Preparation of c5 from a mixed gas + Catalyst for hydrocarbons and method for its preparation and use

Abstract

The present application relates to a kind of catalyst and its preparation method, and the application of the catalyst in the process of mixed gas preparation C5 + Hydrocarbons. Specifically, the present application discloses a catalyst, which comprises: a metal catalyst, the metal catalyst comprising at least four metal oxides; a first molecular sieve catalyst; a second molecular sieve catalyst; and optionally, a third molecular sieve catalyst. Using the catalyst, mixed gas can be directly utilized as raw material with high CO2 content without water gas shift and decarburization treatment, and C5 + Hydrocarbons are synthesized, and the single-pass C5 + Hydrocarbon selectivity is greater than 80%, and the selectivity of C9-C16 components in oil is greater than 60%; the raw material has strong adaptability, short process, good selectivity, and the single-pass C5 + Hydrocarbon space-time yield reaches 0.50 kg / kg·h or more, and has good industrial application prospect.

Description

Technical Field

[0001] This invention relates to the field of energy and chemical catalyst technology, specifically to a method for preparing C5 from a mixed gas. + Catalysts used in hydrocarbon processes and their preparation methods. Background Technology

[0002] my country's crude oil imports are projected to exceed 520 million tons by 2025, with its dependence on foreign oil remaining above 70% for ten consecutive years. Self-sufficiency in refined oil supply remains a core strategic concern in the energy sector. Meanwhile, domestic industries such as coal chemical, steel, and cement emit over 10 billion tons of CO2 annually. A large amount of low-concentration CO2 in industrial waste gas has long been unable to achieve high-value-added resource utilization. The carbon capture and storage (CCUS) model is not only costly but also fails to generate direct economic benefits, hindering its large-scale adoption. Against this backdrop, the technology route of using mixed gas and CO2 to hydrogenate clean hydrocarbon fuels precisely establishes a complete low-carbon closed loop of "carbon capture - green hydrogen consumption - fuel synthesis - transportation decarbonization." This technology route uses the CO2 that would otherwise be emitted as a carbon source for fuel production, combining it with green hydrogen generated from wind and solar power to directly convert it into high-energy-density gasoline and jet fuel products. This avoids the consumption of fossil crude oil and achieves the recycling of carbon resources, perfectly aligning with the core direction of global energy transition. However, since the carbon-oxygen bond energy of CO2 molecules is as high as 750 kJ / mol, in the above-mentioned technology for preparing hydrocarbon fuels using CO2 molecules, the methane selectivity in the final product exceeds 40%, and the technical difficulty of directionally synthesizing long-chain hydrocarbons from the reactants is extremely high, resulting in a very low yield of long-chain jet fuel components.

[0003] In addition, CO2 can also be used in the field of mixed gas to produce oil products, namely the traditional Fischer-Tropsch synthesis process, which uses mixed gas as feedstock to produce oil products. However, the traditional Fischer-Tropsch synthesis process requires the feedstock gas to first undergo a water-gas shift reaction (CO + H2O → CO2 + H2) to adjust the hydrogen-to-carbon ratio, and then undergo a decarbonization process to remove CO2. This process has prominent problems such as long process, high energy consumption, large investment, and high carbon emissions. For this synthesis process, there are already mature industrial practices. For example, the Ningdong 4 million tons / year coal indirect liquefaction demonstration project was successfully completed and produced oil in 2016. After nearly 10 years of long-term industrial operation verification, the project has achieved an overall carbon conversion rate of over 90%, and C5... + Hydrocarbon selectivity remains stable at over 92%.

[0004] In the exploration of this process technology, there are also examples such as Chinese Patent 202411001702.1, which provides a catalyst for producing aviation kerosene distillate from a carbon dioxide-rich mixed gas. The catalyst is a composite metal oxide, comprising, by mass percentage, 40%-70% Fe, 5%-20% Mn, 5%-20% K, and the balance O. When this catalyst is used in the hydrogenation reaction of a carbon dioxide-rich mixed gas to produce aviation kerosene distillate, the CO conversion rate is >55%, the CO2 selectivity is <30%, and the C8-C ratio is [not specified]. 16 The selectivity of hydrocarbon products is >37%. Furthermore, Chinese Patent 202511729736.7 discloses a catalyst for preparing sustainable aviation fuel from a CO2-rich mixed gas. Using nano-sized ZSM-11 molecular sieves as a support, it is added dropwise to Fe(NO3)3·9H2O under stirring in an aqueous solution, stirred, dried at 120℃ for 12 h, calcined at 500-600℃ for 4-6 h, and naturally cooled to room temperature. After H2 reduction, a CO2-rich mixed gas (a CO2 / CO / H2 mixture with a CO2 to CO molar ratio of 1:1) is introduced at a space velocity of 2200 mL·gcat. -1 ·h -1 With a hydrogen-to-carbon ratio of 2:1, a reaction temperature of 420℃, and a pressure of 2MPa, sustainable aviation fuel (C8-C) from petroleum products was obtained. 16 Hydrocarbons accounted for 47.1% of the total product output, of which 90.6% were (C8-C4) hydrocarbons. 16 Aromatic hydrocarbons. However, compared to existing mixed-gas Fischer-Tropsch synthesis technologies that use C5... + Hydrocarbon selectivity remained stable at 92%, and these technologies still lag significantly behind.

