CN112823883B - Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof - Google Patents
Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
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Abstract
The invention discloses an alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst, a preparation method and application thereof. The invention discloses an alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst, which comprises the following components in percentage by mass, based on 100% of the mass of the catalyst: a) 40-70% of CuSiO3；b)20％‑45％Zn2SiO4(ii) a c) 2% -15% of at least one of alkaline earth metal oxide or alkali metal oxide. The catalyst provided by the invention is a Cu-Si system catalyst, has the advantages of high stability, good benzyl alcohol conversion rate and isopropyl benzene selectivity, environment-friendly preparation process and simple and easily-obtained raw materials when being used for hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of catalysts, and relates to an alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst, and a preparation method and application thereof.
Background
Propylene Oxide (PO) is a very important organic compound starting material, second only to the third largest propylene derivatives of polypropylene and acrylonitrile. The main application of the propylene oxide is to produce polyether polyol, and the polyether polyol is an important raw material for producing chemical products such as polyurethane foam, elastomers, adhesives, coatings and the like; in addition, propylene oxide is also widely used in the production of propylene glycol and nonionic surfactants.
At present, three main processes for industrially producing propylene oxide are a chlorohydrin process, an oxidation-co-process and a cumyl peroxide circulation process. Wherein, the propylene oxide device of the chlorohydrination method and the co-oxidation method accounts for more than 99 percent of the total production capacity of the propylene oxide all over the world, wherein, the chlorohydrination method accounts for about 45 percent, and the co-oxidation method accounts for about 54 percent; in the co-oxidation process, 33% of the ethylbenzene process, 18% of the isobutane process and 3% of the cumene hydroperoxide process. The chlorohydrin process causes serious environmental problems in the production process, while the co-oxidation process can avoid environmental pollution, but the economic benefit of the process is influenced by the price fluctuation of co-products due to the large amount of co-produced by-product styrene in the production process. The new PO producing process developed by Sumitomo chemical includes three steps of cumene oxidation, propylene epoxidation and alpha, alpha-dimethyl benzyl alcohol hydrogenolysis. The process has high conversion rate and high selectivity, the byproduct alpha, alpha-dimethyl benzyl alcohol can be subjected to hydrogenolysis to obtain cumene, the cumene can be recycled as a raw material after being oxidized, and the product of the method is only PO, is not influenced by the price fluctuation of the byproduct styrene and can bring more stable economic benefits for manufacturers. However, in the hydrogenolysis process of α, α -dimethylbenzyl alcohol, a Cu — Cr catalyst is used, and the production and use of the catalyst may seriously pollute the environment.
U.S. Pat. No. 4, 6646139, 2 discloses a process for the preparation of cumene by the catalytic hydrogenolysis of α, α -dimethylbenzyl alcohol, in which a copper-chromium system is selected as the hydrogenolysis catalyst. Although the conversion rate of the alpha, alpha-dimethylbenzyl alcohol reaches 100 percent, the selectivity exceeds 97.5 percent. However, the catalyst uses a chromium component in the preparation process, so that the problem of serious environmental pollution exists, and meanwhile, the copper-chromium system also has the problems of poor interaction, low copper dispersion degree and easy sintering of copper at high temperature.
US3337646 provides a process for the gas phase hydrogenolysis of benzyl alcohol to cumene by selecting a nickel-chromium-aluminum system as the hydrogenolysis catalyst and hydrogen as the hydrogen source at 350 ℃. The catalyst disclosed by the method contains chromium element, and the production and use process has great harm to the environment. In addition, the method has high reaction temperature, and the problem of crystal grain growth and sintering of the active component copper exists.
Patent CN104230642A discloses a method for preparing cumene by directly hydrogenolysis of α, α -dimethylbenzyl alcohol, which adopts Pd-C system, and adds at least one of Ni or its oxide, Sn or its oxide; the activity stability of the catalyst is improved, but the addition amount of Pd is large, and the cost of the catalyst is high, so that the catalyst is not beneficial to industrial production and application.
