Cobalt-based heterogeneous catalyst and preparation and application thereof
By developing a solid heterophase catalyst supported by an organic ligand polymer, the problem of difficult separation between the catalyst and the reaction liquid in the existing hydroformylation reaction system is solved, and efficient catalytic reaction performance and good stability are achieved, and good recycling and recycling are achieved.
Patent Information
- Application Number
- CN202311709480.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-13
- Publication Date
- 2025-06-13
AI Technical Summary
The existing hydroformylation reaction systems are homogeneous systems, making it difficult to separate the catalyst from the reaction liquid, and the reaction conditions are harsh and the catalytic activity is low.
A solid heterogeneous catalyst supported by an organic ligand polymer is developed, specifically by solvent thermal polymerization to generate polymers with large specific surface area and multi-stage pore structures, and the metal components are highly dispersed on the organic ligand polymer support through coordination bonds.
It realizes easy separation between the catalyst and the reaction material, improves the catalytic reaction performance and stability, has excellent hydroformylation reaction performance, and has good recycling and recycling in industrial applications.
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Abstract
Description
Technical Field
[0001] The present invention relates to a solid heterogeneous catalyst for hydroformylation reaction, a preparation method thereof and an application thereof, and belongs to the technical field of heterogeneous catalysis. Background Art
[0002] Homogeneous catalytic systems have high catalytic activity and selectivity for target products under relatively mild reaction conditions, but it is difficult to separate the catalyst from the reaction materials. The biggest advantage of heterogeneous catalysis compared with homogeneous catalysis is that the catalyst is easily separated from the reaction materials. The main problems are harsh reaction conditions and relatively low reaction activity, etc. Therefore, the development of new immobilized heterogeneous catalysts that combine the advantages of homogeneous catalysis and heterogeneous catalysis is a hot topic in scientific research. In recent years, the design and synthesis of porous organic polymer materials have gradually become one of the new hot topics in the field of porous material research. Compared with traditional inorganic microporous materials and metal-organic framework materials (MOFs), the framework of organic microporous polymers is composed of pure organic molecules, which are connected to each other by covalent bonds, and have open pores and excellent pore properties. More importantly, due to the diversity of organic chemical synthesis methods, it provides rich synthesis routes and construction methods for the construction of organic molecular networks. Functionalized organic molecules can be purposefully introduced to endow the materials with corresponding properties, and the pore properties of the materials can be regulated by adjusting the structure of organic molecules. In addition, metal-functionalized porous organic polymer materials can introduce catalytically active metal active units into porous organic polymers at fixed points, and achieve high dispersion in the organic copolymer carrier in the form of single atoms. This not only helps to stabilize the metal active sites, but also greatly improves the utilization efficiency of metals.
[0003] The reaction of catalytically preparing aldehyde compounds from olefins and syngas is called hydroformylation. The products of hydroformylation reaction such as aldehydes and derivative products such as alcohols are important chemical industrial products and have very wide applications in the industrial field. At present, the global production of aldehyde and alcohol products through the hydroformylation reaction process has reached 25 million tons / year, and its downstream products are rich in variety, covering fields such as detergents, plasticizers, spices, fragrances, and pharmaceuticals. However, the existing hydroformylation reaction systems are all homogeneous systems, and it is difficult to separate the catalyst from the reaction solution.
[0004] In summary, for the hydroformylation reaction applicable to actual industrial applications, green, highly efficient and recyclable heterogeneous catalysts are the main research direction in this field. Summary of the Invention
[0005] In order to solve the above problems, the purpose of the present invention is to provide a solid heterogeneous catalyst in which a metal active component is supported by an organic ligand polymer, a preparation method thereof and an application thereof.
