarged gas chromatogram identifying the hydrocarbon mixture produced by an exemplary iron-copper-zinc catalyst, including individual hydrocarbon compounds among secondary olefins, aromatic compounds, and cycloalkanes. DETAILED DESCRIPTION

[0016] One of the main obstacles to achieving carbon dioxide sequestration is the efficient use of carbon dioxide or carbon monoxide and the catalytic conversion of carbon dioxide or carbon monoxide into useful chemicals. Plants achieve this goal through dehydrogenases, which utilize transition metals to catalyze the hydrogenation of carbon dioxide into many other building blocks of carbon monoxide, formic acid or cellulose. Artificial systems attempt to replicate this approach, and known chemical methods for carbon dioxide conversion have a history of several decades. However, the energy requirements of many of them are impractical for any large-scale deployment.

[0017] The Fischer-Tropsch (FT) process is one of the most widely used processes for fuel production today for the production of chemicals from carbonaceous feedstocks. First reported by Fischer and Tropsch in 1922 using a basic iron catalyst, the FT process utilizes elevated temperatures and pressures to react CO and H 2 Almost all modern FT processes use commercial catalysts that contain cobalt, iron, iron carbide, or ruthenium deposited on alumina (Al 2 O 3) supports. Thousands of variations of these catalysts have been produced with the ultimate goal of improving the economics of the FT process. From a catalyst development perspective, these improved economics can be achieved by increasing the space-time productivity of the catalyst to enable smaller, more efficient reactor designs, narrowing the distribution of hydrocarbon products, or reducing selectivity to uneconomical byproducts.

[0018] The product distribution produced by the FT process is characterized by CH x The reaction intermediates polymerize on the surface of the FT catalyst. x The monomers polymerize on the surface of the FT catalyst to form C y H z intermediates, which, upon further hydrogenation or dehydrogenation, form paraffins, olefins and other hydrocarbon compounds. x and C y H z The CC coupling on the surface of the FT catalyst is challenging, 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 a chain growth probability variable that is affected by the nucleophilicity of the FT catalyst, the reduction chemical potential of the active site, the effectiveness of the catalyst for CC coupling, and the reaction conditions in the FT reactor.

[0019] In a typical ASF distribution, when the probability of chain growth is low, lighter hydrocarbons (less than pentane) are produced with high selectivity. Under a larger probability of chain growth (close to 1), the carbon number of heavier hydrocarbons is expected to be greater than 21. The industrial FT process currently producing synthetic crude oil (syncrude) produces a widely distributed hydrocarbon product with a carbon number between 1 and 80. This requires a large amount of downstream processing, including but not limited to fractionation and hydroprocessing, to produce a hydrocarbon mixture suitable for use as a sustainable diesel or aviation fuel, wherein the saturated alkanes with a carbon number between 8 and 20 are preferred. Therefore, when a specific fuel product such as a sustainable aviation fuel is desired, the total yield of the FT process is reduced. For example, the maximum selectivity of the industrial FT process following the ASF model for products with a carbon number between 10 and 20 is about 39%. Therefore, it is desirable to develop a gas-liquid process with a chemistry that enables deviation from the ASF model.

[0020] Another method of using synthesis gas (syngas) to produce commodity chemicals is methanol production. Catalysts made of copper and zinc oxide on an alumina support, known as copper-zinc-alumina or "CZA" catalysts, are commonly used to produce methanol, a commodity chemical produced in millions of tons per year, from synthesis gas containing carbon monoxide and hydrogen. Certain variants of the CZA catalyst can be used for CO due to their high selectivity. 2 Hydrogenation to methanol, however, presents several other disadvantages, such as product purity, methane co-production and limited catalyst life. However, this high selectivity for methanol discourages the production of higher alcohols or hydrocarbons for situations where such higher alcohols or hydrocarbons may be desired.

[0021] In any of these processes, a key component is a catalyst for converting the carbonaceous feedstock and hydrogen (or hydrogen equivalent). 2 The main challenge facing catalysts for the conversion of CO 2 A large amount of energy is required to transform it into other compounds. This makes stability and activity very important for CO 2 The key challenge for industrial catalysts for the conversion of CO 2 Some catalysts for the thermochemical reduction of CO have been proposed, but none of them have made the transition to industrial use due to high cost or poor stability. Nickel-based catalysts are mainly used to reduce CO 2 Hydrogenation to CH 4 Co, Fe, Ru, Ir, Zn, Pd, Cu, and Rh compounds have also been used as CO for higher hydrocarbon formation. 2 Several combinations of these elements in bimetallic and trimetallic catalysts with specific ratios have also been tried. However, catalysts based on the low-cost metals listed above (such as Cu, Zn, Fe, Co or Ni) suitable for large-scale commercial deployment (i.e., not Pt group metals such as Ru, Ir and Rh) have not been demonstrated as catalysts for the conversion of CO to 2 Commercial catalysts for hydrogenation to paraffins or other hydrocarbons suitable for use as diesel or aviation fuel.

[0022] This is primarily because previously reported compounds do not show the stability required for scaled-up materials, as these catalysts decay into less active materials in the reactor as they are produced. This is also due to their low selectivity for appropriate hydrocarbons based on the distribution of carbon chain lengths produced under commercial reactor conditions. Prior to the present disclosure, there was no known method for converting CO to CO due to the lack of a stable and efficient catalyst for this process. 2 Converted to CO or CH 4A commercial chemical process in which the carbon dioxide is first converted into a hydrocarbon product suitable for diesel or aviation fuel in no separate step, such as in the Sabatier process.

[0023] The present disclosure provides catalysts made of copper and zinc oxide and using these catalysts to generate CO 2 A method for producing hydrocarbons, wherein the catalyst optionally further comprises a catalyst selected from iron or cobalt for CO 2 The catalyst of the present disclosure comprises a first element (Co or Fe) as a metal that promotes carbon-carbon bond formation. Previously, copper-zinc family catalysts, such as copper and zinc oxide on alumina (CZA) catalysts, have not been demonstrated as catalysts for CO 2 Among other benefits, the modified copper-zinc catalysts disclosed herein catalyze the conversion of carbonaceous feedstock CO to polycarbonate products such as paraffins at a higher rate than any other reported CZA or FT catalysts. 2 , CO or CH 4 These catalysts can also be used to suppress gaseous byproducts (e.g., CH 4 ) is formed to further enable efficient recycling of unreacted gas during product gas recycle in the multi-vent gas-liquid reactor.

