Hydrogenation catalyst, its preparation method and application, and preparation of 1-phenylethanol by liquid phase hydrogenation of acetophenone

Abstract

The application relates to the technical field of catalytic hydrogenation, and discloses a hydrogenation catalyst, a preparation method and application thereof, and preparation of 1-phenylethanol through liquid-phase hydrogenation of acetophenone. The catalyst comprises a SiO2 carrier, an active component Cu, a modified element F and an oxide of a metal M; the metal M is selected from at least one of group ⅡB metal, group ⅥB metal, group V ⅡB metal and group VIII metal; and the F is fluorine. The hydrogenation catalyst has good hydrogenation activity and long service life. When the hydrogenation catalyst is used in hydrogenation reaction, especially in low-temperature liquid-phase hydrogenation reaction, the catalyst has the characteristics of long service life. For example, when the hydrogenation catalyst is used in selective hydrogenation of acetophenone into 1-phenylethanol, the hydrogenation catalyst has the characteristics of low-temperature acetophenone hydrogenation activity, high selectivity and long service life.

Description

Technical Field

[0001] This invention relates to the field of catalytic hydrogenation technology, specifically to a hydrogenation catalyst, its preparation method and application, and the liquid-phase hydrogenation of acetophenone to prepare 1-phenylethanol. Background Technology

[0002] The selective hydrogenation of acetophenone (ACP) to α-methylbenzyl alcohol (MBA) has been studied on various metals. Common acetophenone hydrogenation catalysts include noble metal catalysts with palladium, platinum, ruthenium, and rhodium as active components, nickel-based catalysts, and copper-based catalysts. Noble metal catalysts and nickel-based catalysts are used for the hydrogenation reaction of acetophenone. Although the reaction conditions are mild, the selectivity of α-methylbenzyl alcohol is poor [Wang Youzhen, Qiao Minghua, Hu Huarong, Yan Shirun, Wang Weijiang, Fan Kangnian, Preparation and characterization of Ni-Sn-B / SiO2 amorphous catalyst for high-selectivity hydrogenation of acetophenone, Acta Chimica Sinica, Vol. 62, No. 14, 2004, 1349-1352; Sheng Xudong, Zhang Wei, Lu Mohong. Selective hydrogenation of acetophenone to α-phenylethanol catalyzed by palladium / mesoporous carbon. Fine Petrochemicals, 2015, 32(2): 58-62.]. Copper-based catalysts exhibit good low-temperature activity and strong CO bond selectivity with a relatively weak ability to form C-C bonds, which can improve the selectivity of phenylethanol [Federica Z, Nicoletta R, Rinaldo P. Heterogeneous selective catalytic hydrogenation of aryl ketones to alcohols without additives[J]. Tetrahedron Letters, 2005, 46(21): 3695-3697; Wang Y, Shen YL, Zhao Y J. Insight into the balancing effect of active Cu species for hydrogenation of carbon-oxygen bonds[J]. ACS Catalysis, 2015, 5(10): 6200-6208]. Bertero et al. [Nicolas M. Bertero, Carlos R. Alberto J. Marchi. Catalytic and kinetic study of the liquid-phase hydrogenation of acetophenone over Cu / SiO2 catalyst. [J] Applied Catalysis A: General 349 (2008) 100-109. The kinetics of hydrogenation of acetophenone on Cu / SiO2 catalyst were studied. The results showed that when acetophenone was assumed to be strongly adsorbed on the catalyst surface and phenylethanol was weakly adsorbed on the catalyst, the obtained kinetic model was in good agreement with the actual reaction results. Wang Bing et al. [Wang Bing, Qu Yanan, An Hao, Wang Jinkai, Guo Zhenmei, Lü Zhiguo. Preparation of high-performance nano-Cu / SiO2 catalyst and its catalytic performance on hydrogenation of aromatic ketones. Journal of Qingdao University of Science and Technology (Natural Science Edition), Vol. 41, No. 3, June 2020, 48-55] prepared Cu / SiO2 catalyst by sol-gel method. Compared with coprecipitation method, it has smaller particle size and better dispersion of active species. Finally, the mechanism of acetophenone hydrogenation was investigated. The synergistic effect of Cu0 and Cu+ improved the activity and stability of the catalyst. Sumitomo Chemical Co., Ltd. of Japan has previously reported in patents the use of Cu / SiO2 in the hydrogenation reaction of acetophenone [Oku et al., Sumitomo Chemical Company. US6410806, 2002.; T. Hibi, S. Ito, Sumitomo Chemical Company. US5663458, 1997.]. When the copper content is greater than 65%, the selectivity of α-methylbenzyl alcohol is high. Simultaneously, the addition of an alkali or alkaline earth metal can effectively prevent the hydrogenolysis reaction of α-methylbenzyl alcohol.