[0006] To this end, the present invention provides a solid heterogeneous catalyst for use in hydroformylation reactions, wherein the metal component is metal Co, the organic ligand polymer is a polymer having a large specific surface area and a hierarchical pore structure formed by solvothermal polymerization of a vinyl-containing heteroatom monomer and a vinyl-containing carbon skeleton monomer, and the metal component forms a coordination bond with the heteroatoms in the organic ligand polymer backbone and is highly dispersed and stably present on the organic ligand polymer support.
[0007] In a preferred embodiment, the metal component accounts for 0.5-10.0% of the total weight of the solid heterogeneous catalyst.
[0008] In a preferred embodiment, the vinyl-containing heteroatom ligand is one or more selected from the following:
[0009]
[0010] In a preferred embodiment, the vinyl-containing carbon skeleton monomer is one or more selected from the following:
[0011]
[0012] In a preferred embodiment, the specific surface area of the organic ligand polymer is 500-3000 m 2 / g, the pore volume is 0.5-5.0 cm 3 / g, and the pore size distribution is in the range of 0.2-100.0 nm.
[0013] In a preferred embodiment, the method for preparing the solid heterogeneous catalyst includes the following preparation steps: a) adding a radical initiator and then a vinyl-containing carbon skeleton monomer to a solvent containing a vinyl-containing heteroatom ligand monomer under an inert gas protection atmosphere at 273-473 K, and stirring for 0.5-50 hours; b) allowing the solution of step a) to stand in a hydrothermal autoclave for 1-50 hours under an inert gas protection atmosphere at 273-473 K to carry out a solvothermal polymerization reaction; c) vacuum removing the solvent at a temperature of 273-473 K after step b) to obtain the organic ligand polymer; d) placing the organic ligand polymer in a solvent containing an active metal component, stirring for 1-50 hours under an inert gas protection atmosphere at 273-473 K, and then vacuum removing the solvent at a temperature of 273-473 K to obtain the solid heterogeneous catalyst in which the active metal component is supported on the organic ligand polymer.
[0014] In a preferred embodiment, the solvent used in steps a) and d) of the catalyst preparation method is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; the radical initiator used in step a) is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azodiisooctanenitrile.
[0015] In a preferred embodiment, the molar ratio of the vinyl-containing heteroatom monomer to the radical initiator in the catalyst preparation method is 300:1 to 10:1.
[0016] In a preferred embodiment, the application of the solid heterogeneous catalyst in the hydroformylation reaction refers to carrying out the hydroformylation reaction of an olefin raw material with an H 2 / CO mixed gas in a fixed bed, trickle bed, slurry bed or autoclave reactor, wherein the reaction temperature is 273 - 573K, the reaction pressure is 0.05 - 20.0 MPa, the liquid hourly space velocity is 0.01 - 20.0 h -1 , and the gas hourly space velocity is 100 - 20000 h -1 .
[0017] In a preferred embodiment, the inert gas atmosphere during the synthesis of the organic ligand polymer is one or more of argon, helium and nitrogen.
[0018] The beneficial effects of the present invention include but are not limited to the following aspects:
[0019] Compared with the existing hydroformylation catalysts, the solid heterogeneous catalyst of the present invention has a simple catalyst preparation method; the metal component and the heteroatom in the polymer support are stably present on the support due to coordination; the polymer support has a large specific surface area and a hierarchical pore structure, and the metal component can be highly dispersed on the support, so that the solid heterogeneous catalyst of the present invention has excellent catalytic reaction performance and high stability. In addition, the catalyst of the present invention is a heterogeneous catalyst macroscopically, so it has obvious advantages in aspects such as recovery and recycling and separation from reactants and products, and has broad industrial application prospects.
[0020] Explanation of the attached tables
[0021] Table 1 shows the experimental data results of the examples listed in the present invention. Explanation of the drawings
[0022] Figure 1 is a schematic diagram of the synthesis route of the solid heterogeneous catalyst of the present invention.