[0024] In certain embodiments, the present disclosure provides a catalyst comprising iron oxide, the catalyst optionally further comprising one or more additional metals selected from copper and / or zinc. In certain such embodiments, the one or more additional metals contribute to CO 2 In certain embodiments, the catalyst comprising iron oxide can be used to convert CO 2 converted into long-chain hydrocarbons.

[0025] As further described herein, the catalysts of the present disclosure preferably comprise one or more additional metals (Cu and / or Zn) as CO promoting 2 Previously, iron-based catalysts such as iron oxide catalysts have not been demonstrated as a promising catalyst for CO 2 Effective catalyst for hydrogenation to high carbon products such as paraffins.

[0026] In certain aspects, the present disclosure provides a method for producing a 2 and H 2The novelty of the method compared to previous CZA-based methods is that it produces multi-carbon species, and in particular long-chain alkanes with carbon numbers between 6 and 20, whereas previous CZA-based methods only produced products with carbon numbers between 1 and about 5. In addition, the method differs from the FT-based method in that CO 2 The CO in the feed stream of a typical cobalt-catalyzed FT process is 2 The increased concentration allows the reactor to produce exclusively methane, as known to those of ordinary skill in the art. Thus, the present invention represents an important step forward in gas-liquid chemistry by using catalysts and reaction conditions in which CO 2 and H 2 In some embodiments, the present invention uses cobalt to promote C—C bonding and chain growth while preventing CH4 from being generated through a combination of reactor conditions, adaptive monitoring of reaction products, and catalyst composition. 4 The production of.

[0027] In certain aspects, the present disclosure provides a method for producing a 2 and H 2 Chemical methods for producing long-chain hydrocarbons via alcohol intermediates. In some embodiments, alcohols are co-produced with 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 in a chemical reaction of the long-chain hydrocarbons that occurs in a single reactor. In these cases, the long-chain hydrocarbons are produced by first producing the alcohol and then dehydrating the alcohol to produce a combined CH x intermediates or free olefins, such as ethylene or propylene. x The intermediate or free olefin is further oligomerized to produce long chain hydrocarbons. In some embodiments, the alcohol is a byproduct of the chemical reaction of the long chain hydrocarbons occurring in a single reactor.

[0028] In certain aspects, the present disclosure provides a chemical method for producing long-chain hydrocarbons from a carbonaceous feedstock that does not follow an ASF distribution. In some embodiments, the ASF distribution deviates from the traditional FT method due to the uniqueness of the mechanism. In some embodiments, the present invention provides a method for producing a narrower distribution of desired hydrocarbons for diesel and aviation fuels compared to the traditional FT method. In some embodiments, the present invention provides a method for selectively producing straight-chain alkanes with a carbon number between 6 and 26. In some embodiments, the present invention provides a method for selectively producing straight-chain alkanes with a carbon number between 8 and 16. In some embodiments, the present invention provides a method for selectively producing hydrocarbons with a carbon number between 6 and 30.

[0029] In certain aspects, the present disclosure provides catalysts for producing long chain hydrocarbons from carbonaceous feedstocks, wherein there is a clear difference between Co-promoted catalysts and Fe-promoted catalysts. Figure 1 As shown in , Co-promoted copper-zinc catalysts typically fully hydrogenate long-chain hydrocarbons to produce saturated straight-chain alkanes with carbon numbers between 6 and 30. Figure 2 As shown in , Fe-promoted copper-zinc catalysts typically partially hydrogenate long-chain hydrocarbons to produce a mixture of saturated alkanes, olefins, and smaller concentrations of branched and cycloalkanes, aromatic compounds, alcohols, and carboxylic acids. In some embodiments, the present invention uses various ratios of Co and Fe in a catalyst comprising copper and zinc oxide to control the extent of branching or hydrogenation of reaction intermediates. 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.

[0030] In certain aspects, the present disclosure provides methods for adaptively monitoring a reactor to continuously generate CO in a single reactor. 2 and H 2 A method for producing long chain hydrocarbons without forming by-products. 2 and H 2 During the production of long-chain hydrocarbons, there is a narrow operating window of temperature, pressure, and gas composition that enables the production of liquid products without any gaseous byproducts. The present invention provides a method for real-time monitoring of the composition of a gaseous recirculation loop in a gas-liquid reactor system and adaptively adjusting the feed gas ratio and temperature. In some embodiments, real-time monitoring of the composition of the gaseous recirculation loop is achieved by a syngas analyzer that uses thermal conductivity detection to determine H 2 The relative concentration of CO is determined using infrared detection. 2 , CO, CH 4 In some embodiments, software or operator intervention is used to adjust the CO based on the outlet composition of the detector. 2 and H 2 The feed ratio is 50% to 100% to avoid the formation of non-recyclable by-products such as CH 4 .

[0031] catalyst

[0032] In certain aspects, the present disclosure provides a catalyst comprising: copper; zinc; one or more first elements, the one or more first elements selected from iron or cobalt; oxygen; optionally, aluminum; optionally, one or more second elements, the one or more second elements selected from Group V, Group VI, Group VII, Group VIII, Group IX, Group X, and Group XI metals (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel); and optionally, one or more Group IA metals, and wherein the one or more first elements are present in an amount of about 1 wt.% to about 40 wt.% (e.g., about 1 wt.% to about 10 wt.%, about 25 wt.% to about 40 wt.%, about 30 wt.% to about 40 wt.%, or about 35 wt.% to about 40 wt.%) based on the total amount of the copper, the zinc, the one or more first elements, the optional second element, and the optional Group IA metal.

[0033] In some embodiments, the one or more first elements are present in an amount of about 0.5 wt.%, about 1 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%, about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 26 wt.%, about 27 wt.%, about 28 wt.%, about 29 wt.%, about 30 wt.%, about 31 wt.%, about 32 wt.%, about 33 wt.%, about 34 wt.%, about 35 wt.%, about 36 wt.%, about 37 wt.%, about 38 wt.%, about 39 wt.%, about 40 wt.%, about 41 wt.%, about 42 wt.%, about 43 wt.%, about 44 wt.%, about 45 wt.%, about 46 wt.%, about 47 wt.%, about 48 wt.%, about 49 wt.%, about 50 wt.%, about 51 wt.%, about 52 %, about 7wt.%, about 18wt.%, about 19wt.%, about 20wt.%, about 21wt.%, about 22wt.%, about 23wt.%, about 24wt.%, about 25wt.%, about 26wt.%, about 27wt.%, about 28wt.%, about 29wt.%, about 30wt.%, about 31wt.%, about 32wt.%, about 33wt.%, about 34wt.%, about 35wt.%, about 36wt.%, about 37wt.%, about 38wt.%, about 39wt.% or about 40wt.%. In some embodiments, the one or more first elements are present in an amount of 1-10 wt.%, 10-20 wt.%, or 20-30 wt.%, 20-25 wt.%, 22-24 wt.%, 25-40 wt.%, 30-40 wt.%, or 35-40 wt.%, based on the total amount of copper, zinc, the one or more first elements, the optional second element, and the optional Group IA metal.