[0005] Therefore, how to directly and efficiently convert a mixture of CO and / or CO2 and H2 into C5 + Reducing CO2 selectivity and overcoming single-pass selectivity limitations in hydrocarbon fractions are technical challenges that urgently need to be addressed in this field. Summary of the Invention

[0006] To address the aforementioned problems still existing in the field of energy and chemical engineering, catalysts are crucial. This invention provides a method for preparing C5 from a mixed gas. + This catalyst combination for hydrocarbon fractions eliminates the need for water-gas shift hydrogenation and decarbonization treatment of the feed gas mixture, allowing direct production of C5 from a high-CO2 content, low-hydrogen-to-carbon ratio mixture. + Hydrocarbon fractions can also be directly synthesized into C5 using a CO + H2 mixture or a CO + H2 mixture. + Hydrocarbon fractions, and C5 content in single-pass liquid oil products. + The selectivity of hydrocarbon fractions reaches over 80%, and C5... +The space-time yield of hydrocarbon fractions reaches over 0.50 kg / kg catalyst·h.

[0007] To achieve the above objectives, the present invention provides the following technical solution: In a first aspect, the present invention provides a catalyst comprising: a metal catalyst comprising at least four metal oxides; a first molecular sieve catalyst; a second molecular sieve catalyst; and optionally, a third molecular sieve catalyst.

[0008] In a second aspect, the present invention provides a method for preparing the catalyst described herein, comprising the preparation of a metal catalyst, a first molecular sieve catalyst, and a second molecular catalyst.

[0009] In a third aspect, the present invention provides a method for preparing C5 using a mixed gas. + A method for processing hydrocarbons, comprising treating a gas mixture using the catalyst described in this invention to obtain C5. + Hydrocarbons.

[0010] Using a mixed gas of H2+CO and / or CO2 as feed, and employing the catalyst provided by this invention, at 200℃-450℃ and 0.1-10 MPa pressure, the volumetric space velocity is 1000-35000 h⁻¹. -1 Under operating conditions, C5 can be obtained. + Hydrocarbons, C5 + Hydrocarbon selectivity is greater than 80%, and C9-C16 component selectivity in oil products is greater than 60%.

[0011] The present invention unexpectedly discovered that, in the process of preparing hydrocarbon fuels using mixed gases, the combined use of a metal catalyst and two or more molecular sieve catalysts can significantly improve the C5 concentration during the process conversion. + Hydrocarbon selectivity and C9-C16 component selectivity. Furthermore, this invention develops a novel metal catalyst, and through extensive experiments, it has been found that, compared to conventional metal catalysts in the art, the metal catalyst developed in this invention, comprising four metal oxides—Fe2O3, MnO2, Al2O3, and K2O—significantly improves C5 selectivity. + It improves hydrocarbon selectivity and C9-C16 component selectivity, while also significantly reducing methane selectivity during the process conversion, thereby reducing unnecessary byproducts and significantly improving the yield of this process route.

[0012] In addition, compared with the prior art, the present invention can achieve at least the following beneficial effects: (1) The catalyst combination of the present invention does not require water-gas shift hydrogenation and decarbonization treatment of the raw material mixture. It can directly utilize the mixture with high CO2 content, or directly feed CO2+H2. The methane selectivity is low and the raw material adaptability is strong. (2) Using the method of the present invention, the hydrocarbon products synthesized by the conversion of the mixture have C5 + Hydrocarbon selectivity is greater than 80%, and C9-C16 component selectivity in oil products is greater than 60%. Attached Figure Description

[0013] Figure 1 : Showing C5 in the embodiments and comparative examples of this application + Comparison of hydrocarbon selectivity with C9-C16 selectivity in liquids. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] In a first aspect, the present invention provides a catalyst comprising: a metal catalyst comprising at least four metal oxides; a first molecular sieve catalyst; a second molecular sieve catalyst; and optionally, a third molecular sieve catalyst.

[0016] In some embodiments, the metal catalyst comprises at least four metal oxides selected from the following metals: Fe, Co, Mn, K, Na, Zn, Al, Zr, Mg, Ca, La, and Ce.

[0017] In some embodiments, the metal catalyst comprises Fe2O3, MnO2, Al2O3, and K2O.

[0018] In some embodiments, the metal catalyst comprises, by mass, 10%-65% Fe2O3, 0-20% MnO2, 8%-35% Al2O3 and 5%-15% K2O.

[0019] In some embodiments, the metal catalyst comprises, by weight, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 41%, 42%, 43%, 44%, 45%, 50%, 51%, 52%, 53%, 54%, 55%, 60%, and 65% Fe2O3.

[0020] In some embodiments, the metal catalyst comprises, by mass, 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% MnO2.

[0021] In some embodiments, the metal catalyst comprises, by weight, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, and 35% Al2O3.

[0022] In some embodiments, the metal catalyst comprises, by mass, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% K₂O.