[0003] The catalysts used to prepare α-methylbenzyl alcohol from acetophenone are hydrogenation catalysts, and none of the above reports have addressed the deactivation of the catalyst under low-temperature reaction conditions. Summary of the Invention

[0004] In high-temperature hydrogenation, catalysts can deactivate due to carbon buildup. However, the inventors discovered that side reactions that generate water are generally involved in hydrogenation reactions. For example, after acetophenone is hydrogenated to produce 1-phenylethanol, the reaction of 1-phenylethanol undergoing hydrogenolysis to produce ethylbenzene and water is always unavoidable. If the reaction is carried out at a lower temperature, the accumulation of water can also lead to catalyst deactivation. This is the main problem that hydrogenation catalysts face.

[0005] Based on this, the purpose of this invention is to overcome the problem of easy deactivation of hydrogenation catalysts in the prior art, especially under low-temperature hydrogenation conditions, and to provide a hydrogenation catalyst, its preparation method and application, for the liquid-phase hydrogenation of acetophenone to 1-phenylethanol. This hydrogenation catalyst has good hydrogenation activity and long service life. When it is used in hydrogenation reactions, especially in low-temperature liquid-phase hydrogenation reactions, the catalyst has the characteristic of long service life. For example, when it is used for the selective hydrogenation of acetophenone to 1-phenylethanol, it has the characteristics of low-temperature acetophenone hydrogenation activity, high selectivity, and long service life.

[0006] The first aspect of the present invention provides a hydrogenation catalyst comprising: a SiO2 support, an active component Cu, a modifying element F, and an oxide of a metal M; wherein the metal M is selected from at least one of Group IIB, Group VIB, Group VIIB, and Group VIII metals; and F is fluorine.

[0007] The second aspect of the present invention provides a method for preparing the hydrogenation catalyst of the present invention, the method comprising: (1) a kneading compound containing a copper source, a metal M source, a SiO2 source and an F source is optionally shaped and heat-treated to obtain a catalyst precursor; (2) reducing the catalyst precursor obtained in step (1) to obtain the hydrogenation catalyst.

[0008] A third aspect of the present invention provides the application of the catalyst described herein in hydrogenation reactions.

[0009] The fourth aspect of the present invention provides a method for preparing 1-phenylethanol by liquid-phase hydrogenation of acetophenone, the method comprising: in the presence of the hydrogenation catalyst described in the present invention, contacting a mixture of acetophenone-containing raw materials with hydrogen to carry out a hydrogenation reaction to obtain a material containing 1-phenylethanol.

[0010] The hydrogenation catalyst of the present invention, when used in hydrogenation reactions, especially liquid-phase hydrogenation reactions, can better improve catalyst activity, enabling hydrogenation reactions to be carried out at lower temperatures. It can also reduce the possibility of dehydration side reactions and the possibility of water accumulation at the active sites of the catalyst, thereby improving the stability of the hydrogenation catalyst of the present invention at low-temperature reactions. For example, when the hydrogenation catalyst of the present invention is used in the liquid-phase hydrogenation of acetophenone to prepare 1-phenylethanol, it can achieve high acetophenone conversion and 1-phenylethanol selectivity. Moreover, the hydrogenation catalyst can be stably operated for 3000 hours without significant performance degradation, making it better suited for industrial production of 1-phenylethanol by hydrogenation of acetophenone. Attached Figure Description

[0011] Figure 1 These are the hydroxyl infrared spectra of hydrogenation catalyst CM-1 in Example 1 and hydrogenation catalyst cCM-1 in Comparative Example 1. Detailed Implementation

[0012] 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.

[0013] The first aspect of the present invention provides a hydrogenation catalyst comprising: a SiO2 support, an active component Cu, a modifying element F, and an oxide of a metal M; wherein the metal M is selected from at least one of Group IIB, Group VIB, Group VIIB, and Group VIII metals; and F is fluorine.

[0014] In this invention, the hydrogenation catalyst exhibits good catalytic activity and selectivity for the target product after hydrogenation. Especially under low-temperature hydrogenation reaction conditions, the hydrogenation catalyst of this invention has the advantages of better hydrogenation activity, high selectivity for the target product, and long service life.

[0015] According to the present invention, in some embodiments, the metal M is selected from at least one of Zn, Mn, Co, Cr, Mo, and Ni. Using the aforementioned embodiments, the oxide of metal M can better synergize with the active component to increase the catalytic activity of the catalyst, especially its catalytic activity and stability in low-temperature liquid-phase hydrogenation reactions.

[0016] According to some preferred embodiments of the present invention, the metal M is at least one selected from Zn, Mn, Co, and Mo. By employing the aforementioned embodiments, the synergistic effect between the oxide of metal M and the active component can be further increased to enhance the catalytic activity of the hydrogenation catalyst.