[0034] In some embodiments, the catalyst comprises a cobalt-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide. In some embodiments, the cobalt is present in the form of cobalt oxide. In some embodiments, the copper is present in the form of copper oxide. In some embodiments, the molar ratio of cobalt to copper to zinc (Co:Cu:Zn) is about 0.1-3 based on cobalt, about 1-4 based on copper, and about 0.5-1.5 based on zinc. In some embodiments, the Co:Cu:Zn ratio is in the range of 1-2 based on cobalt, 1-3 based on copper, and 0.5-1 based on zinc. In some embodiments, the Co:Cu:Zn ratio is about 1:2.5:1. In some embodiments, zinc is preferably 0.3–1 of the molar content of copper. In some embodiments, cobalt is preferably 0.1–1 of the molar content of copper.

[0035] In some embodiments, the catalyst comprises an iron-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide. In some embodiments, the iron is present in the form of iron oxide. In some embodiments, the copper is present in the form of copper oxide. In some embodiments, the molar ratio of iron to copper to zinc (Fe:Cu:Zn) is about 0.05-3 for iron, about 1-4 for copper, and about 0.5-4 for zinc. In some embodiments, the Fe:Cu:Zn ratio is in the range of 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, zinc is preferably 0.3–1 of the molar content of copper. In some embodiments, iron is preferably 0.5–5 of the molar content of copper.

[0036] In certain embodiments, the catalyst of the present disclosure includes copper (e.g., reduced copper nanoparticles) and zinc oxide supported on an iron carrier. In further embodiments, the iron carrier is iron oxide. In yet further embodiments, copper exists in the form of copper oxide. In still further embodiments, the catalyst includes iron, copper and zinc having a Fe:Cu:Zn ratio of about 0.05 to about 3 in terms of iron, about 1 to about 3 in terms of copper, and about 0.5 to about 3 in terms of zinc. In certain embodiments, the Fe:Cu:Zn ratio is about 0.4 to about 3 in terms of iron, about 0.4 to about 3 in terms of copper, and about 0.4 to about 3 in terms of zinc. In certain preferred embodiments, the Fe:Cu:Zn ratio is about 2.3:1:1. In certain preferred embodiments, the molar content of zinc included in the catalyst is about 0.3 times to about 1 times the molar content of copper. In certain preferred embodiments, the molar content of iron included in the catalyst is about 0.5 times to about 5 times the molar content of copper.

[0037] In some embodiments, the catalyst comprises one or more elements selected from transition metals or Group VI, Group VII, Group VIII, Group IX, Group X, or Group 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.

[0038] In some embodiments, the one or more second elements include manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel.

[0039] 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.

[0040] In some embodiments, the catalyst comprises one or more second elements at a molar ratio of about 0.15 to about 2 relative to copper. In some embodiments, the catalyst comprises one or more second elements at 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 at a molar ratio of about 0.15 to about 1 relative to copper. In some embodiments, the catalyst comprises one or more second elements at 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 at 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 at a molar ratio of about 0.15 to about 0.25 relative to copper.

[0041] In some embodiments, the catalyst comprises copper at a molar ratio of about 0.5 to about 5 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 1 to about 10 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2 to about 9 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2.3 to about 8.4 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2.3 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 8.4 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 1.5 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 1.0 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 0.75 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 0.5 relative to the one or more first elements.

[0042] In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.4 to about 1 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 1.5 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 1.0 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.75 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.5 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.4 relative to copper.

[0043] 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, niobium is present in a molar ratio of about 0.05 to about 1 relative to copper. In some embodiments, niobium is present in a molar ratio of about 0.2 relative to copper. In some embodiments, niobium is present in a molar ratio of about 0.3 relative to copper. In some embodiments, niobium is present in a molar ratio of about 0.1 relative to copper.

[0044] In some embodiments, the catalyst comprises one or more Group IA metals. In some embodiments, the catalyst comprises one or more Group IA or Group 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 Group 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 Group 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 Group 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 Group 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 Group IIA metals in a molar ratio of about 0.15 relative to copper.

[0045] In some embodiments, the catalyst comprises one or more Group IA metals. In some embodiments, one or more Group IA or Group IIA metals comprise potassium, sodium, or cesium. In some embodiments, one or more Group IA or Group IIA metals consist of potassium, sodium, or cesium. In some embodiments, one or more Group IA or Group IIA metals comprise potassium. In some embodiments, one or more Group IA or Group IIA metals comprise sodium. In some embodiments, one or more Group IA or Group IIA metals comprise cesium. In some embodiments, one or more Group IA or Group IIA metals consist of potassium. In some embodiments, one or more Group IA or Group IIA metals consist of sodium. In some embodiments, one or more Group IA or Group IIA metals consist of cesium.

[0046] In some embodiments, the catalyst comprises potassium at a molar ratio 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 relative to copper. In some embodiments, the catalyst comprises potassium at a molar ratio of about 0.09 relative to copper.

[0047] In certain embodiments, the catalyst comprises iron in a molar ratio of about 0.1 to about 10 relative to copper. In further embodiments, the catalyst comprises iron in a molar ratio of about 0.1 to about 1 relative to copper. In still further embodiments, the catalyst comprises iron in a molar ratio of about 0.1 to about 0.2 relative to copper. In certain embodiments, the catalyst comprises iron in a molar ratio of about 0.5 to about 1 relative to copper. In certain embodiments, the catalyst comprises iron in a molar ratio 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 relative to copper.

[0048] In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.1 to about 10 relative to copper. In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.1 to about 1 relative to copper. In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.1 to about 0.2 relative to copper. In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.5 to about 1 relative to copper. In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.1 relative to copper. In some embodiments, the catalyst comprises aluminum in a molar ratio of about 0.2 relative to copper.

[0049] In some embodiments, the catalyst includes zinc oxide.

[0050] In some embodiments, the catalyst includes copper oxide.

[0051] In some embodiments, the catalyst includes cobalt oxide.

[0052] In some embodiments, the catalyst comprises iron oxide.

[0053] In some embodiments, the catalyst includes nickel oxide.

[0054] In some embodiments, the catalyst includes alumina.