Patent CN102464567A discloses a method for preparing cumene by the direct hydrogenolysis of α, α -dimethylbenzyl alcohol, wherein the catalyst used comprises the following components in weight percent: a) 15.0-45.0% of CuO; b) 15.0-45.0% ZnO; c) 2-25% MnOx; d) 15.0-55.0% Al2O3(ii) a e) 2.0-20.0% of at least one selected from MgO, CaO or BaO. There is also a problem of poor stability.
In conclusion, the existing alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst Cu-Al system has poor stability, the Pd-C system has high production cost, and the Cu-Cr system has serious environmental pollution.
Disclosure of Invention
The technical problems to be solved by the invention are that the existing alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst has poor stability, high manufacturing cost and serious environmental pollution in the production process.
In order to solve the technical problem, the invention provides an alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst, which comprises the following components in percentage by mass based on 100% of the mass of the catalyst:
a)40％-70％CuSiO3；
b)20％-45％Zn2SiO4；
c) 2% -15% of at least one selected from alkaline earth metal oxides or alkali metal oxides.
In some embodiments, the catalyst contains the following components in percentage by mass based on 100% by mass of the catalyst:
a)50％-65％CuSiO3；
b)25％-40％Zn2SiO4；
c) 5% -10% of at least one of alkaline earth metal oxide or alkali metal oxide.
In some embodiments, in the above catalyst, the alkaline earth metal oxide is selected from one or more of MgO, CaO, BaO, SrO.
In some embodiments, the catalyst of any of the above, wherein the alkali metal oxide is selected from Li2O、Na2O、K2One or more of O.
In some embodiments, the catalyst described in any of the above may have the following composition: 65% CuSiO3-25％Zn2SiO4-5％MgO-5％Na2O、40％CuSiO3-45％Zn2SiO4-15％Li2O、70％CuSiO3-20％Zn2SiO4-10％MgO、60％CuSiO3-30％Zn2SiO4-10％MgO、60％CuSiO3-32％Zn2SiO4-5％MgO-3％Na2O、50％CuSiO3-40％Zn2SiO4-5％MgO-5％Na2O、65％CuSiO3-33％Zn2SiO4-2％Na2O、65％CuSiO3-30％Zn2SiO4-5％Na2O。
In order to solve the above technical problems, the present invention further provides a method for preparing any one of the α, α -dimethylbenzyl alcohol hydrogenolysis catalysts described above, comprising the steps of:
1) dissolving copper salt and zinc salt in deionized water to obtain a salt solution;
2) dropwise adding the salt solution obtained in the step 1) and a sodium silicate aqueous solution in a parallel flow manner under the stirring condition, and ensuring that the pH value is 6-8 in the precipitation process to obtain a precipitate;
3) washing, drying and roasting the precipitate obtained in the step 2) to obtain catalyst raw powder;
4) crushing the raw catalyst powder obtained in the step 3), adding an alkali metal salt solution and/or an alkaline earth metal salt solution, and then molding and roasting to obtain the catalyst;
wherein the solvent of the alkali metal salt solution and/or the alkaline earth metal salt solution is water.
In some embodiments, in the above method, the copper salt in step 1) is copper nitrate or copper chloride; and/or
The zinc salt in the step 1) is zinc nitrate or zinc chloride; and/or
The alkali metal salt in the step 4) is one or more of sodium nitrate, potassium nitrate, lithium nitrate, sodium chloride, lithium chloride and potassium chloride; and/or
The alkaline earth metal salt in the step 4) is one or more of magnesium nitrate, calcium nitrate, barium nitrate, strontium nitrate, magnesium chloride, calcium chloride, barium chloride and strontium chloride.
In some embodiments, in the above method, the concentration of the aqueous sodium silicate solution in the step 2) is 0.1 to 3mol/L, preferably 0.5 to 1.5 mol/L;
the temperature of the precipitation reaction in step 2) is 50 ℃ to 80 ℃.
In some embodiments, in any of the above methods, the washing of step 3) is deionized water washing, the drying temperature is no more than 150 ℃, and the calcination temperature is in the range of 300 ℃ to 700 ℃, preferably 400 ℃ to 500 ℃.