[0023] In some embodiments, the first molecular sieve catalyst comprises a first molecular sieve, P2O5, a modified oxide, and one selected from alumina, zirconium oxide, and silicon oxide; wherein the first molecular sieve is ZSM-5, SAPO-34, SAPO-18, ZSM-23, Beta, MCM-22, MCM-41, USY, or a combination thereof; wherein the modified oxide is a metal oxide of the IB, IIB, or VIIIB clusters and a lanthanide rare earth element oxide MV.

[0024] In some embodiments, the first molecular sieve catalyst comprises, by weight, 15%-70% of a first molecular sieve, 5%-15% of P2O5, 0%-3% of modified oxide, and 25%-65% of alumina, zirconium oxide, or silicon oxide.

[0025] In some embodiments, the first molecular sieve catalyst comprises, by weight, 15%-70% of a first molecular sieve, 5%-15% of P2O5, 0%-3% of modified oxide, and 25%-65% of alumina.

[0026] In some embodiments, the modified oxide is modified iron oxide.

[0027] In some embodiments, the second molecular sieve catalyst comprises: a second molecular sieve, P2O5, and one or more selected from alumina, zirconium oxide, and silicon oxide; wherein the second molecular sieve is ZSM-5, Beta, MCM-22, MCM-41, USY, mordenite, or a combination thereof.

[0028] In some embodiments, the second molecular sieve catalyst comprises, by weight, 15%-75% of a second molecular sieve, 0-15% of P2O5, and 25%-85% of one or more selected from alumina, zirconium oxide, and silicon oxide.

[0029] In some embodiments, the second molecular sieve catalyst comprises, by weight, 15%-75% of a second molecular sieve, 0-15% of P2O5, and 25%-85% of alumina and silica.

[0030] In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.2-1:5; preferably 1:0.8-1:25, more preferably 1:1.5 to 1:3; and / or the ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:0.1-1:10; preferably 1:0.5-1:1.5; more preferably 1:1-1:1.75.

[0031] In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.2-1:5; preferably 1:0.8-1:25, more preferably 1:1.5 to 1:3; and the ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:0.1-1:10; preferably 1:0.5-1:1.5; more preferably 1:1-1:1.75.

[0032] In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.2-1:5. In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.8-1:25. In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:1.5 to 1:3. In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:2, 1:21, or 1:2. 2, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:3, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:4, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, 1:5.

[0033] In some embodiments, the ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:0.1 to 1:10. In some embodiments, the ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:0.5 to 1:1.5. In some embodiments, the ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:1 to 1:1.75. In some embodiments, the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.1, 1:0.5, 1:0.75, 1:1, 1:1.5, 1:1.75, 1:2, 1:2.5, 1:2.75, 1:3, 1:3.5, 1:3.75, 1:4, 1:4.5, 1:4.75, 1:5, 1:5.5, 1:5.75, 1:6, 1:6.5, 1:6.75, 1:7, 1:7.5, 1:7.75, 1:8, 1:8.5, 1:8.75, 1:9, 1:9.5, 1:9.75, or 1:10.

[0034] In some embodiments, the third molecular sieve catalyst comprises: a third molecular sieve, P2O5, and one or more selected from alumina, zirconium oxide, and silicon oxide; wherein the third molecular sieve is ZSM-5, Beta, MCM-22, MCM-41, USY, mordenite, or a combination thereof.

[0035] In some embodiments, the third molecular sieve catalyst comprises, by weight, 15%-75% of a third molecular sieve, 0-15% of P2O5, and 25%-85% of alumina.

[0036] In a second aspect, the present invention provides a method for preparing the catalyst described herein, comprising the preparation of a metal catalyst, a first molecular sieve catalyst, and a second molecular catalyst.

[0037] In some embodiments, the preparation of the metal catalyst includes: S1. Partially acidify the aluminum source at room temperature, preferably for 0.5-12 hours, with a pH value of 0.1-3.0; S2. Add metal salt and dissolve to form slurry A; The slurry A obtained from S3 and neutralization precipitation S2 has a pH value of 7.0-10.5. After filtration, filter cake B is obtained. The filter cake B obtained in S4 and S3 is mixed with at least one salt or alkali selected from K, Na, Mg, and Ca, spray-dried, and calcined to obtain the metal catalyst.

[0038] In some embodiments, the method for preparing the first molecular sieve catalyst includes: S1. Dissolve the metal salt of the modified oxide and add it to the molecular sieve to make slurry A; S2. Add silica sol, aluminum glue, zirconium glue, or a mixture thereof to the slurry A obtained in S1, and stir and disperse thoroughly to obtain slurry B; S3. Spray dry the slurry B obtained in S2 and calcine it to obtain the first molecular sieve catalyst.

[0039] In some embodiments, the method for preparing the second molecular sieve catalyst includes: S1. Dissolve phosphoric acid or ammonium phosphate, add to molecular sieve and stir to make slurry C; S2. Add silica sol, alumina glue, zirconium glue, or a mixture thereof to the slurry C obtained in S1, and stir thoroughly to disperse and obtain slurry D. S3. Spray dry the slurry D prepared in S2 and calcine it to obtain the second molecular sieve catalyst.