[0055] In certain embodiments, the one or more Group IA or Group IIA metals include or consist of sodium or cesium. In the catalysts of the present disclosure, replacing potassium with sodium or cesium does not substantially affect the catalytic activity, and both sodium and cesium have been found to provide the same stability as potassium. This is in contrast to known syngas catalysts, where the selection of potassium, sodium or cesium greatly affects the activity.

[0056] In some embodiments, the catalyst comprises aluminum oxide (Al 2 O 3 ) or consists of, wherein aluminum is present in a molar ratio of about 0.02 to about 3 relative to copper. In some embodiments, aluminum is present in a molar ratio of about 0.1 to about 0.8 relative to copper. In some embodiments, aluminum is present in a molar ratio of about 0.7 relative to copper. In some embodiments, aluminum oxide can be added as a support to increase the surface area of ​​copper and zinc, or generated in situ as a component of the catalyst, for example, by co-precipitation of aluminum nitrate with the first element, copper, and zinc precursors.

[0057] In certain embodiments, the catalyst comprises iron oxide (e.g., Fe 3 O 4 , Fe 2 O 3In further embodiments, iron is present in a molar ratio of about 0.2 to about 20 relative to copper. In still further embodiments, iron is present in a molar ratio of about 0.2 to about 10, about 0.2 to about 5, about 0.2 to about 2, about 0.2 to about 1, about 0.2 to about 0.5, about 1 to about 20, about 1 to about 10, or about 1 to about 2 relative to copper. In still further embodiments, iron is present in a molar ratio selected from about 1, about 2, about 5, about 10, about 15, and about 20 relative to copper.

[0058] In some embodiments, the catalyst includes iron oxide as a support to increase the surface area of ​​copper and zinc. In other embodiments, the iron oxide is generated in situ as a component of the catalyst, for example by co-precipitating iron nitrate with copper and zinc precursors.

[0059] In some embodiments, the catalyst comprises copper, zinc oxide, cobalt, and aluminum oxide. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises: cobalt; copper, the molar ratio of copper relative to cobalt is about 8.4; zinc, the molar ratio of zinc relative to cobalt is about 3.3; and aluminum oxide, wherein the molar ratio of aluminum relative to cobalt is about 1.8. In some embodiments, the catalyst comprises: copper, the molar ratio of copper relative to cobalt is about 8.4; zinc oxide, the molar ratio of zinc oxide relative to cobalt is about 3.3; and aluminum oxide, the molar ratio of aluminum oxide relative to cobalt is about 0.9.

[0060] In some embodiments, the catalyst comprises copper, zinc oxide, nickel, and aluminum oxide. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises nickel; copper, the molar ratio of copper relative to nickel is about 2.5; zinc, the molar ratio of zinc relative to cobalt is about 1; and aluminum oxide, wherein the molar ratio of aluminum relative to nickel is about 0.7. In some embodiments, the catalyst comprises copper, the molar ratio of copper relative to nickel is about 2.5; zinc oxide, the molar ratio of zinc oxide relative to nickel is about 1; and aluminum oxide, the molar ratio of aluminum oxide relative to nickel is about 0.35.

[0061] In some embodiments, the catalyst comprises copper, zinc oxide, iron, and aluminum oxide. In some such embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises: iron; copper, the molar ratio of copper relative to iron is about 2.3; zinc, the molar ratio of zinc relative to iron is about 2.3; and aluminum oxide, wherein the molar ratio of aluminum relative to iron is about 0.8. In some embodiments, the catalyst comprises: copper, the molar ratio of copper relative to iron is about 2.3; zinc oxide, the molar ratio of zinc oxide relative to iron is about 2.3; and aluminum oxide, the molar ratio of aluminum oxide relative to iron is about 0.4.

[0062] In some embodiments, the catalyst comprises copper, zinc oxide, cobalt, aluminum oxide, 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, wherein the molar ratio of copper to cobalt is about 8.4; zinc, wherein the molar ratio of zinc to cobalt is about 3.3; aluminum oxide, wherein the molar ratio of aluminum to cobalt is about 1.8; and one or more Group IA or Group IIA metals, wherein the molar ratio of the one or more Group IA or Group IIA metals to cobalt is about 0.14. In some embodiments, the catalyst comprises: copper, wherein the molar ratio of copper to cobalt is about 8.4; zinc oxide, wherein the molar ratio of zinc oxide to cobalt is about 3.3; aluminum oxide, wherein the molar ratio of aluminum oxide to cobalt is about 0.9; and one or more Group IA or Group IIA metals, wherein the molar ratio of the one or more Group IA or Group IIA metals to cobalt is about 0.14.

[0063] In some embodiments, the catalyst comprises copper, zinc oxide, nickel, aluminum oxide, 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, wherein the molar ratio of copper relative to nickel is about 2.5; zinc, wherein the molar ratio of zinc relative to nickel is about 1; aluminum oxide, wherein the molar ratio of aluminum relative to nickel is about 0.7; and a Group IA, wherein the molar ratio of the Group IA relative to nickel is about 0.1. In some embodiments, the catalyst comprises: copper, wherein the molar ratio of copper relative to nickel is about 2.5; zinc oxide, wherein the molar ratio of zinc oxide relative to nickel is about 1; aluminum oxide, wherein the molar ratio of aluminum oxide relative to nickel is about 0.35; and one or more Group IA or Group IIA metals, wherein the molar ratio of the one or more Group IA or Group IIA metals relative to nickel is about 0.1.

[0064] In some embodiments, the catalyst comprises copper, zinc oxide, iron, aluminum oxide, 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, wherein the molar ratio of copper relative to iron is about 2.3; zinc, wherein the molar ratio of zinc relative to iron is about 2.3; aluminum oxide, wherein the molar ratio of aluminum relative to iron is about 0.4; and one or more Group IA or Group IIA metals, wherein the molar ratio of the one or more Group IA or Group IIA metals relative to iron is about 0.4. In some embodiments, the catalyst comprises: copper, wherein the molar ratio of copper relative to iron is about 2.5; zinc oxide, wherein the molar ratio of zinc oxide relative to iron is about 1; aluminum oxide, wherein the molar ratio of aluminum oxide relative to iron is about 0.35; and one or more Group IA or Group IIA metals, wherein the molar ratio of the one or more Group IA or Group IIA metals relative to iron is about 0.1.

[0065] In some embodiments, the catalyst includes Cu, Zn, Al, O and alkali metals. In certain embodiments, the catalyst includes Cu, Zn, Fe and O. In some embodiments, the catalyst includes Cu, Zn, Ni, Al, O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Fe, Al, O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Co, Fe, Al, O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Co, Al, O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Co, Nb, Al and O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Co, Ni, Al and O and alkali metals. In some embodiments, the catalyst includes Cu, Zn, Co, Mo, Al and O and alkali metals.