[0023] Figure 2 is the N of the solid heterogeneous catalyst of the present invention2 Adsorption - desorption isotherm and pore size distribution curve diagram. Detailed implementation manners
[0024] To better illustrate the preparation method of the catalyst of the present invention and its application in the hydroformylation reaction, some examples of the preparation of catalyst samples and their application in the reaction process are given below. However, the present invention is not limited to the listed examples. Unless otherwise specifically stated, the "percentage" used in this application is based on weight.
[0025] Example 1
[0026] Under the atmosphere of 298K and argon protection, 4.0 g of p - divinylbenzene was dissolved in 50 ml of tetrahydrofuran solvent. 0.1 g of free - radical initiator azobisisobutyronitrile was added to the above - mentioned solution, and then 3.0 g of N - vinylpyrrolidone was added, and the mixture was stirred for 0.5 h. The stirred solution was transferred to a hydrothermal autoclave and polymerized by solvothermal method for 24 h under the atmosphere of 373K and inert gas protection. After the above polymerization, it was cooled to room temperature, and the solvent was removed by vacuum pumping at 333K, and the corresponding porous organic polymer was obtained.
[0027] Under the atmosphere of 298K and inert gas protection, 0.105 g of dicobalt octacarbonyl was dissolved in 50 ml of tetrahydrofuran solvent, and 1.0 g of the above - prepared porous organic polymer was added, and the mixture was stirred for 24 h. Subsequently, the solvent was removed by vacuum pumping at 333K, and a solid heterogeneous catalyst with a metal component supported by an organic ligand polymer was obtained.
[0028] 1 g of the above - prepared solid heterogeneous catalyst was added to a trickle - bed reactor, and a mixture of hydrogen and CO (molar ratio 1:1) was introduced. The gas hourly space velocity was 5000 h -1 , and the liquid 1 - octene raw material was pumped into the reactor by a high - pressure metering pump to start the reaction. The reaction temperature was 140 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of liquid 1 - octene was 0.1 h -1 . The liquid product was collected in a cold - trap collection tank. The liquid product was analyzed by HP - 7890N gas chromatography equipped with an HP - 5 capillary column and an FID detector, and 1,4 - dioxane was used as the internal standard. The reaction tail gas was analyzed online by HP - 7890N gas chromatography equipped with a Porapak - QS column and a TCD detector.
[0029] The schematic diagram of the synthesis route of the solid heterogeneous catalyst of the present invention is shown in Figure 1 , and the N 2 Adsorption - desorption isotherm and pore size distribution curve diagram of the solid heterogeneous catalyst of the present invention are shown in Figure 2 , and the results show that this catalyst has a good specific surface area and a rich hierarchical pore structure. The specific reaction results are shown in Table 1.
[0030] Example 2
[0031] In Example 2, during the metal loading process, except for weighing 0.135 g of cobalt(III) acetylacetonate to replace 0.105 g of dicobalt octacarbonyl, the remaining catalyst preparation process was the same as that in Example 1.
[0032] 1 g of the above-prepared solid heterogeneous catalyst was added to a fixed-bed reactor, and a hydrogen and CO mixed gas (molar ratio of the two 1:1) was introduced, with a gas hourly space velocity of 5000 h -1 , and the gas-liquid mixed 2-isobutene raw material was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature was 140 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of the gas-liquid mixed 2-isobutene was 0.5 h -1 . The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using 1,4-dioxane as the internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.
[0033] Example 3
[0034] In Example 3, during the metal loading process, except for weighing 0.126 g of cobalt acetate to replace 0.205 g of dicobalt octacarbonyl, the remaining catalyst preparation process was the same as that in Example 1.
[0035] 1 g of the above-prepared solid heterogeneous catalyst was added to a trickle-bed reactor, and a hydrogen and CO mixed gas (molar ratio of the two 1:1) was introduced, with a gas hourly space velocity of 5000 h -1 , and the liquid 2-hexene raw material was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature was 150 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of the liquid 2-hexene was 0.1 h -1 . The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using 1,4-dioxane as the internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.