[0040] In some embodiments, the preparation of the metal catalyst includes the following steps: S1. Take a measured amount of boehmite and partially acidify it with nitric acid (treat at room temperature -95℃ for 0.5-12h), controlling the pH value at 0.1-3.0; then add a measured amount of metal salt and dissolve to prepare slurry A; S2. Slurry A is neutralized and precipitated with ammonia water with a concentration of 8-20%, and the pH value is controlled to 7.0-10.5. Then it is filtered to obtain filter cake B. S3. Filter cake B is slurried with deionized water, and at least one of the measured salts or bases of K, Na, Mg, and Ca is added. After being mixed evenly, it is spray-dried and calcined at 300℃-600℃ for 0.5-12h to obtain a metal oxidation catalyst.

[0041] In some embodiments, the preparation of the first molecular sieve catalyst includes the following steps: S1. Take a measured amount of the metal salt of the modified oxide, dissolve it in deionized water, and then add a measured amount of molecular sieve and stir to make a slurry. S2. Take a measured amount of silica sol, alumina glue, zirconium glue, or their mixture and add it to the slurry prepared in S1, and stir and disperse it thoroughly. S3. Spray dry the slurry prepared in S2 and calcine it at 300℃-600℃ for 0.5-12h to obtain the first molecular sieve catalyst.

[0042] In some embodiments, the preparation of the second molecular sieve catalyst includes the following steps: S1. Take a measured amount of phosphoric acid or ammonium phosphate, dissolve it in deionized water, and then add a measured amount of molecular sieve and stir to make a slurry. S2. Take a measured amount of silica sol, alumina glue, zirconium glue, or their mixture and add it to the slurry prepared in S1, and stir and disperse it thoroughly. S3. Spray dry the slurry prepared in S2 and calcine it at 300℃-600℃ for 0.5-12h to obtain the first molecular sieve catalyst.

[0043] In a third aspect, the present invention provides a method for preparing C5 using a mixed gas. + A method for processing hydrocarbons, comprising treating a gas mixture using the catalyst described in this invention to obtain C5. + Hydrocarbons.

[0044] In some embodiments, the molar ratio of H2 to (CO + CO2) in the mixed gas is 1:2-6:1, preferably 1.8-3.0:1. In some embodiments, the molar ratio of H2 to (CO + CO2) in the mixed gas is 1.8-3.0:1. In some embodiments, the ratio of CO to CO2 is arbitrary.

[0045] In some embodiments, the reaction conditions for the gas mixture are: 200°C-450°C, 0.1-10 MPa pressure, and a volumetric hourly space velocity (VHSV) of 1000-35000 h⁻¹. -1 The mixed gas feed reacts under the action of the catalyst to obtain C5. + C5 hydrocarbons + Hydrocarbon selectivity is greater than 80%.

[0046] definition As used herein, the term "metal catalyst" refers to a metal-based catalyst that comprises various metal oxides, with the metal element or its oxide as the active component, which can accelerate the process of a chemical reaction.

[0047] As used herein, the term "mixture" refers to a mixture of gases including carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), nitrogen (N2), and methane (CH4), which is used to catalytically synthesize C5 in a reactor. + The raw material gas for hydrocarbon products.

[0048] As used in this article, “by mass” for metal catalysts refers to the percentage by mass of the metal oxides as calculated from the weight of the metal oxides contained in the metal catalyst.

[0049] As used in this article, the term "C5" + "Hydrocarbons" refers to all hydrocarbon compounds whose molecules contain 5 or more carbon atoms.

[0050] As used in this article, the term "C5" +"Hydrocarbon selectivity" refers to the selection of hydrocarbons with ≥5 carbon atoms (C5+) among all hydrocarbon products generated in a reaction. + The mass or mole fraction of carbon is usually expressed as a percentage (%) based on the carbon base.

[0051] As used herein, the term "C9-C16 selectivity" refers to the fact that all hydrocarbon products generated in the reaction have between 9 and 16 carbon atoms (C9-C16). 16 The mass or mole fraction of hydrocarbons in a substance is usually expressed as a percentage (%) based on the carbon base.

[0052] As used herein, the term "aluminum source" refers to any raw material that provides available aluminum (Al) in the reaction system, encompassing metals, inorganic salts, oxides, and minerals. Examples include, but are not limited to, aluminum powder, boehmite, aluminum foil, aluminum granules / shavings, aluminum sulfate, aluminum nitrate, aluminum phosphate, aluminum oxide, and aluminum hydroxide.

[0053] Example The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. Equivalent substitutions or improvements made by those skilled in the art without departing from the concept of the present invention should fall within the scope of protection of the present invention.

[0054] The raw material metal salts or oxides are all industrial products; The pseudoboehmite comes from Shandong Aluminum Corporation of China. Tetrapropylammonium hydroxide and other template agents are sourced from Kent Catalytic Materials Co., Ltd. The molecular sieve raw powder comes from Huainan Liuyuanhuan New Material Co., Ltd.; The catalysts used in the following examples were prepared according to the following preparation example: Catalyst Preparation Example 1 (Metal Catalyst A1) 210g of 65% nitric acid was added to 1120g of deionized water, followed by 513.8g of boehmite. The mixture was stirred at 80℃~90℃ for 6 hours to obtain a slurry. Separately, 3280g of ferric nitrate nonahydrate and 206.9g of manganese nitrate were mixed with the above slurry, and the pH was adjusted to 9.2 with ammonia water for co-precipitation. The precipitate was aged at 50℃~90℃ for 8 hours, filtered, and washed to obtain a filter cake. This filter cake was then mixed with 189.2g of potassium hydroxide and 500g of deionized water, stirred thoroughly, spray-dried, and then calcined at 500℃ for 2 hours to obtain metal oxide catalyst particles, labeled as metal oxide catalyst A1.

