CN109821530B - Cobalt-based catalyst and method for applying cobalt-based catalyst to propylene epoxidation reaction - Google Patents
Cobalt-based catalyst and method for applying cobalt-based catalyst to propylene epoxidation reaction Download PDFInfo
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Abstract
A cobalt-based catalyst for propylene epoxidation, which is a catalyst used for producing propylene oxide by subjecting propylene to catalytic epoxidation reaction under the condition that oxygen is used as an oxygen source, wherein cobalt and X in an oxidized state are supported on a carrier containing tungsten oxide and/or molybdenum oxide in a Co/(Co + X) atomic ratio range of 0.05-0.99, wherein X represents at least 1 element selected from the group consisting of nickel, gold, palladium, platinum, ruthenium, silver, lanthanum and copper.
Description
Technical Field
The invention provides a method for catalyzing propylene to generate epoxypropane by epoxidation reaction under the condition of taking oxygen as an oxygen source by using a novel cobalt-based catalyst.
Background
Propylene Oxide (PO) is an important basic organic chemical raw material. The method is mainly used for producing polyurethane, unsaturated resin, surfactant and the like. The epoxypropane is also an important raw material of fine chemical products, and the downstream derived products of the epoxypropane are nearly hundreds of, and are widely applied to a plurality of industries such as automobiles, buildings, food, medicines, cosmetics and the like.
Currently, industrial methods for producing propylene oxide mainly include chlorohydrin method and co-oxidation method (Halcon method), and the production capacities of these two methods account for more than 95% of the worldwide PO production capacity. The chlorohydrin method seriously pollutes the environment, and equipment is seriously corroded, so that the chlorohydrin method is gradually eliminated. The co-oxidation method overcomes the defects of the chlorohydrin method, but has long flow and large investment, and is severely limited by the market of co-products because a large amount of co-products are generated.
In view of the disadvantages of industrial PO production process, people have been devoted to research a PO green clean production process with simple flow, less byproducts and no pollution for many years. Since 1998 Haruta M (Hayashi T, Tanaka K, Haruta M.Selective vacuum-phase epoxidation of propylene over Au/TiO2catalysts in the presence of oxygen and hydrogen [ J ]. Journal of Catalysis,1998,178:566), it was reported that gold-supported heterogeneous catalysts became a hotspot in the field after selective catalytic epoxidation of propylene to propylene oxide under an atmosphere of H2-O2.
Disclosure of Invention
In order to fill up the technical blank in China, an Au supported catalyst is invented for the problem group, the proportion of the rest components in the obtained catalyst has great influence on the crystallinity of gold, and the better the crystallinity of gold is, the better the catalytic activity and the selectivity are. The cobalt-based gold nano catalyst has the advantages of high reaction activity, good stability and the like, the conversion rate of propylene is 12 percent at most, and the selectivity of propylene oxide is 68 percent at most.
The implementation method of the invention is as follows:
a cobalt-based catalyst for propylene epoxidation, which is a catalyst used for producing propylene oxide by epoxidation of propylene under the condition that oxygen is used as an oxygen source,
wherein cobalt and X in an oxidation state are supported on a carrier in a Co/(Co + X) atomic ratio range of 0.05 to 0.99,
wherein X represents at least 1 element selected from the group consisting of nickel, gold, palladium, platinum, ruthenium, silver, lanthanum and copper.
A cobalt-based catalyst comprising composite nanoparticles consisting of cobalt in an oxidized state and X, where X represents at least 1 element selected from the group consisting of cobalt, nickel, gold, palladium, platinum, ruthenium, silver, lanthanum and copper.
The composite nanoparticles in the cobalt-based catalyst are particles in which X is used as a core and the surface of the core is coated with cobalt in an oxidized state.
The cobalt-based catalyst, in addition to the composite nanoparticles described above, is supported on a carrier, and further, Co in an oxidized state is supported on the carrier alone.
The cobalt-based catalyst is characterized in that the Co in the oxidation state is an oxide of cobalt and/or a composite oxide containing cobalt.