[0036] Example 4
[0037] In Example 4, during the polymer synthesis process, except for weighing 4 g of m-divinylbenzene to replace 4 g of p-divinylbenzene, the remaining catalyst preparation process was the same as that in Example 1.
[0038] 1 g of the above-prepared solid heterogeneous catalyst was added to a trickle-bed reactor, and a hydrogen and CO mixture (molar ratio of the two 1:1) was introduced, with a gas hourly space velocity of 5000 h -1 , and the liquid 1-hexene raw material was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature was 150 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of liquid 1-hexene was 0.1 h -1 . The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using 1,4-dioxane as an internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.
[0039] Example 5
[0040] In Example 5, 1 g of the solid heterogeneous catalyst prepared in Example 1 above was charged into a fixed-bed reactor, and a hydrogen, CO, and propylene mixture (molar ratio of the three 1:1:1) was introduced, with a gas hourly space velocity of 3000 h -1 , the reaction temperature was 130 °C, and the reaction pressure was 3 MPa. The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using 1,4-dioxane as an internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The specific reaction results are shown in Table 1.
[0041] Example 6
[0042] In Example 6, during the polymer synthesis process, except that 4 g of 4,4'-divinyl-1,1'-biphenyl was weighed instead of 4 g of p-divinylbenzene, the remaining catalyst preparation process and reaction conditions were the same as those in Example 1. The specific reaction results are shown in Table 1.
[0043] Example 7
[0044] In Example 7, during the polymer synthesis process, except that 2.5 g of 2-vinylcyclopentanone was weighed instead of 3.0 g of N-vinylpyrrolidone, the remaining catalyst preparation process and reaction conditions were the same as those in Example 1. The specific reaction results are shown in Table 1.
[0045] Example 8
[0046] In Example 8, during the polymer synthesis process, except that dichloromethane solvent was used to replace tetrahydrofuran solvent in an equal volume, the remaining catalyst preparation process and reaction conditions were the same as those in Example 1. The specific reaction results are shown in Table 1.
[0047] Example 9
[0048] In Example 9, except that the radical initiator is replaced with benzoyl peroxide in an equal mass to azobisisobutyronitrile, the remaining catalyst preparation process and reaction conditions are the same as those in Example 1. The specific reaction results are shown in Table 1.
[0049] Example 10
[0050] In Example 10, except that 0.1 g of azobisisobutyronitrile as the radical initiator is replaced with 0.25 g of azobisisobutyronitrile, the remaining catalyst preparation process and reaction conditions are the same as those in Example 1. The specific reaction results are shown in Table 1.
[0051] Example 11
[0052] 0.2 g of the solid heterogeneous catalyst prepared in Example 1 above was loaded into a high-pressure autoclave reactor. Then, 5 mmol of 2-octene and 5 g of toluene were added in sequence. The reaction kettle was sealed, and syngas (H2 / CO volume ratio of 1) was charged to 3 MPa. The temperature was slowly raised to 150 °C by a temperature controller and reacted for 24 h. After the reaction, the reaction kettle was cooled to room temperature, the excess reaction gas was slowly released, the catalyst was filtered and separated. The obtained product was added with 1,4-dioxane as an internal standard and analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector. The conversion rate of the reactant 2-octene was 99.7%, and the products were nonanal and nonanol. The total selectivity of aldehyde / alcohol was about 88.9% (aldehyde: alcohol = 6.0: 4.0). The specific reaction results are shown in Table 1.
[0053] Comparative Example 1
[0054] Compared with Example 11, 0.2 g of triphenylphosphine and 0.021 g of dicarbonylrhodium acetylacetonate were weighed and loaded into a high-pressure autoclave reactor. Then, 5 mmol of 2-octene and 5 g of toluene were added in sequence. The reaction kettle was sealed, and syngas (H2 / CO volume ratio of 1) was charged to 3 MPa. The temperature was slowly raised to 150 °C by a temperature controller and reacted for 24 h. After the reaction, the reaction kettle was cooled to room temperature, the excess reaction gas was slowly released, filtered and separated. The obtained product was added with 1,4-dioxane as an internal standard and analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector. The conversion rate of the reactant 2-octene was 76.1%, and the products were nonanal and nonanol. The total selectivity of aldehyde / alcohol was about 46.6% (aldehyde: alcohol = 5.5: 4.5). The specific reaction results are shown in Table 1.