In some embodiments, in any of the above methods, the temperature of the calcination in step 4) ranges from 300 ℃ to 700 ℃, preferably from 400 ℃ to 500 ℃.
In order to solve the technical problems, the invention also provides an application of any one of the alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalysts in catalyzing alpha, alpha-dimethylbenzyl alcohol and cumene to prepare cumene.
The catalyst provided by the invention is a Cu-Si system catalyst, has the advantages of high stability, good benzyl alcohol conversion rate and isopropyl benzene selectivity, environment-friendly preparation process and simple and easily-obtained raw materials when being used for hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, and is suitable for industrial production.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1 catalyst a
112g of copper nitrate trihydrate and 66.7g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 8, and the precipitation temperature is 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. Dissolving 13.7g of sodium nitrate and 32g of magnesium nitrate hexahydrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and forming, and roasting at 450 ℃ for the second time to obtain the catalyst a. The catalyst a comprises the following components in percentage by mass, based on 100% of the mass of the catalyst a: 65% of CuSiO3-25％Zn2SiO4-5％MgO-5％Na2O。
Example 2 catalyst b
68.9g of copper nitrate trihydrate and 120g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 8, and the precipitation temperature is 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. And dissolving 69g of lithium nitrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting, and roasting at 450 ℃ to obtain the catalyst b. And the mass of the catalyst b is 100%, and the catalyst b comprises the following components in percentage by mass: 40% CuSiO3-45％Zn2SiO4-15％Li2O。
Example 3 catalyst c
120.8g of copper nitrate trihydrate and 53.4g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 7, and the precipitation temperature is 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. And dissolving 64.1g of magnesium nitrate hexahydrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and molding, and roasting at 450 ℃ for the second time to obtain the catalyst c. Based on the mass of the catalyst c as 100%, the catalyst c comprises the following components in percentage by mass: 70% CuSiO3-20％Zn2SiO4-10％MgO。
Example 4 catalyst d
103g of copper nitrate trihydrate and 80g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 7, and the precipitation temperature is 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. And dissolving 64g of magnesium nitrate hexahydrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and forming, and roasting at 450 ℃ for the second time to obtain the catalyst d. Based on the mass of the catalyst d as 100%, the catalyst d comprises the following components in percentage by mass: 60% CuSiO3-30％Zn2SiO4-10％MgO。
Example 5 catalyst e
103.4g of copper nitrate trihydrate and 85.4g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1mol/L. The prepared nitrate solution and 1mol/L sodium silicate aqueous solution are stirred in parallel and dripped into a flask for coprecipitation, and the precipitation temperature is 50 ℃. And keeping the solution temperature at 50 ℃ after the dropwise addition is finished, continuing stirring and aging for 2.5 hours, washing the precipitate with deionized water, filtering, drying at 100 ℃ overnight, and roasting at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. 8.2g of sodium nitrate and 32g of magnesium nitrate hexahydrate are dissolved in 24g of water and then fully mixed with the catalyst raw powder, tabletting and forming are carried out after drying, and the catalyst a is obtained after secondary roasting at 450 ℃. The catalyst a comprises the following components in percentage by mass, based on 100% of the mass of the catalyst a: 60% CuSiO3-32％Zn2SiO4-5％MgO-3％Na2O。
Example 6 catalyst f
86g of copper nitrate trihydrate and 106.7g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 6, and the precipitation temperature is 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. Dissolving 13.7g of sodium nitrate and 32g of magnesium nitrate hexahydrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and forming, and roasting at 450 ℃ for the second time to obtain the catalyst a. The catalyst a comprises the following components in percentage by mass, based on 100% of the mass of the catalyst a: 50% CuSiO3-40％Zn2SiO4-5％MgO-5％Na2O。