The carrier in the cobalt-based catalyst contains one of silicon dioxide, magnesium oxide, tungsten oxide and molybdenum oxideOne or a combination of two silica-based compositions containing silicon, tungsten and molybdenum in a molar amount based on the total molar amount of silicon, tungsten and molybdenum
Silicon in the molar% range,
Tungsten in the molar% range,
In the range of mole% of molybdenum,
magnesium in the mole% range.
A cobalt-based catalyst having a composition ratio of tungsten oxide to cobalt in terms of W/Co atomic ratio of
The composition ratio of molybdenum oxide and cobalt in Mo/Co atomic ratio is
The composition ratio of cobalt to magnesium oxide is calculated by the atomic ratio of Mg to Co
The cobalt-based catalyst prepared has a specific surface area of
The maximum frequency of pore diameters is
Pore volume of
Having a particle diameter of
The cobalt-based catalyst is prepared in the form of powder, granules, blocks, spheres, columns or other shapes.
A method for producing a cobalt-based catalyst, comprising the steps of:
1) preparation of the support
Mixing precursors of silicon oxide and magnesium oxide, acid solution and deionized water, stirring for 0.5-8h at 25-90 ℃, cooling to room temperature, dropwise adding precursor aqueous solution of tungsten oxide and/or molybdenum oxide with the concentration of 5-20%, stirring for 10-60min at room temperature to obtain uniform solid solution suspension, standing for 4-12h at 50-90 ℃, aging for 12-48h at room temperature to obtain uniform solid solution suspension, carrying out rotary evaporation on gel to remove water, carrying out vacuum drying at 80-120 ℃ to obtain powdery solid, placing the solid in a tubular furnace, roasting under any atmosphere of hydrogen, oxygen, air, nitrogen or argon, carrying out programmed heating at the rate of 50-200 ℃/h, heating to 800 ℃ from room temperature, roasting for 2-20h, and naturally cooling to obtain an oxide carrier;
2) preparation of cobalt-based catalyst
Sequentially adding a carrier, a precipitator, soluble X metal salt, soluble cobalt metal salt and deionized water into a reactor, uniformly mixing, stirring and reacting for 1-10h at 50-80 ℃, cooling the mixture to room temperature, filtering under reduced pressure to obtain a solid, vacuum-drying the solid at 50-90 ℃ for 0.5-5h, roasting the solid in a muffle furnace at 200-800 ℃, preferably at 300-600 ℃, for 2-20h, preferably for 2-8h, and naturally cooling to obtain the catalyst.
The catalyst preparation method can be an impregnation method or a uniform precipitation method, preferably a uniform precipitation method, wherein a precipitant precursor used in the uniform precipitation method is selected from one or more than two of urea, hexamethyltetramine, urea and dimethyl oxalate, and urea and oxalic acid.
In the step 1), the carrier is one or the combination of two of SiO2 precursor, magnesium oxide, tungsten oxide and molybdenum oxide precursor, the SiO2 precursor is one or more than two of silica sol, column chromatography silica gel with 60-400 meshes, preferably 200-300 meshes, thin layer chromatography silica gel, superfine kaolin or tetraethoxysilane, the mass ratio in the carrier is 50-90%,the precursor of magnesium oxide is one or more of magnesium oxalate, magnesium acetate, magnesium nitrate, magnesium chloride, magnesium hydroxide, magnesium carbonate or magnesium oxide, the mass ratio of magnesium oxide in the carrier is 5-45%, and the precursors of tungsten oxide and molybdenum oxide are (NH)4)6W7O24·6H2O and (NH)4)6Mo7O24·6H2O, the mass ratio of the tungsten oxide and/or molybdenum oxide precursor in the carrier is 0-45%;
the acid solution is one or two of hydrochloric acid and nitric acid, the mass concentration of the hydrochloric acid is 10-37%, the adding amount is 0.1-2.0 times of the mass of the carrier, the mass concentration of the nitric acid is 30-65%, and the adding amount is 0.1-2.0 times of the mass of the carrier;
the addition amount of the precipitator in the step 2) is 0.2-1.2 times of the mass of the carrier, the molar ratio of Co to X in the soluble cobalt metal salt and the soluble X metal salt is 0.2-100, the addition amount of the soluble cobalt metal salt is 0.1-0.3 times of the mass of the carrier, and the addition amount of the deionized water is 20-100 times of the total mass of the solid material.