[0055] Comparative Example 2
[0056] Compared with Example 1, under an inert gas protection atmosphere at 298K, 0.105 grams of dicarbonylacetylacetonato rhodium was weighed and dissolved in 50 ml of tetrahydrofuran solvent. 1.0 gram of the porous organic polymer prepared in Comparative Example 1 was added, and the mixture was stirred for 24 hours. Subsequently, the solvent was removed under vacuum at 333K, and a solid heterogeneous catalyst with a metal component supported by an organic ligand polymer was obtained.
[0057] 1 g of the solid heterogeneous catalyst prepared above was added to a trickle-bed reactor, and a mixture of hydrogen and CO (molar ratio 1:1) was introduced. The gas hourly space velocity was 5000 h -1 , and the liquid 1-octene raw material was pumped into the reactor by a high-pressure metering pump to start the reaction. The reaction temperature was 140 °C, the reaction pressure was 3 MPa, and the liquid hourly space velocity of liquid 1-octene was 0.1 h -1 . The liquid product was collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using 1,4-dioxane as an internal standard. The reaction tail gas was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The conversion rate of the reactant 1-octene was 81.1%, and the products were nonanal and nonanol. The total selectivity of aldehyde / alcohol was about 52.2% (aldehyde:alcohol = 5.4:4.6). For the specific reaction results, refer to Table 1.
[0058] The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. Those skilled in the art understand that other changes and modifications can be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.
[0059] Table 1. Hydroformylation reaction results
[0060]
[0061]
[0062] Note: The product of hydroformylation of each type of hydrocarbon is an aldehyde / alcohol with one more carbon atom.
[0063] The results show that a novel type of Co-based polymer heterogeneous catalyst designed and developed in this invention application has extremely high hydroformylation reaction activity, not only for high-carbon and low-carbon terminal olefins, but also for internal olefins such as 2-isobutene, 2-hexene, and 2-octene, with high conversion rates and overall aldehyde / alcohol selectivities.
[0064] Compared with the traditional triphenylphosphine-rhodium-based homogeneous catalytic system (Comparative Example 1), this catalyst has a higher conversion rate of 2-octene and an overall selectivity of aldehyde / alcohol (Example 11); in the hydroformylation reaction of 1-octene in a continuous trickle-bed reactor, it can be seen that this catalyst also has more excellent reaction performance; in addition, due to the heterogeneous state of the catalyst of this invention patent, it is also easier to recover and utilize in industry, avoiding the difficulties in the catalyst recycle reaction.
Claims
1. A cobalt-based heterogeneous catalyst, which is composed of a metal component and an organic ligand polymer, wherein the metal component is metal Co, and the organic ligand polymer is a polymer formed by solvothermal copolymerization of a heteroatom monomer containing vinyl and a carbon skeleton monomer containing vinyl; the molar ratio of the heteroatom monomer containing vinyl to the carbon skeleton monomer containing vinyl is 0.05:1 to 20:1, preferably 0.2:1 to 5:1, more preferably 0.5:1 to 2:
1.
2. The solid heterogeneous catalyst according to claim 1, wherein: the metal component forms a coordination bond with the heteroatoms in the organic ligand polymer backbone and exists on the organic ligand polymer support; the metal component accounts for 0.01-20.0% in the total weight of the solid heterogeneous catalyst, preferably 0.05-10.0%, more preferably 0.1-5.0%.
3. The catalyst according to claim 1, wherein: the heteroatom ligand containing vinyl is one or more selected from the following.