[0055] XRF analysis showed that Fe2O3 accounted for 52.16%, MnO2 accounted for 6.59%, Al2O3 accounted for 28.89%, and K2O accounted for 12.37%.

[0056] Catalyst Preparation Example 2 (Metal Catalyst A2) Dissolve 95.2g of zinc oxide in 270g of 65% nitric acid, then add 650g of deionized water and 320g of boehmite. Stir at 80℃-90℃ for 4h to obtain a slurry. Separately, mix 2340g of ferric nitrate nonahydrate, 147.6g of manganese nitrate, and 195.7g of cobalt nitrate hexahydrate with the above slurry, adjust the pH to 9.0 with ammonia water, and co-precipitate. After aging the precipitate at 550℃-90℃ for 8h, filter, and wash, obtain a filter cake. Mix the filter cake with 65g of calcium oxide, 135.9g of potassium hydroxide, and 300g of deionized water, stir thoroughly, spray dry, and then calcine at 500℃ for 2h to obtain metal oxide catalyst particles, labeled as metal oxide catalyst A2.

[0057] XRF analysis showed that Fe2O3 accounted for 42.62%, MnO2 accounted for 5.38%, Al2O3 accounted for 20.61%, K2O accounted for 10.18%, and others accounted for 21.21%.

[0058] Catalyst Preparation Example 3 (First Molecular Sieve Catalyst Z1) Take 1000g of deionized water, add 12.2g of ferric nitrate decanoate, dissolve, and then add 800g of nano ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 80 to prepare a modified molecular sieve slurry; take 1550g of boehmite and add it to 2100g of deionized water, add 181g of 75% phosphoric acid and 618g of 65% nitric acid, mix evenly, and heat to 80℃ for 6h to obtain phosphorus-modified aluminum sol; add the aluminum sol to the molecular sieve slurry, stir and mix evenly, spray dry the slurry, and calcine at 500℃ for 3h to obtain the first molecular sieve catalyst, labeled as the first molecular sieve catalyst Z1.

[0059] In the first molecular sieve catalyst Z1, the molecular sieve content is 40.26%, the alumina content is 54.61%, the P2O5 content is 5.01%, and the modified iron oxide accounts for 0.12%.

[0060] Catalyst Preparation Example 4 (Second Molecular Sieve Catalyst Z2) Take 1500g of deionized water, add 54.5g of 75% phosphoric acid, dissolve it, and then add 1000g of Beta molecular sieve with a silicon-to-aluminum ratio of 100 to prepare a modified molecular sieve slurry. Add 4230g of 30% silica sol and 800g of pseudoboehmite to the molecular sieve slurry. After the components are stirred and mixed evenly, the slurry is spray-dried and calcined at 550℃ for 2h to obtain the first molecular sieve catalyst, which is labeled as the second molecular sieve catalyst Z2.

[0061] The second molecular sieve catalyst Z2 contains 34.98% molecular sieve, 63.97% alumina + silica, and 1.05% P2O5.

[0062] Catalyst Preparation Example 5 (Second Molecular Sieve Catalyst Z3) Take 1000g of deionized water, add 68g of 75% phosphoric acid, dissolve, and then add 1000g of Beta molecular sieve with a silicon-to-aluminum ratio of 30 to prepare a modified molecular sieve slurry; take 1350g of boehmite and add it to 2000g of deionized water, add 189g of 75% phosphoric acid and 588g of 65% nitric acid, mix evenly, and then heat to 80℃ for 6h to obtain phosphorus-modified aluminum sol; add the aluminum sol to the molecular sieve slurry, stir and mix evenly, spray dry the slurry, and calcine at 550℃ for 4h to obtain the first molecular sieve catalyst, labeled as the second molecular sieve catalyst Z3.

[0063] The second molecular sieve catalyst Z3 contains 47.93% molecular sieve, 45.29% alumina, and 6.77% P2O5.

[0064] Catalyst preparation Comparative Example 1 (Fe-Mn-K based metal catalyst B1) Take 609g of deionized water, add 708.2g of ferric nitrate nonahydrate, 46.5g of manganese nitrate, and 1.40g of basic copper carbonate dissolved in 3g of nitric acid. After mixing evenly, add 2.0g of caustic soda flakes and 20.0g of potassium hydroxide. After mixing, heat to -50℃, and then add ammonium carbonate while stirring rapidly. Control the pH value to 7.0-7.5, and then continue to heat at 80-90℃ for 6 hours. Finally, add 60g of 30% silica sol and mix thoroughly. Spray dry the slurry at 200℃ and then calcine at 500℃ for 2 hours to obtain metal catalyst particles, labeled as metal catalyst B1.

[0065] XRF analysis showed that the composition was: Fe2O3 71.73%, MnO2 9.43%, Na2O 0.79%, K2O 8.33%, CuO 0.52%, and SiO2 9.21%.