The method for catalyzing propylene epoxidation into propylene oxide by using the cobalt-based catalyst is characterized in that propylene is subjected to catalytic epoxidation reaction in the presence of a mixed gas of oxygen, hydrogen and nitrogen to prepare the propylene oxide. The reaction conditions are as follows: the reaction temperature is 100-350 ℃, the reaction pressure is 0.1-5MPa, the molar ratio of the propylene to the oxygen is 0.1-2, and the molar ratio of the propylene to the hydrogen is 0.1-2.
Evaluation of catalyst: weighing a certain amount of catalyst, adding the catalyst into a fixed bed reactor, introducing propylene, hydrogen, oxygen and nitrogen, heating to react, stopping the reaction after reacting for a certain time, and sampling and analyzing.
The advantages of the invention are as follows:
according to the invention, a novel cobalt-based catalyst is provided for preparing propylene oxide by catalyzing the epoxidation of propylene. The catalyst takes cheap cobalt as a main component of the catalyst instead of noble metals such as Pd, Pt and the like, and has the advantages of low noble metal consumption, high reaction activity, good stability and the like.
Detailed Description
The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
Examples of preparation of the support
Example 1
Stirring 5.0g of ethyl orthosilicate, 2.0g of magnesium hydroxide, 3.0g of 35% concentrated hydrochloric acid and 60mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and dropwise adding 10g of 10% NH4)6W7O24·6H2Stirring the O aqueous solution at room temperature for 15min to obtain a uniform solid solution suspension, standing at 80 ℃ for 8h, aging at room temperature for 48h, removing water from the gel by rotary evaporation, and drying at 110 ℃ in vacuum to obtain a powdery solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-WO3 metal composite oxide carrier.
Example 2
Stirring 6.0g of ethyl orthosilicate, 2.0g of magnesium hydroxide, 3.0g of 35% concentrated hydrochloric acid and 60mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and dropwise adding 8g of 10% NH4)6W7O24·6H2Stirring the O aqueous solution at room temperature for 15min to obtain a uniform solid solution suspension, standing at 80 ℃ for 8h, aging at room temperature for 48h, removing water from the gel by rotary evaporation, and drying at 110 ℃ in vacuum to obtain a powdery solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-WO3 metal composite oxide carrier.
Example 3
Stirring 4.0g of ethyl orthosilicate, 2.0g of magnesium hydroxide, 3g of 35% concentrated hydrochloric acid and 60mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and dropwise adding 8g of 10% NH4)6Mo7O24·6H2Stirring the O aqueous solution for 15min at room temperature to obtain a uniform solid solutionStanding the suspension at 80 deg.C for 8 hr, aging at room temperature for 48 hr, removing water from the gel by rotary evaporation, and vacuum drying at 110 deg.C to obtain powdered solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-MoO3 metal composite oxide carrier.
Example 4
Stirring 6.0g of ethyl orthosilicate, 3.0g of magnesium hydroxide, 3g of 35% concentrated hydrochloric acid and 60mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and dropwise adding 6g of 10% NH4)6Mo7O24·6H2Stirring the O aqueous solution at room temperature for 15min to obtain a uniform solid solution suspension, standing at 80 ℃ for 8h, aging at room temperature for 48h, removing water from the gel by rotary evaporation, and drying at 110 ℃ in vacuum to obtain a powdery solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-MoO3 metal composite oxide carrier.