4. The method according to claim 1, wherein: the carbon skeleton monomer containing vinyl is one or more selected from the following.
5. The solid heterogeneous catalyst according to any one of claims 1-4, wherein: The specific surface area of the organic ligand polymer is 500 - 3000 m 2 / g, the pore volume is 0.5 - 5.0 cm 3 / g, and the pore size distribution is in the range of 0.2 - 100.0 nm.
6. A method for preparing the solid heterogeneous catalyst according to any one of claims 1-5, the method comprising: a) At 223-473K, under an inert atmosphere, in an organic solvent, add a heteroatom monomer containing vinyl, add a carbon skeleton monomer containing vinyl, add or not add a crosslinking agent, and then add a radical initiator. After mixing, stir the mixture for 0.1-50 hours, and the preferred stirring time range is 0.3-1 hour; b) Transfer the mixed solution obtained in step a) to a synthesis autoclave, at 273K-473K (preferably 323K-423K, more preferably 363K-423K), under an inert atmosphere, use solvothermal polymerization method, and let it stand for 1-100 hours for polymerization reaction (preferably 6-72 hours, more preferably 12-48 hours) to obtain a heteroatom-containing porous organic polymer; c) Vacuum-remove the solvent from the polymer obtained in step b) at room temperature to obtain an organic polymer containing exposed heteroatoms with a hierarchical pore structure, which is the support of the heterogeneous catalyst; In step a), the molar ratio of the heteroatom monomer containing vinyl to the carbon skeleton monomer containing vinyl is 0.05:1 to 20:1, preferably 0.2:1 to 5:1, more preferably 0.5:1 to 2:
1. Before polymerizing into an organic polymer, the concentration range of the heteroatom monomer containing vinyl in the organic solvent is 0.01-1000 g / L (preferably 0.1-100 g / L, more preferably 0.5 g-50 g / L).
7. The method according to claim 6, wherein, In the case where the vinyl-containing heteroatom monomer described in step a) is added with a crosslinking agent, the molar ratio of the vinyl-containing heteroatom monomer to the added crosslinking agent is 0.01:1 to 10:1 (preferably 0.03:1 to 8:1, more preferably 0.05:1 to 5:1); In the case where the vinyl-containing heteroatom monomer described in step a) is not added with a crosslinking agent but added with a radical initiator, the molar ratio of the vinyl-containing heteroatom monomer to the radical initiator is 300:1 to 10:1, preferably 100:1 to 5:1, more preferably 50:1 to 3:
1.
8. According to the method described in claim 6, characterized in that, the solvent used in steps a) and b) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; the radical initiator used in step a) is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile.
9. An application of the solid heterogeneous catalyst according to any one of claims 1-5, characterized in that, in the presence of the solid heterogeneous catalyst, the olefin raw material and syngas are subjected to the hydroformylation reaction in a fixed bed, trickle bed, slurry bed or autoclave reactor, wherein the reaction temperature is 273-573K (preferably 323-473K, more preferably 363-523K), and the reaction pressure is 0.05-20.0MPa (preferably 0.3-9.0MPa, more preferably 0.6-6MPa); When the olefin raw material is in liquid state, the liquid hourly space velocity is 0.01 - 20.0 h -1 (preferably 0.1 - 15.0 h -1 , more preferably 0.3 - 10.0 h -1 ); The gas hourly space velocity is 100 - 20000 h -1 (preferably 300 - 15000.0 h -1 , more preferably 500 - 12000.0 h -1 ). When the olefin raw material is in a gaseous state, its molar ratio to the CO and H 2 is 1:1:1 - 1:100:100 (preferably 1:1:1 - 1:50:50, more preferably 1:1:1 - 1:20:20).
10. According to the application described in claim 9, characterized in that, the olefin is selected from one or more of the following: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 2-isobutene, 3-isobutene, 2-hexene, 2-octene.