Example 7 catalyst g
112g of copper nitrate trihydrate and 88g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 8, and the precipitation temperature is 60 ℃. Dripping deviceAfter the addition is finished, the solution temperature is kept at 50 ℃, the stirring and the aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried at 100 ℃ overnight, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. Dissolving 5.5g of sodium nitrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and molding, and roasting at 450 ℃ for the second time to obtain the catalyst a. The catalyst a comprises the following components in percentage by mass, based on 100% of the mass of the catalyst a: 65% CuSiO3-33％Zn2SiO4-2％Na2O。
EXAMPLE 8 catalyst h
112g of copper nitrate trihydrate and 80g of zinc nitrate hexahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ion and zinc ion) concentration of 1 mol/L. And (3) enabling the prepared nitrate solution and 1mol/L sodium silicate aqueous solution to flow in parallel, stirring and dripping into a flask for coprecipitation, wherein the precipitation pH is 8, and the precipitation temperature is 80 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered by deionized water, dried overnight at 100 ℃, and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed. Dissolving 13.7g of sodium nitrate in 24g of water, fully mixing with the catalyst raw powder, drying, tabletting and molding, and roasting at 450 ℃ for the second time to obtain the catalyst a. The catalyst a comprises the following components in percentage by mass, based on 100% of the mass of the catalyst a: 65% CuSiO3-30％Zn2SiO4-5％Na2O。
Comparative example 1
112g of copper nitrate trihydrate and 92g of chromium nitrate nonahydrate were dissolved in deionized water to prepare a nitrate solution having a metal cation (i.e., copper ions and chromium ions) concentration of 1mol/L, and a copper-chromium catalyst, i.e., the catalyst of comparative example 1, was prepared by coprecipitation using a 1mol/L sodium carbonate solution as a precipitant. Based on the mass of the catalyst as 100%, the catalyst in comparative example 1 comprises the following components in percentage by mass: 65% of CuO-35% of Cr2O3。
Comparative example 2
112g of copper nitrate trihydrateDissolving the mixture in deionized water to prepare a nitrate solution with the copper ion concentration of 1mol/L, taking a sodium carbonate solution of 1mol/L as a precipitator, dropwise adding the prepared nitrate solution and the prepared sodium carbonate solution into silica sol of which the mass fraction is 20 percent of 175g in a cocurrent manner while stirring, and keeping the precipitation temperature at 50 ℃. After the dropwise addition, the solution temperature is kept at 50 ℃, the stirring and aging are continued for 2.5 hours, then the precipitate is washed and filtered, the precipitate is dried at 100 ℃ overnight, and the precipitate is roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed and then tableted to obtain the catalyst of comparative example 2. The catalyst of comparative example 2 comprises the following components in percentage by mass, based on 100% of the mass of the catalyst: 65% of CuO-35% of SiO2。
Comparative example 3
112g of copper nitrate trihydrate and 93g of zinc nitrate hexahydrate are dissolved in deionized water to prepare a nitrate solution with the concentration of metal cations (namely, copper ions and zinc ions) being 1mol/L, the prepared nitrate solution is dropwise added into a 1mol/L sodium silicate aqueous solution while stirring for coprecipitation, the precipitation pH is 8, and the precipitation temperature is 50 ℃. After the dropwise addition, the stirring and aging are continued for 2.5 hours, and then the precipitate is washed, filtered, dried at 100 ℃ overnight and roasted at 500 ℃ for 6 hours to obtain the catalyst raw powder. The obtained catalyst raw powder was crushed and then tableted to obtain the catalyst of comparative example 3. Based on the mass of the catalyst as 100 percent, the catalyst of comparative example 3 comprises the following components in percentage by mass: 65% CuSiO3-35％Zn2SiO4。
Test example
The catalysts prepared in examples 1 to 8 and comparative examples 1 to 3 were activated using a reducing gas of a hydrogen-nitrogen mixture gas in which hydrogen was 5% by volume. The activation temperature is 200 ℃ and the activation time is 24 hours.