[0066] 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.

[0067] In some embodiments, the elemental composition of the catalyst 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 , wherein A is an alkali metal, and further wherein the relative amounts of the elemental components are as described above.

[0068] In some embodiments, 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 , wherein the relative amounts of the elemental components are as described above.

[0069] In some embodiments, the catalyst is selected from one of the following exemplary catalysts: Al 2 O 3 CuO(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, Cu(ZnO)CoMoK on the catalyst, wherein the relative amounts of the elemental components are as described above. In certain embodiments, the catalyst is 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) .

[0070] In a further aspect, provided herein is a catalyst for producing paraffinic hydrocarbons, the catalyst comprising:

[0071] One or more metals;

[0072] Optionally, one or more second elements, the one or more second elements selected from copper and zinc;

[0073] Optionally, one or more Group VI, Group VII, Group VIII, Group IX, Group X, or Group XI metal additives;

[0074] Optionally, a Group IA or Group IIA metal promoter.

[0075] In certain embodiments, the one or more metals are selected from cobalt, iron, nickel, indium, yttrium, lanthanum, 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 still further embodiments, the one or more metals are a combination of iron and cobalt.

[0076] In certain embodiments, the one or more metals are present in the form of oxides, nitrides, or carbides. 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 oxides, nitrides, or carbides.

[0077] In certain embodiments, one or more Group VI, Group VII, Group VIII, Group IX, Group X, or Group 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 Group IIA metal promoter, when present, is a Group IA element. In still further embodiments, the Group IA or Group 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 wt.% to about 40 wt.% of the total amount of the one or more metals, the second element, the optional one or more Group VI, Group VII, Group VIII, Group IX, Group X, or Group XI metal additives, and the optional Group IA or Group IIA metal promoter.

[0078] In certain aspects, the systems and methods of the present disclosure involve using hydrogenation catalysts and isomerization catalysts to isomerize or hydrogenate, respectively, a percentage of the hydrocarbons produced. In certain embodiments, the hydrogenation catalysts and isomerization catalysts of the present disclosure may be independently selected from the catalysts described below.

[0079] 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 AlCl 3 . In a further embodiment, the isomerization catalyst and / or hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc. In a still further embodiment, the isomerization catalyst and / or hydrogenation catalyst is Pt on β-zeolite. In certain embodiments, the isomerization catalyst and / or hydrogenation catalyst of the present disclosure comprises an isomerization catalyst metal and a zeolite carrier. In a further embodiment, the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo. In a further embodiment, the zeolite carrier is selected from SiAlO x 、SO 4 -ZrO 2 , Y-zeolite, β-zeolite, ZSM5, ZSM22, SAPO11, SAPO31, SAPO41 and TiO 2 In still further embodiments, 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.

[0080] In certain embodiments, the isomerization metal includes about 0.5wt% to about 40wt% of an isomerization catalyst and / or a hydrogenation catalyst. In a further embodiment, the isomerization metal includes about 0.5wt% of an isomerization catalyst and / or a hydrogenation catalyst. In a further embodiment, the isomerization metal includes about 1wt% of an isomerization catalyst and / or a hydrogenation catalyst. In a still further embodiment, the isomerization metal includes about 10wt% of an isomerization catalyst and / or a hydrogenation catalyst. In certain embodiments, the isomerization metal includes about 20wt% of an isomerization catalyst and / or a hydrogenation catalyst. In a further embodiment, the isomerization metal includes about 30wt% of an isomerization catalyst and / or a hydrogenation catalyst. In a still further embodiment, the isomerization metal includes about 40wt% of an isomerization catalyst and / or a hydrogenation catalyst.

[0081] In certain embodiments, when the isomerization catalyst is Pt / Al 2 O 3 When the isomerization temperature is about 250°C, the isomerization pressure is about 750 psi. In certain embodiments, when the isomerization catalyst is a zeolite-based catalyst, the isomerization temperature is about 300°C, and the isomerization pressure is about 750 psi.

[0082] Catalytic composition

[0083] In certain aspects, the present disclosure provides a catalytic composition comprising a catalyst disclosed herein and one or more of an additional support. The additional support may be any suitable material that can serve as a catalyst support.

[0084] In some embodiments, the additional support comprises one or more materials selected from oxides, nitrides, fluorides, silicates or carbides of elements selected from the group consisting of 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 the group consisting of aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron and tin. In some preferred embodiments, the additional support comprises gamma-alumina. In certain embodiments, the additional support is selected from carbon, silica, zeolites, alumina, zirconia, titanium oxide and silicon carbide. In certain embodiments, the additional support is selected from carbon, silica, zeolites, alumina, iron oxide, zirconium oxide, titanium oxide and silicon carbide. In some embodiments, the additional support is alumina formed in situ as part of the catalyst. In some embodiments, the additional support is selected from but not limited to Al 2 O 3 、ZrO 2 SnO 2 、SiO 2, ZnO and TiO 2 In some embodiments, the additional carrier is selected from Al 2 O 3 、ZrO 2 SnO 2 、SiO 2 , ZnO and TiO 2 In some embodiments, the additional carrier 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 .

[0085] In some embodiments, the additional support comprises one or more carbon-based materials. In some embodiments, the carbon-based material is selected from activated carbon, carbon nanotubes, graphene, and graphene oxide.

[0086] In some embodiments, the additional support is a mesoporous material. In some embodiments, the additional support has a mesoporous volume of about 0.01 cc / g to about 3.0 cc / g.

[0087] In some embodiments, the surface area of ​​the additional carrier is about 10 m 2 / g to about 1000m 2 In some preferred embodiments, the surface area of ​​the catalytic composition disclosed herein including additional supports and catalysts is about 10 m 2 / g to about 1000m 2 / g.

[0088] In some embodiments, the catalytic composition is in the form of particles having an average size of about 10 nm to about 5 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 20 nm to about 5 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 50 nm to about 1 μm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 100 nm to about 500 nm. In some embodiments, the catalytic composition is in the form of particles having an average size of about 50 nm to about 300 nm.

[0089] In some embodiments, the catalytic composition comprises from about 5 wt.% to about 80 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 5 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 20 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 30 wt.% to about 70 wt.% of the catalyst.

[0090] 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.