[0066] Catalyst Comparative Example 2 (Metal Catalyst B2) Metal catalyst A3 was prepared using the method described above. Analysis showed that the contents of each metal oxide in the catalyst were: Fe2O3 65.42%, MnO2 11.23%, K2O 9.45%, CuO 0.63%, and SiO2 13.27%.

[0067] Catalyst Comparative Example 2 (Metal Catalyst B3) Metal catalyst A3 was prepared using the method described above. Analysis showed that the contents of each metal oxide in the catalyst were: Fe2O3 55.67%, MnO2 21.34%, K2O 8.79%, Na2O 1.37%, and SiO2 12.83%.

[0068] Catalyst Comparative Example 2 (Metal Catalyst B4) Metal catalyst A3 was prepared using the method described above. Analysis showed that the contents of each metal oxide in the catalyst were: Fe2O3 72.80%, MnO2 7.38%, K2O 8.12%, Na2O 0.68%, CuO 0.68%, and SiO2 10.34%.

[0069] Catalyst Comparative Example 2 (Metal Catalyst B5) Metal catalyst A3 was prepared using the method described above. Analysis showed that the contents of each metal oxide in the catalyst were: Fe2O3 67.32%, MnO2 11.83%, K2O 9.88%, Na2O 0.68%, CuO 2.30%, and SiO2 8.67%.

[0070] In the following examples, reactions were conducted and results were compared under different reaction conditions with different gas mixtures and different catalyst combinations.

[0071] Example 1 Using a mixed gas (volume composition of 66.2% H2 + 23% CO + 6.8% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 30% metal catalyst A1, 20% first molecular sieve catalyst Z1, and 50% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 300℃, reaction pressure 5 MPa, and volumetric hourly space velocity 3000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0072] Example 2 Using a mixed gas (volume composition of 69.7% H2 + 9.3% CO + 17.0% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 40% metal catalyst A1, 20% first molecular sieve catalyst Z1, 20% second molecular sieve catalyst Z2, and 20% third molecular sieve catalyst Z3, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 350℃, reaction pressure 2.5 MPa, and volumetric hourly space velocity 10000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0073] Example 3 Using a mixed gas (volume composition of 70.7% H2 + 5.0% CO + 20.3% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 40% metal catalyst A2, 20% first molecular sieve catalyst Z1, and 40% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 350℃, reaction pressure 3.0 MPa, and volumetric hourly space velocity 15000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0074] Example 4 Using a mixed gas (volume composition of 67.2% H2 + 19.0% CO + 9.8% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 30% metal catalyst A2, 20% first molecular sieve catalyst Z1, 30% second molecular sieve catalyst Z2, and 20% third molecular sieve catalyst Z3, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 3.0 MPa, and volumetric hourly space velocity 8000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0075] Example 5 Using a mixed gas (volume composition of 72.0% H2 + 0% CO + 24.0% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 25% metal catalyst A2, 30% first molecular sieve catalyst Z1, and 45% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volumetric hourly space velocity 6000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0076] Example 6 Using a mixed gas (volume composition of 69.0% H2 + 12.0% CO + 15.0% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 50% metal catalyst A1, 10% first molecular sieve catalyst Z1, 20% second molecular sieve catalyst Z2, and 20% third molecular sieve catalyst Z3, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 330℃, reaction pressure 2.0 MPa, and volumetric hourly space velocity 6000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0077] Example 7 Using a mixed gas (volume composition of 64.0% H2 + 32.0% CO + 0% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 25% metal catalyst A1, 20% first molecular sieve catalyst Z1, 35% second molecular sieve catalyst Z2, and 20% third molecular sieve catalyst Z3, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 5.0 MPa, and volumetric hourly space velocity 8000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0078] Example 8 Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 50% metal catalyst A2, 20% first molecular sieve catalyst Z1, and 30% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volume hourly space velocity 12000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 1.

[0079] Comparative Example 1 The experiment was conducted using a mixed gas and two combined catalysts for comparison.

[0080] Using a mixed gas (volume composition of 66.2% H2 + 23.0% CO + 6.8% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 40% metal catalyst A1 and 60% first molecular sieve catalyst Z1, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 3.0 MPa, and volumetric hourly space velocity 8000 h⁻¹. -1 The following reaction is shown in Table 1. The catalyst combination, reaction conditions, and reaction results are summarized in Table 1. Metal oxide catalyst A1, combined with only one type of molecular sieve catalyst, has its product distribution in C5. + The selectivity of both C9 and C16 decreased.

[0081] Comparative Example 2 The experiment compared the mixed gas and two combined catalysts, including the comparison of the metal catalyst.

[0082] Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 50% metal catalyst B1 and 50% first molecular sieve catalyst Z1, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 3.0 MPa, and volumetric hourly space velocity 8000 h⁻¹. -1 The reaction proceeded as follows. The catalyst combination, reaction conditions, and reaction results are summarized in Table 1. Using a comparative metal catalyst B1 (different from the metal catalyst described in this invention), combined with a molecular sieve catalyst, the product distribution showed a high methane content of up to 11.5%, and C5... +The selectivity of C9 to C16 is relatively low.

[0083] Comparative Example 3 The experiment compared the mixed gas and two combined catalysts, including the comparison of metal catalysts.