[0017] According to some preferred embodiments of the present invention, the metal M is Co.

[0018] According to some preferred embodiments of the present invention, the metal M is Mo.

[0019] According to the present invention, in some preferred embodiments, the metal M is Co and Mo; wherein, when Co and Mo are used simultaneously, there is no specific requirement for their ratio, for example, the mass ratio of Co to Mo based on the corresponding oxides is 1:(0.5-5), including but not limited to 1:0.5, 1:1, 1:2, 1:5.

[0020] According to the present invention, in some embodiments, the content of F in the hydrogenation catalyst is 0.5-5 wt%, preferably 1-3 wt%. By employing the aforementioned embodiments, the possibility of dehydration side reactions in the hydrogenation reaction can be reduced, as can the possibility of water accumulation at the active sites of the catalyst, thereby improving the stability of the hydrogenation catalyst, especially its stability under low-temperature liquid-phase conditions.

[0021] According to the present invention, in some embodiments, the content of the oxide of metal M in the hydrogenation catalyst is 0.5-15 wt%, preferably 1-10 wt%. Using the aforementioned embodiments, the catalytic activity of the hydrogenation catalyst can be better improved, especially its catalytic activity when used under cryogenic liquid phase conditions.

[0022] According to the present invention, in some embodiments, the content of Cu in the hydrogenation catalyst is 30-75 wt%, preferably 48-67 wt%. Using the aforementioned embodiments, the catalytic activity of the hydrogenation catalyst can be better improved, especially its catalytic activity when used under cryogenic liquid phase conditions.

[0023] According to the present invention, in some embodiments, the content of the support in the hydrogenation catalyst is 5-69 wt%, preferably 20-50 wt%. Using the aforementioned embodiments, the hydrogenation catalyst exhibits better catalytic activity and stability.

[0024] A second aspect of the present invention provides a method for preparing the hydrogenation catalyst of the present invention, the method comprising:

[0025] (1) A kneaded compound containing copper source, metal M source, SiO2 source and F source is optionally shaped and heat-treated to obtain a catalyst precursor.

[0026] (2) The catalyst precursor obtained in step (1) is reduced to obtain the hydrogenation catalyst.

[0027] In this invention, the hydrogenation catalyst prepared by the method of this invention not only has good catalytic hydrogenation activity, but also reduces the possibility of dehydration side reactions and the possibility of water accumulation at the active site of the catalyst during use, thereby improving the stability of the catalyst at low temperature.

[0028] According to the present invention, it is understood that the kneaded compound containing copper source, metal M source, SiO2 source and F source is obtained by kneading components such as copper source, metal M source, SiO2 source and F source. The kneading method and apparatus can be any method and apparatus in the art, such as kneading in a kneading machine. The kneading time can be selected as needed, such as kneading for 10-60 minutes.

[0029] According to some embodiments of the present invention, the copper source is selected from at least one of copper nitrate, hydrochloride and basic carbonate.

[0030] According to the present invention, in some embodiments, the metal M source is selected from at least one of the following: nitrate, hydrochloride, metal acid salt, and basic carbonate of metal M.

[0031] According to some embodiments of the present invention, the SiO2 source is selected from silica powder and / or silica sol.

[0032] In this invention, the silica sol is a dispersion of nano-sized silica particles in water, which can be obtained commercially, for example, silica sol AN-40 with a mass concentration of 40 wt%.

[0033] According to the present invention, in some embodiments, the F source is selected from HF and / or ammonium fluoride; wherein HF is generally present in the form of an aqueous solution and can be obtained commercially, such as hydrofluoric acid, which is an aqueous solution of HF. In this invention, hydrofluoric acid with a concentration of 40 wt% is used as an example for illustrative purposes.

[0034] According to the present invention, in order to better form the kneaded compound, in some embodiments the kneaded compound also contains water; the amount of water can be selected as needed, for example, the amount of water is 5%-150% of the mass of the copper source.

[0035] According to the present invention, when using water, water can be directly kneaded with raw materials such as copper source, metal M source, SiO2 source and F source, or at least one of copper source, metal M source, SiO2 source and F source can be prepared into an aqueous solution of a certain concentration using water and then kneaded, or at least one of copper source, metal M source, SiO2 source and F source can be prepared into an aqueous solution of a certain concentration using a portion of water and then added to the remaining water for kneading.

[0036] According to the present invention, in order to better form the kneaded compound and subsequently obtain a hydrogenation catalyst of a certain shape as needed, in some embodiments, the kneaded compound further contains an extrusion aid; wherein, the specific type of extrusion aid is not particularly limited, for example, the extrusion aid is selected from at least one of citric acid, guar gum powder and graphite powder, preferably citric acid and / or guar gum powder.