[0091] In some embodiments, the catalyst is a nanoparticle catalyst. In some embodiments, the particle size of the catalyst on the surface of the support is about 1nm to 5nm. In some embodiments, the particle size of the catalyst on the surface of the support is about 5nm to 100nm. In some embodiments, the particle size of the catalyst on the surface of the support is 100-500nm. In some embodiments, the particle size of the particles that have not been agglomerated is 100-500nm.

[0092] Preparation method

[0093] The catalysts and catalytic compositions of the present disclosure may be prepared by any suitable method. In certain aspects, the present disclosure provides a method for preparing the catalysts or catalytic compositions disclosed herein, the method comprising preparing the catalyst by coprecipitation, wet impregnation or ball milling.

[0094] In some embodiments, the method comprises the following steps:

[0095] (a) providing a first solution, wherein the first solution comprises a cobalt source, a copper source, a zinc source, an aluminum source, an alkali and water;

[0096] (b) heating the first solution at a first temperature for a first period of time, thereby producing a first reaction mixture;

[0097] (c) heating the first reaction mixture at a second temperature for a second period of time to remove the water, thereby producing a solid precursor; and

[0098] (d) heating the solid precursor to a third temperature for a third period of time, thereby separating the catalyst.

[0099] In some embodiments, the method comprises the following steps:

[0100] (a) providing a second solution, wherein the second solution comprises a cobalt source, a copper source, a zinc source, an iron source and water;

[0101] (b) providing a third solution, wherein the third solution comprises a base;

[0102] (c) heating the third solution at a third temperature for a third period of time;

[0103] (d) adding alumina to the third solution, thereby producing a second reaction mixture;

[0104] (e) adding the second solution to the second reaction mixture at a fourth temperature for a fourth period of time, thereby producing a third reaction mixture;

[0105] (f) heating the third reaction mixture at a fifth temperature for a fifth time period, thereby producing a solid precursor;

[0106] (g) separating the solid precursor;

[0107] (h) contacting the solid precursor with a solution comprising a Group IA metal, thereby producing a catalyst precursor; and

[0108] (i) heating the catalyst precursor to a sixth temperature for a sixth period of time, thereby separating the catalyst.

[0109] In some embodiments, the method comprises 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 an alkaline precipitant such as a carbonate to increase the pH of the solution containing the metal salt, thereby precipitating solid particles, drying the solid particles, and calcining the solid particles to form a solid catalyst.

[0110] In certain embodiments, the base comprises a carbonate and a cation selected from the group consisting of potassium, sodium, ammonium, lithium, and cesium. In other embodiments, the base comprises a bicarbonate and a cation selected from the group consisting of potassium, sodium, ammonium, lithium, and cesium.

[0111] In some embodiments, the method comprises the steps of providing a first solution, the first solution comprising a cobalt source; and introducing the first solution into a preformed copper-zinc alumina material by incipient wetness or wet impregnation, followed by drying and calcining to form a solid catalyst.

[0112] In some embodiments, the method comprises the steps of: mixing a cobalt source and a carrier in a milling jar to provide a first mixture; ball milling the first mixture for 2 hours to 2 weeks to provide a first precipitate; filtering the first precipitate and heating it to a first temperature to provide a ball-milled cobalt source;

[0113] mixing the ball-milled cobalt source with a copper source and a zinc source and an alumina source to provide a second mixture; and separating a solid material from the second mixture.

[0114] In some embodiments, the method further comprises mixing the solid material with one or more Group IA metal sources. 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 before introducing the solid material into the flow reactor.

[0115] Hydrogenation method

[0116] In certain aspects, the present disclosure provides methods for making a carbonaceous feedstock (i.e., CO 2 ) into a liquid product mixture, the method comprising contacting a catalyst of the catalytic composition disclosed herein with a feed mixture at a reducing temperature and a reducing pressure, thereby providing a liquid product mixture, the feed mixture comprising CO 2 and reducing agent gas.

[0117] In some embodiments, the reducing agent gas is H 2 In some embodiments, the reducing agent gas is a hydrocarbon, such as CH 4 In a preferred embodiment, the hydrocarbon is CH 4 In certain such embodiments, CH 4 is a component of a gas mixture that also includes other hydrocarbons, such as ethane, propane or butane. 4 The gas mixture may be (or may be derived from) flare gas, waste gas, natural gas, etc.

[0118] 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.

[0119] In some embodiments, the reduction temperature is from about 100°C to about 600°C. In some embodiments, the reduction temperature is from about 275°C to about 350°C. In some embodiments, the reduction temperature is about 275°C. In some embodiments, the reduction temperature is about 300°C.

[0120] In some embodiments, the reduction pressure is about 50 psi to about 3000 psi. In some embodiments, the reduction pressure is about 900 psi to about 1100 psi. In some embodiments, the reduction pressure is about 1000 psi.

[0121] In some embodiments, the CO in the feed mixture 2 The partial pressure of CO in the feed mixture is about 20 psi to about 1500 psi. 2The partial pressure of CO in the feed mixture is about 200 psi to about 800 psi, about 200 psi to about 600 psi, about 200 psi to about 400 psi, or about 300 psi 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 is about 330 psi.

[0122] In some embodiments, the reducing agent gas in the feed mixture: CO 2 The ratio of the reductant gas in the feed mixture to the CO is about 10:1 to about 1:10. 2 The ratio of the reductant gas in the feed mixture to the CO is about 5:1 to about 0.5:1. In some embodiments, the reductant gas in the feed mixture to the CO 2 The ratio of the reductant gas in the feed mixture to the CO is about 4:1 to about 1:1. In some embodiments, the reductant gas in the feed mixture to the CO 2 The ratio is about 3:1.

[0123] In some embodiments, the liquid product mixture includes methanol.In some embodiments, the liquid product mixture includes methanol, ethanol and n-propanol.In some embodiments, the liquid product mixture includes methanol, ethanol, acetic acid and n-propanol.In some embodiments, the amount of ethanol and higher alcohols accounts for at least 10wt.% of the total amount.In some embodiments, the amount of ethanol and higher alcohols accounts for at least 7wt.% of the total amount of the liquid product mixture.In some embodiments, the amount of ethanol and higher alcohols accounts for at least 5wt.% of the total amount of the liquid product mixture.In some embodiments, the amount of ethanol and higher alcohols accounts for at least 2wt.% 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 about 1:5 to about 1:10.In some embodiments, the amount of formic acid in the liquid product mixture is less than 10ppm.In some embodiments, the amount of isopropanol in the liquid product mixture is less than 10ppm.