The raw material for evaluating the catalyst is a mixed solution of alpha, alpha-dimethylbenzyl alcohol and cumene, wherein the content of the alpha, alpha-dimethylbenzyl alcohol is 20 percent by mass percent, and the balance is the cumene. The loading of the catalyst is 10ml, the reaction temperature is 180 ℃, the reaction pressure is 2.0MPa, and H is2The mol ratio of the alpha, alpha-dimethyl benzyl alcohol is 10.0, the space velocity of the volume of the raw material is 3.0h-1Evaluation time 100The results of the evaluation are shown in Table 1.
The reaction time when both the benzyl alcohol conversion and cumene selectivity were greater than 90% was specified as the catalyst life.
TABLE 1 hydrogenolysis of various catalysts alpha, alpha-dimethylbenzyl alcohol
From the evaluation results, compared with the catalyst of the comparative example, the catalyst prepared by the method provided by the invention has better benzyl alcohol conversion rate and cumene selectivity under the reaction conditions, can still keep higher hydrogenolysis reaction activity and stability after longer reaction time, does not pollute the environment in the preparation process of the catalyst, has wide sources of raw materials of the catalyst, obtains better technical effect, and is suitable for industrial production.
Claims (12)
1. An alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst, which comprises the following components in percentage by mass based on 100% of the mass of the catalyst:
a)40％-70％CuSiO3；
b)20％-45％Zn2SiO4；
c) 2% -15% of at least one of alkaline earth metal oxide or alkali metal oxide.
2. The catalyst of claim 1, wherein: the catalyst comprises the following components in percentage by mass based on 100% of the mass of the catalyst:
a)50％-65％CuSiO3；
b)25％-40％Zn2SiO4；
c) 5% -10% of at least one of alkaline earth metal oxide or alkali metal oxide.
3. The catalyst of claim 1, wherein: the alkaline earth metal oxide is selected from one or more of MgO, CaO, BaO and SrO.
4. A catalyst according to any one of claims 1 to 3, characterized in that: the alkali metal oxide is selected from Li2O、Na2O、K2One or more of O.
5. A method of preparing the α, α -dimethylbenzyl alcohol hydrogenolysis catalyst as claimed in any one of claims 1-4 comprising the steps of:
1) dissolving copper salt and zinc salt in deionized water to obtain a salt solution;
2) dropwise adding the salt solution obtained in the step 1) and a sodium silicate aqueous solution in a parallel flow manner under the stirring condition, and ensuring the pH value to be 6-8 in the precipitation process to obtain a precipitate;
3) washing, drying and roasting the precipitate obtained in the step 2) to obtain catalyst raw powder;
4) crushing the raw catalyst powder obtained in the step 3), adding an alkali metal salt solution and/or an alkaline earth metal salt solution, and then molding and roasting to obtain the catalyst;
wherein, the solvent of the alkali metal salt solution and/or the alkaline earth metal salt solution is water.
6. The method of claim 5, wherein: the copper salt in the step 1) is copper nitrate or copper chloride; and/or
The zinc salt in the step 1) is zinc nitrate or zinc chloride; and/or
The alkali metal salt in the step 4) is one or more of sodium nitrate, potassium nitrate, lithium nitrate, sodium chloride, lithium chloride and potassium chloride; and/or
The alkaline earth metal salt in the step 4) is one or more of magnesium nitrate, calcium nitrate, barium nitrate, strontium nitrate, magnesium chloride, calcium chloride, barium chloride and strontium chloride.
7. The method of claim 5, wherein: the temperature of the precipitation reaction in the step 2) is 50-80 ℃.
8. The method according to any one of claims 5-7, wherein: the washing in the step 3) is deionized water washing, the drying temperature is not more than 150 ℃, and the roasting temperature range is 300-700 ℃.
9. The method of claim 8, wherein: the roasting temperature range of the step 3) is 400-500 ℃.
10. The method according to any one of claims 5 to 7, wherein: the roasting temperature range of the step 4) is 300-700 ℃.
11. The method of claim 10, wherein: the roasting temperature range of the step 4) is 400-500 ℃.
12. Use of the α, α -dimethylbenzyl alcohol hydrogenolysis catalyst as claimed in any one of claims 1-4 for catalyzing α, α -dimethylbenzyl alcohol to cumene.
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