Example 5
Stirring 5.0g of ethyl orthosilicate, 2.0g of magnesium hydroxide, 3g of 35% concentrated hydrochloric acid and 60mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and sequentially dropwise adding 6g of 10% NH4)6W7O24·6H2O aqueous solution and 4g of 10% strength (NH)4)6Mo7O24·6H2Stirring the O aqueous solution at room temperature for 15min to obtain a uniform solid solution suspension, standing at 80 ℃ for 8h, aging at room temperature for 48h, removing water from the gel by rotary evaporation, and drying at 110 ℃ in vacuum to obtain a powdery solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-WO3-MoO3 metal composite oxide carrier.
Example 6
Stirring 5.0g of 200-300 mesh column chromatography silica gel, 2.0g of magnesium hydroxide, 1.5g of 35% concentrated hydrochloric acid and 70mL of deionized water at 80 ℃ for 1h, cooling to room temperature, and sequentially dropwise adding 5g of 10% NH4)6W7O24·6H2O aqueous solution and 4g of 10% strength (NH)4)6Mo7O24·6H2Stirring the O aqueous solution at room temperature for 15min to obtain uniform solid solution suspension, standing at 80 ℃ for 8h, aging at room temperature for 48h, removing water from the gel by rotary evaporation, and vacuum drying at 100 ℃ to obtain powdery solid. Placing the solid in a tube furnace, carrying out temperature programmed roasting under nitrogen, starting at 30 ℃, heating to 300 ℃ at the speed of 2.25 ℃/min, keeping the temperature at 300 ℃ for 4h, starting at 300 ℃, heating to 600 ℃ at the speed of 2.5 ℃/min, and keeping the temperature at 600 ℃ for 4 h. Naturally cooling to obtain the SiO2-MgO-WO3-MoO3 metal composite oxide carrier.
TABLE 1 composition of catalyst support in each example
| Experimental number | Silicon source | Carrier composition | Carrier numbering |
| Example 1 | Tetraethoxysilane (pH 4.5) | SiO2-MgO-WO3 | Carrier A |
| Example 2 | Tetraethoxysilane (pH 4.5) | SiO2-MgO-WO3 | Carrier B |
| Example 3 | Tetraethoxysilane (pH 4.5) | SiO2-MgO-MoO3 | Carrier C |
| Example 4 | Tetraethoxysilane (pH 4.5) | SiO2-MgO-MoO3 | Carrier D |
| Example 5 | Tetraethoxysilane (pH 4.5) | SiO2-MgO-WO3-MoO3 | Carrier E |
| Example 6 | 200-mesh 300-mesh column chromatography silica gel | SiO2-MgO-WO3-MoO3 | Vector F |
Catalyst preparation examples
Example 7
Adding 1g of carrier A, 0.4g of urea, 22.0mg of chloroauric acid, 0.16g of cobalt nitrate and 70mL of deionized water into a reactor in sequence, uniformly mixing, stirring and reacting at 80 ℃ for 4h, cooling the mixture to room temperature, filtering under reduced pressure to obtain a solid, vacuum-drying the solid at 80 ℃ for 1h, and calcining the solid in a muffle furnace at 500 ℃ for 2 h. And naturally cooling to obtain the catalyst A.
Example 8
Adding 1g of carrier B, 0.6g of hexamethyltetramine, 20.0mg of chloroauric acid, 0.12g of cobalt nitrate and 70mL of deionized water into a reactor in sequence, uniformly mixing, stirring and reacting at 80 ℃ for 4 hours, cooling the mixture to room temperature, and filtering under reduced pressure. The solid was dried under vacuum at 80 ℃ for 1h and calcined in a muffle furnace at 600 ℃ for 2 h. And naturally cooling to obtain the catalyst B.
Example 9
1g of carrier C, 1.2g of hexamethyltetramine, 21.5mg of chloroauric acid, 0.20g of cobalt nitrate and 60mL of deionized water are sequentially added into a reactor and uniformly mixed, the mixture is stirred and reacted for 4 hours at 80 ℃, and after the mixture is cooled to room temperature, the mixture is decompressed and filtered. The solid was dried under vacuum at 80 ℃ for 1h and calcined in a muffle furnace at 500 ℃ for 2 h. And naturally cooling to obtain the catalyst C.