[0124] In some embodiments, the liquid product mixture includes hydrocarbons. In some embodiments, the liquid product mixture includes paraffins. As used herein, the term "paraffin" refers to hydrocarbons that are preferably straight-chain, but may include branched hydrocarbons. Exemplary paraffins have a carbon number of 6-20, preferably 9-16.

[0125] For the processes described herein, the term "liquid product mixture" refers to a product that is liquid at atmospheric pressure and temperature.

[0126] In certain embodiments, the liquid product mixture includes paraffin, olefin and other hydrocarbon.In certain embodiments, the amount of paraffin accounts for at least 50wt.% of total non-aqueous product.In certain embodiments, the amount of paraffin accounts for at least 10wt.% of the total amount of liquid product mixture.In certain embodiments, the amount of paraffin accounts for at least 5wt.% of the total amount of liquid product mixture.In certain embodiments, the amount of paraffin accounts for at least 2wt.% of the total amount of liquid product mixture.In certain embodiments, the molar ratio of the total amount of paraffin and carbon-containing product in the liquid product mixture is about 1:2 to about 1:10.In certain embodiments, the amount of formic acid in the liquid product mixture is less than 1,000ppm.In certain embodiments, the amount of isopropanol in the liquid product mixture is less than 1,000ppm.

[0127] It is an object of the present invention to use low GHSV (gas hourly space velocity) to provide high gas product recyclability and avoid certain byproducts 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 wt% formaldehyde or methane. In some embodiments, the method produces less than about 0.05 wt% formaldehyde or methane. In some embodiments, the method produces less than about 50 ppm formaldehyde or methane. In some embodiments, the method produces less than about 5 ppm formaldehyde or methane.

[0128] In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 10. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 100. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 500. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 1,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 2,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 5,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 10,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 20,000 or more.

[0129] In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 20,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 10,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 5,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 2,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 1,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 500. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is from about 10 to about 100.

[0130] In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 10. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 100. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 500. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 1,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 2,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 5,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 10,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is less than about 20,000.

[0131] In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 100. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 500. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 1,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 2,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 5,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 10,000. In some embodiments, the GHSV of the reactant gas and the recycle gas introduced into the reactor is 20,000.

[0132] 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.

[0133] 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 isomerized product mixture including linear paraffins, branched paraffins, and / or cycloparaffins.

[0134] In further embodiments, the isomerized product mixture comprises:

[0135] Another C 1-8 hydrocarbon;

[0136] Another C 9-15 hydrocarbons, the additional C 9-15 Hydrocarbons include straight chain alkanes, branched chain alkanes, and cycloalkanes; and

[0137] Another C 16+ hydrocarbon.

[0138] In some embodiments, the numerals used to describe and claim certain embodiments of the present disclosure are modified by the term "about" in some cases. In some embodiments, numerical parameters should be interpreted according to the number of reported significant figures and by applying conventional rounding techniques. Although the wide range of numerical values ​​and parameters of some embodiments of the present invention are approximate values, the numerical values ​​described in the specific examples are reported as accurately as possible. The numerical values ​​presented in some embodiments of the present invention may contain certain errors that are inevitably produced by the standard deviation present in its corresponding test measurement.

[0139] 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.

[0140] Examples

[0141] Having now generally described the invention, the invention will be more readily understood by reference to the following examples, which are included merely for the purpose of illustrating certain aspects and embodiments of the invention and are not intended to limit the invention.

[0142] Example 1: Elemental composition of an exemplary cobalt copper zinc alumina catalyst.

[0143] Metal oxides CuO ZnO CoO <![CDATA[Al 2 THE 3 ]]> MgO wt% 59.0％ 23.2％ 7.1％ 9.3％ 1.4％ Metal content Cu Zn Co Al Mg wt% 47.1％ 18.7％ 5.6％ 4.9％ 0.8％

[0144] Example 2: Synthesis of an exemplary cobalt copper zinc alumina catalyst by combined coprecipitation and wet impregnation.

[0145] A first solution comprising zinc nitrate (1 molar equivalent), copper nitrate (3 molar equivalents), aluminum nitrate (1.4 molar equivalents) and a second solution comprising sodium carbonate (9.7 molar equivalents) were combined in a reactor. The resulting mixture was rapidly stirred and heated at 70-90°C for 2 hours and then filtered. The resulting solid material was dried at 110°C under air for 12 hours and crushed, heated to 350°C in air at a heating rate of 2°C / min, and calcined at 350°C for 6 hours. After calcination, the resulting powder was then further ground with a mortar and pestle. The powder was granulated and a mixture containing Co(NO 3 ) 2 6H 2 A liquid of O (8 wt% Co in aqueous solution) was added to the pelletized catalyst by incipient wetness impregnation and heated to produce a cobalt copper zinc alumina catalyst (CCZA).

[0146] Example 3: Synthesis of exemplary iron catalysts by co-precipitation and wet impregnation.

[0147] A first solution consisting of ferric nitrate (1 molar equivalent) and an alkaline solution comprising sodium carbonate (1.2 molar equivalents) were combined in a reactor at about 60°C. The resulting mixture was rapidly stirred and heated at 70°C to 90°C for 2 hours, then filtered and dried. The resulting solid material was dried at 110°C for 12 hours under air, and the resulting solid material was crushed, heated to 350°C at a heating rate of 2°C / min in air, and calcined at 350°C for 6 hours. After calcination, the resulting powder was further ground with a mortar and pestle.

[0148] Example 4: Elemental composition of iron copper zinc catalyst with and without alumina.

[0149] Iron-copper-zinc catalyst without alumina (FCZK)

[0150] Metal oxides CuO ZnO <![CDATA[Fe 2 THE 3 ]]> <![CDATA[K 2 CO 3 ]]> wt% 37.7％ 38.5％ 18.9％ 4.9％ Metal content Cu Zn Fe K wt% 30.1％ 31.0％ 13.2％ 2.8％

[0151] Iron-copper-zinc-alumina catalyst

[0152] Metal oxides CuO ZnO <![CDATA[Fe 2 THE 3 ]]> <![CDATA[Al 2 THE 3 ]]> wt% 35.7％ 36.5％ 17.9％ 10.0％ Metal content Cu Zn Fe Al wt% 28.5％ 29.3％ 12.5％ 5.3％

[0153] Example 5: CO in the presence of an exemplary cobalt copper zinc catalyst 2 reduction.

[0154] CO in the presence of CCZA was carried out over the course of 14 days under the following conditions: 2 reduction:

[0155] 3:1 H 2 :CO 2 ratio;

[0156] GHSV is about 2000h-1 ;

[0157] CO 2 The one-way conversion rate is about 30%;

[0158] The temperature is 270°C;

[0159] The pressure is 1000 psi.