[0084] Using a mixed gas (volume composition of 72.0% H2 + 0% CO + 24.0% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 40% metal catalyst B1 and 60% first molecular sieve catalyst Z1, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 3.0 MPa, and volumetric hourly space velocity 12000 h⁻¹. -1 The reaction proceeded as follows. The catalyst combination, reaction conditions, and reaction results are summarized in Table 1. Using a comparative metal catalyst B1 (different from the metal catalyst described in this invention), combined with one molecular sieve catalyst, the product distribution showed a high methane content of up to 23.3%, and C5... + The selectivity of C9 to C16 is relatively low.

[0085] Comparative Example 4 The experiment compared the mixed gas and two combined catalysts, including the metal oxide catalyst.

[0086] Using a mixed gas (volume composition of 66.2% H2 + 23.0% CO + 6.8% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 40% metal oxide catalyst B1, 20% first molecular sieve catalyst Z1, and 40% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The reaction was then carried out by introducing the mixed gas. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 320℃, reaction pressure 3.0 MPa, and volume hourly space velocity 8000 h⁻¹. -1 The reaction proceeded as follows. The catalyst combination, reaction conditions, and reaction results are summarized in Table 1. Using a comparative metal catalyst B1 (different from the metal catalyst described in this invention), combined with two molecular sieve catalysts, the product distribution showed a high methane content of 8.7%, and C5... + The selectivity of C9 to C16 is relatively low.

[0087] Comparative Example 5 Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture of 50% metal catalyst B2, 20% first molecular sieve catalyst Z1, and 30% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volume hourly space velocity 12000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 2.

[0088] Comparative Example 6 Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture consisting of 50% metal catalyst B3, 20% first molecular sieve catalyst Z1, and 30% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volumetric hourly space velocity 12000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 2.

[0089] Comparative Example 7 Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture of 50% metal catalyst B4, 20% first molecular sieve catalyst Z1, and 30% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volume hourly space velocity 12000 h⁻¹. -1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 2.

[0090] Comparative Example 8 Using a mixed gas (volume composition of 68.1% H2 + 15.6% CO + 12.3% CO2 + 4% N2) as raw material, and a catalyst mixture of 50% metal catalyst B5, 20% first molecular sieve catalyst Z1, and 30% second molecular sieve catalyst Z2, the mixture was loaded into a reactor and reduced with H2 at a maximum temperature of 400℃. The mixed gas was then introduced to carry out the reaction. Online chromatographic analysis was performed, and the collected liquid oil was also analyzed for composition. The reaction conditions were: reaction temperature 310℃, reaction pressure 4.0 MPa, and volume hourly space velocity 12000 h⁻¹.-1 The reaction proceeded as follows. A summary of the catalyst combination, reaction conditions, and reaction results is shown in Table 2.

[0091] The process conditions and reaction results of the above examples are summarized in Tables 1 and 2.

[0092] In Tables 1 and 2: 1. The calculation method for the single-pass conversion rate of (CO+CO2) is the volume of (CO+CO2) in the exhaust gas / the volume of (CO+CO2) in the feed. 100%; 2. The calculation method for the selectivity of C9-C16 hydrocarbons in liquid oil products is based on the proportion of C9-C16 hydrocarbons in the total hydrocarbons in simulated distillation analysis; 3. The calculation method for the space-time yield of liquid oil products is based on the chromatographic analysis of C5 at the reactor outlet. + 4. The methane selectivity is calculated by using chromatographic analysis of the proportion of methane to total hydrocarbons at the reactor outlet.

[0093] Table 1: Summary of experimental conditions and results for Examples 1-8 and Comparative Examples 1-4

[0094] Table 2: Summary of experimental conditions and results for Example 1 and Comparative Examples 5-8

[0095] As shown in Tables 1 and 2, the catalyst combination of the present invention exhibits good adaptability to mixed gases containing CO, CO2, and H2 with different hydrogen-to-carbon ratios; without water-gas shift and decarbonization treatment, the single-pass C5... + Hydrocarbon selectivity reached over 80%, peaking at 92.51%, with C9-C16 hydrocarbon components accounting for over 70% of the liquid oil, significantly exceeding the theoretical upper limit of ASF distribution (approximately 41%). Methane selectivity was below 10%, and the space-time yield of the liquid oil was 0.35 kg / kg catalyst.h -1 The highest concentration reached 0.623 kg / kg catalyst.h -1 ; Compared to the comparative example, under the non-target catalyst combination, the single-pass C5 of the comparative example was... + The selectivity for hydrocarbons and the selectivity for C9-C16 hydrocarbon components in liquid oil products are significantly reduced.

[0096] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst comprising: Metal catalyst, wherein the metal catalyst comprises at least four metal oxides; First molecular sieve catalyst; Second molecular sieve catalyst; and Optionally, a third molecular sieve catalyst.

2. The catalyst according to claim 1, wherein the metal catalyst comprises at least four metal oxides selected from the group consisting of Fe, Co, Mn, K, Na, Zn, Al, Zr, Mg, Ca, La and Ce.

3. The catalyst according to claim 1 or 2, wherein the metal catalyst comprises Fe2O3, MnO2, Al2O3 and K2O.

4. The catalyst according to any one of claims 1-3, wherein the metal catalyst comprises, by mass, 10%-65% Fe2O3, 0-20% MnO2, 8%-35% Al2O3 and 5%-15% K2O.