Example 10
Adding 1g of carrier D, 1.0g of hexamethyltetramine, 21.0mg of chloroauric acid, 0.18g of cobalt nitrate and 50mL of deionized water into a reactor in sequence, uniformly mixing, stirring and reacting at 80 ℃ for 5 hours, cooling the mixture to room temperature, and filtering under reduced pressure. The solid was dried under vacuum at 80 ℃ for 1h and calcined in a muffle furnace at 500 ℃ for 2 h. And naturally cooling to obtain the catalyst D.
Example 11
Adding 1g of carrier E, 0.6g of hexamethyltetramine, 21.0mg of chloroauric acid, 0.18g of cobalt nitrate and 70mL of deionized water into a reactor in sequence, uniformly mixing, stirring and reacting at 70 ℃ for 4 hours, cooling the mixture to room temperature, and filtering under reduced pressure. The solid was dried under vacuum at 80 ℃ for 1h and calcined in a muffle furnace at 600 ℃ for 2 h. And naturally cooling to obtain the catalyst E.
Example 12
1g of carrier F, 0.9g of hexamethyltetramine, 21.0mg of chloroauric acid, 0.18g of cobalt nitrate and 80mL of deionized water are sequentially added into a reactor and uniformly mixed, the mixture is stirred and reacted for 4 hours at 80 ℃, and after the mixture is cooled to room temperature, the mixture is decompressed and filtered. The solid was dried under vacuum at 80 ℃ for 1h and calcined in a muffle furnace at 600 ℃ for 2 h. And naturally cooling to obtain the catalyst F.
Experimental results for the use of the above catalyst in the epoxidation of propylene:
2.0g of catalyst is added into the fixed bed reactor, propylene, hydrogen, oxygen and nitrogen are blown in at the speed of 500mL/H, the volume ratio of the mixed gas group of propylene/H2/O2/N2 is 10/10/10/70, the pressure is 2Kg/cm3, the reaction is continuously carried out at the temperature of 250-350 ℃ to prepare the propylene oxide, and the experimental result of the reaction for 1H is shown in Table 2.
TABLE 2 evaluation of the Synthesis catalysts
| Number of Experimental examples | Propylene conversion/% | Selectivity/%) |
| Experimental example 7 | 6.6 | 64.6 |
| Experimental example 8 | 11.8 | 61.9 |
| Experimental example 9 | 9.0 | 62.4 |
| Experimental example 10 | 6.2 | 66.5 |
| Example 11 | 10.6 | 66.8 |
| Example 12 | 8.2 | 68.2 |
Claims (4)
1. The application of a cobalt-based catalyst in propylene epoxidation reaction is characterized in that: the catalyst comprises composite nanoparticles consisting of cobalt in the oxidic state and X,
cobalt and X in an oxidation state are supported on the carrier in a Co/(Co + X) atomic ratio range of 0.05-0.99,
wherein X represents at least 1 element selected from nickel, gold, palladium, platinum, ruthenium, silver and copper;
the cobalt-based catalyst catalyzes propylene to carry out epoxidation reaction in the presence of mixed gas of oxygen, hydrogen and nitrogen to prepare propylene oxide; the reaction temperature is 100-350 ℃, the reaction pressure is 0.1-5MPa, the molar ratio of the propylene to the oxygen is 0.1-2, and the molar ratio of the propylene to the hydrogen is 0.1-2;
the composite nano-particles are particles formed by coating cobalt with an oxidized state on the surface by taking X as a core; the preparation method of the cobalt-based catalyst comprises the following steps:
1) preparation of the support
Mixing precursors of silicon oxide and magnesium oxide, acid solution and deionized water, stirring for 0.5-8h at 25-90 ℃, cooling to room temperature, dropwise adding precursor aqueous solution of tungsten oxide and/or molybdenum oxide with the concentration of 5-20%, stirring for 10-60min at room temperature to obtain uniform solid solution suspension, standing for 4-12h at 50-90 ℃, aging for 12-48h at room temperature to obtain uniform solid solution suspension, carrying out rotary evaporation on gel to remove water, carrying out vacuum drying at 80-120 ℃ to obtain powdery solid, placing the solid in a tubular furnace, roasting under any atmosphere of hydrogen, oxygen, air, nitrogen or argon, carrying out programmed heating at the rate of 50-200 ℃/h, heating to 800 ℃ from room temperature, roasting for 2-20h, and naturally cooling to obtain an oxide carrier;