[0160] The composition of the liquid product fraction resulting from the reaction is shown in Table 1.

[0161] Table 1: Chemical species and approximate relative abundance of products in gas chromatography analysis of CCZA catalyst products.

[0162]

[0163]

[0164] Example 6: CO using an iron-copper-zinc catalyst 2 Catalytic reduction to hydrocarbons.

[0165] CO in the presence of FCZK was carried out over the course of 14 days under the following conditions: 2 reduction:

[0166] 3:1 H 2 :CO 2 ratio;

[0167] GHSV is about 5000h -1 ;

[0168] CO 2 The one-way conversion rate is about 20%;

[0169] The temperature is 270°C;

[0170] The pressure is 1000 psi.

[0171] The composition of the liquid product fraction resulting from the reaction is shown in Table 2.

[0172] Table 2: Chemical species and approximate relative abundance of products in gas chromatography analysis of FCZK catalyst products.

[0173]

[0174]

[0175] Example 7: General Procedure for Hydroisomerization of Paraffins

[0176] The paraffins were fed into an isomerization reactor loaded with a hydroisomerization catalyst (Pt on β-zeolite, 0.5 wt% Pt). The reaction was carried out at 750 psi and 250°C, with the molar ratio of hydrogen to hydrocarbon set to 500 and a liquid weight hourly space velocity of 1.0 h -1 In the case of carbon chain number between C 8 With C 15 The paraffins are converted into a mixture of saturated normal alkanes and isoalkanes in a selectivity range between 2.0 and 1.5.

[0177] Incorporated by Reference

[0178] All publications and patents mentioned herein are hereby incorporated by reference in their entirety to the same extent as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In the event of a conflict, the present application, including any definitions herein, will control.

[0179] Equivalent form

[0180] Although specific embodiments of the present invention have been discussed, the above description is illustrative rather than restrictive. After reading this specification and the following claims, many variations of the present invention will become apparent to those skilled in the art. The full scope of the present invention should be determined by reference to the full scope of the claims and their equivalents and the specification and these variations.

Claims

1. A catalyst for producing a liquid product mixture, the catalyst comprising: one or more metals selected from cobalt, iron, nickel, indium, yttrium, lanthanum or combinations thereof; one or more second elements selected from copper, zinc, or combinations thereof; optionally, one or more Group VI, Group VII, Group VIII, Group IX, Group X, or Group XI metal additives; and Group IA or IIA metal promoters, The liquid product mixture comprises paraffins and olefins.

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

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

4. The catalyst of claim 1, wherein the one or more metals is a combination of iron and cobalt.

5. The catalyst of claim 1, wherein the one or more metals are present in the form of oxides, nitrides or carbides.

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

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

8. The catalyst of claim 1, wherein the one or more second elements are copper and zinc.

9. The catalyst of claim 1, wherein the one or more second elements are present in the form of oxides, nitrides or carbides.

10. The catalyst of claim 1 wherein 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.

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

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

13. The catalyst of claim 1, wherein the one or more second elements are present in an amount of about 0.5 wt. % to about 40 wt. % based on the total amount of the one or more metals, the second element, the optional one or more Group VI, Group VII, Group VIII, Group IX, Group X or Group XI metal additives and the Group IA or Group IIA metal promoter.

14. A catalytic composition comprising the catalyst according to claim 1 and an additional support.

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

16. A method for converting CO2 and a reducing gas into long-chain hydrocarbons, the method comprising: contacting a feed mixture comprising CO2 and the reducing gas with a first catalyst at a reducing temperature and a reducing pressure to produce a product mixture comprising long-chain hydrocarbons; wherein the first catalyst comprises iron and a second element selected from copper and zinc; wherein the product mixture comprises a gaseous product mixture and a liquid product mixture; wherein the liquid product mixture comprises an aqueous liquid product mixture and a non-aqueous liquid product mixture; and The non-aqueous liquid product mixture comprises hydrocarbons with carbon numbers between 6 and 30.

17. The method of claim 16, wherein the product mixture comprises: i) less than about 0.5 wt % formaldehyde or methane; ii) less than about 0.05 wt % formaldehyde or methane; iii) less than about 50 ppm formaldehyde or methane; iv) less than about 25 ppm formaldehyde or methane; or v) less than about 5 ppm formaldehyde or methane.

18. The process of claim 16, wherein the non-aqueous liquid product mixture comprises paraffins, olefins, and other hydrocarbons.

19. The method of claim 16, wherein the non-aqueous liquid product mixture comprises linear alkanes having carbon numbers between 6 and 26 or linear alkanes having carbon numbers between 8 and 16.

20. The method of claim 18, wherein the amount of the paraffin is: i) at least 2 wt.% of the liquid product mixture; ii) at least 5 wt.% of the liquid product mixture; iii) at least 10 wt.% of the liquid product mixture; or iv) at least 50 wt.% of the liquid product mixture.

21. The method of any one of claims 16, 18 or 20, wherein the amount of paraffins in the liquid product mixture to the total amount of carbon-containing products is from about 1:2 to about 1:

10.

22. The process of claim 16 or 17, wherein the amount of formic acid in the liquid product mixture is less than 1,000 ppm; and / or the amount of isopropanol in the liquid product mixture is less than 1,000 ppm.

23. The process of claim 16, wherein the feed mixture comprises CO, optionally in an amount of 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.

24. The method of claim 16, wherein the method further comprises: monitoring the product mixture; capturing unreacted components and partially reacted components from the feed mixture to produce a recycled gas mixture; combining the recycled gas mixture with the feed mixture; as well as The ratio of the recirculated gas mixture to the feed mixture is adjusted.

25. The process of claim 16 or 24, further comprising contacting the product mixture and the isomerization gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to obtain an isomerized product mixture comprising linear paraffins, branched paraffins and / or cycloparaffins.

26. The method of claim 16, wherein the liquid product mixture comprises linear hydrocarbons having carbon numbers between 6 and 20 or between 9 and 16.

27. The method of claim 16 or 26, wherein the first catalyst further comprises carbon, silica, zeolite, alumina, zirconia, titania, and silicon carbide.

28. The method of claim 16, wherein the first catalyst further comprises a Group IA or Group IIA element promoter.

29. The method of claim 28, wherein the Group IA or Group IIA element promoter is selected from lithium, sodium, potassium or cesium.

30. The method of any one of claims 16, 28 or 29, wherein the second element is zinc.

31. The method of claim 30, wherein iron, zinc, or both iron and zinc are present in the form of oxides, nitrides, or carbides.

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