5. The catalyst according to any one of claims 1-4, wherein the first molecular sieve catalyst comprises a first molecular sieve, P2O5, a modified oxide, and one selected from alumina, zirconium oxide, and silicon oxide; The first molecular sieve is ZSM-5, SAPO-34, SAPO-18, ZSM-23, Beta, MCM-22, MCM-41, USY or a combination thereof; The modified oxides are metal oxides of the IB, IIB, and VIIIB groups, as well as lanthanide rare earth element oxides MV.

6. The catalyst according to any one of claims 1-5, wherein the first molecular sieve catalyst comprises, by weight, 15%-70% of a first molecular sieve, 5%-15% of P2O5, 0%-3% of modified oxide, and 25%-65% of alumina, zirconium oxide, or silicon oxide; Preferably, the first molecular sieve catalyst comprises, by weight, 15%-70% of a first molecular sieve, 5%-15% of P2O5, 0%-3% of modified oxide, and 25%-65% of alumina.

7. The catalyst according to any one of claims 1-6, wherein the modified oxide is modified iron oxide.

8. The catalyst according to any one of claims 1-7, wherein the second molecular sieve catalyst comprises: a second molecular sieve, P2O5, and one or more selected from alumina, zirconium oxide, and silicon oxide; wherein the second molecular sieve is ZSM-5, Beta, MCM-22, MCM-41, USY, mordenite, or a combination thereof.

9. The catalyst according to any one of claims 1-8, wherein the second molecular sieve catalyst comprises, by weight, 15%-75% of a second molecular sieve, 0-15% of P2O5, and 25%-85% of one or more selected from alumina, zirconium oxide, and silica; Preferably, the second molecular sieve catalyst comprises, by weight, 15%-75% of a second molecular sieve, 0-15% of P2O5, and 25%-85% of alumina and silica.

10. The catalyst according to any one of claims 1-9, wherein the ratio of the metal catalyst to the molecular sieve catalyst is 1:0.2-1:5; preferably 1:0.8-1:25, more preferably 1:1.5 to 1:3; and / or The ratio of the first molecular sieve catalyst to the second molecular sieve catalyst is 1:0.1-1:10; preferably 1:0.5-1:1.5; more preferably 1:1-1:1.

75.

11. The catalyst according to any one of claims 1-10, wherein the third molecular sieve catalyst comprises: a third molecular sieve, P2O5, and one or more selected from alumina, zirconium oxide, and silicon oxide; wherein the third molecular sieve is ZSM-5, Beta, MCM-22, MCM-41, USY, mordenite, or a combination thereof.

12. The catalyst according to any one of claims 1-11, wherein the third molecular sieve catalyst comprises, by weight, 15%-75% of a third molecular sieve, 0-15% of P2O5, and 25%-85% of alumina.

13. A method for preparing a metal catalyst according to any one of claims 1-12, comprising: S1. Partially acidify the aluminum source at room temperature, preferably for 0.5-12 hours, with a pH value of 0.1-3.0; S2. Add metal salt and dissolve to form slurry A; The slurry A obtained from S3 and neutralization precipitation S2 has a pH value of 7.0-10.

5. After filtration, filter cake B is obtained. The filter cake B obtained in S4 and S3 is mixed with at least one salt or alkali selected from K, Na, Mg, and Ca, spray-dried, and calcined to obtain the metal catalyst.

14. A method for preparing a first molecular sieve catalyst according to any one of claims 1-12, comprising: S1. Dissolve the metal salt of the modified oxide and add it to the molecular sieve to make slurry A; S2. Add silica sol, aluminum glue, zirconium glue, or a mixture thereof to the slurry A obtained in S1, and stir and disperse thoroughly to obtain slurry B; S3. Spray dry the slurry B obtained in S2 and calcine it to obtain the first molecular sieve catalyst.

15. A method for preparing a second molecular sieve catalyst according to any one of claims 1-12, comprising: S1. Dissolve phosphoric acid or ammonium phosphate, add to molecular sieve and stir to make slurry C; S2. Add silica sol, alumina glue, zirconium glue, or a mixture thereof to the slurry C obtained in S1, and stir thoroughly to disperse and obtain slurry D. S3. Spray dry the slurry D prepared in S2 and calcine it to obtain the second molecular sieve catalyst.

16. A method for preparing a catalyst according to any one of claims 1-12, comprising the method according to claims 13-15.

17. A method for preparing C5 using a mixed gas + A method for hydrocarbons, comprising treating a gas mixture with a catalyst according to any one of claims 1-12 to obtain C5. + Hydrocarbons.

18. The method according to claim 17, wherein the molar ratio of H2 to (CO+CO2) in the mixed gas is 1:2-6:1, preferably 1.8-3.0:

1.

19. The method according to claim 17 or 18, wherein the reaction conditions of the mixed gas are: 200°C-450°C, 0.1-10 MPa pressure, and volumetric hourly space velocity (VHSV) of 1000-35000 h⁻¹. -1 The mixed gas feed reacts under the action of the catalyst to obtain C5. + C5 hydrocarbons + Hydrocarbon selectivity is greater than 80%.

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