2) preparation of cobalt-based catalyst
Sequentially adding a carrier, a precipitator, soluble X metal salt, soluble cobalt metal salt and deionized water into a reactor, uniformly mixing, stirring and reacting for 1-10h at 50-80 ℃, cooling the mixture to room temperature, filtering under reduced pressure to obtain a solid, vacuum-drying the solid for 0.5-5h at 50-90 ℃, placing the solid in a muffle furnace at 300-600 ℃, roasting for 2-8h, and naturally cooling to obtain a catalyst; the carrier comprises 55-95 mol% of silicon, 0-30 mol% of tungsten and 0-35 mol% of molybdenum relative to the total molar weight of silicon, magnesium, tungsten and molybdenum, and the mol% of tungsten and molybdenum are not 0 at the same time and are not 5-35 mol% of magnesium; the composition ratio of tungsten oxide to cobalt in W/Co atomic ratio in the carrier is 0-100, the composition ratio of molybdenum oxide to cobalt in Mo/Co atomic ratio is 0-100, the composition ratio of cobalt to magnesium oxide in Mg/Co atomic ratio is 0.8-100, and the atomic ratios of W/Co and Mo/Co are not 0 at the same time.
2. Use according to claim 1, characterized in that: the preparation method of the catalyst is a uniform precipitation method, wherein a precipitant parent substance used by the uniform precipitation method is selected from one of urea, hexamethyltetramine, urea and dimethyl oxalate, and urea and oxalic acid.
3. Use according to claim 1, characterized in that: in the step 1), the silica precursor is one or more than two of silica sol, 200-mesh 300-mesh column chromatography silica gel, thin layer chromatography silica gel, ultrafine kaolin or tetraethoxysilane, the mass ratio of the silica precursor in the carrier is 50-90%, the magnesium oxide precursor is one or more than two of magnesium oxalate, magnesium acetate, magnesium nitrate, magnesium chloride, magnesium hydroxide, magnesium carbonate or magnesium oxide, the mass ratio of the magnesium oxide in the carrier is 5-45%, and the tungsten oxide precursor and the molybdenum oxide precursor are respectively (NH)4）6W7O24 .6H2O and (NH)4）6Mo7O24 .6H2O, the mass ratio of the precursor of the tungsten oxide and/or the molybdenum oxide in the carrier is 0-45%, and the mass ratio of the precursor of the tungsten oxide and/or the molybdenum oxide in the carrier is not 0 at the same time;
the acid solution is one or two of hydrochloric acid and nitric acid, the mass concentration of the hydrochloric acid is 10-37%, the adding amount is 0.1-2.0 times of the mass of the carrier, the mass concentration of the nitric acid is 30-65%, and the adding amount is 0.1-2.0 times of the mass of the carrier;
the addition amount of the precipitator in the step 2) is 0.2-1.2 times of the mass of the carrier, the molar ratio of Co to X in the soluble cobalt metal salt and the soluble X metal salt is 0.2-100, the addition amount of the soluble cobalt metal salt is 0.1-0.3 times of the mass of the carrier, and the addition amount of the deionized water is 20-100 times of the total mass of the solid material.
4. Use according to claim 1, characterized in that: the specific surface area of the catalyst is 20-350 m2The maximum frequency of pore diameter is 3-80 nm, the pore volume is 0.1-1.0 mL/g, the particle diameter is 10-500 um, and the shape can be one or more than two of powder, granule, block, sphere and column.
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