[0037] According to the present invention, the amount of the extrusion aid is not particularly limited as long as it affects the purpose of the present invention. In some embodiments, the amount of the extrusion aid is 1%-20% of the mass of the copper source.

[0038] According to the present invention, "optional molding" means that molding may or may not be performed depending on the desired shape of the final hydrogenation catalyst, preferably molding, and the molding method may be a conventional molding method in the art, such as extruding the kneaded compound into strips in a twin-screw extruder, wherein the diameter of the strips may be 1.0-3.0 mm and the length may be 2-15 mm.

[0039] According to some embodiments of the present invention, the heat treatment process includes drying and calcination.

[0040] According to the present invention, the drying conditions are not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the drying conditions include a drying temperature of 80-150°C.

[0041] According to the present invention, in some embodiments, the drying conditions include a drying time of 5-20 hours.

[0042] According to the present invention, the calcination conditions are not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the calcination conditions include a calcination temperature of 300-500°C.

[0043] According to the present invention, in some embodiments, the calcination conditions include a calcination time of 2-10 hours.

[0044] According to the present invention, in some embodiments, the reduction process involves a reduction reaction of the catalyst precursor in the presence of hydrogen. Using the aforementioned embodiments, the prepared hydrogenation catalyst exhibits better catalytic activity and stability.

[0045] According to some preferred embodiments of the present invention, the conditions for the reduction reaction include: a hydrogen pressure of 0.1-1 MPa.

[0046] According to some preferred embodiments of the present invention, the conditions for the reduction reaction include: a hydrogen gas hourly space velocity of 200-1000 h⁻¹. -1 .

[0047] According to some preferred embodiments of the present invention, the conditions for the reduction reaction include a reduction temperature of 160-270°C. Using the aforementioned embodiments, the hydrogenation catalyst prepared exhibits better catalytic activity and stability.

[0048] According to some preferred embodiments of the present invention, the conditions for the reduction reaction include a reduction time of 2-10 hours.

[0049] A third aspect of the present invention provides the application of the catalyst described herein in hydrogenation reactions.

[0050] The catalyst in this invention exhibits better catalytic activity and stability when used in hydrogenation reactions.

[0051] According to some preferred embodiments of the present invention, the catalyst described herein is used in a liquid-phase hydrogenation reaction.

[0052] Liquid-phase hydrogenation reactions are generally carried out at low temperatures. The hydrogenation catalyst in this invention not only has high catalytic activity in low-temperature liquid-phase hydrogenation reactions, but also reduces the possibility of dehydration side reactions and the possibility of water accumulation at the active sites of the catalyst, thereby improving the stability of the catalyst in low-temperature reactions.

[0053] According to some preferred embodiments of the present invention, the hydrogenation catalyst is used in the liquid-phase hydrogenation of ketone compounds.

[0054] The fourth aspect of the present invention provides a method for preparing 1-phenylethanol by liquid-phase hydrogenation of acetophenone, the method comprising: in the presence of the hydrogenation catalyst described in the present invention, contacting a mixture of acetophenone-containing raw materials with hydrogen to carry out a hydrogenation reaction to obtain a material containing 1-phenylethanol.

[0055] In this invention, the hydrogenation catalyst of this invention is used in the liquid-phase hydrogenation of acetophenone to prepare 1-phenylethanol, which can achieve a high conversion rate of acetophenone and a high selectivity of 1-phenylethanol; and when the catalyst is stably operated for 3000h, the conversion rate of acetophenone and the selectivity of 1-phenylethanol do not decrease significantly. The hydrogenation catalyst of this invention can be well used in the industrial production of 1-phenylethanol by liquid-phase hydrogenation of acetophenone.

[0056] According to the present invention, the acetophenone-containing raw material mixture refers to the raw material mixture of acetophenone and solvent. The present invention does not have any special restrictions on the type of solvent. For example, the solvent in the raw material mixture can be an alkanol; wherein, preferably, the alkanol is a C1-C5 alkyl alcohol, and more preferably methanol and / or ethanol.

[0057] According to the present invention, there is no particular limitation on the concentration of acetophenone in the raw material mixture containing acetophenone, for example, a raw material mixture with a concentration of 10-50 wt% acetophenone.

[0058] According to the present invention, those skilled in the art can select conditions favorable to the hydrogenation reaction as needed. In some embodiments, the conditions for the hydrogenation reaction include: the mass hourly space velocity (WHSV) of acetophenone in the feed mixture is 0.1-1.0 h⁻¹. -1 Preferably, it is 0.3-0.6h. -1 including but not limited to 0.35h -1 0.4h -1 0.45h -1 0.5h -10.55h -1 wait.

[0059] According to the present invention, in some embodiments, the conditions for the hydrogenation reaction include: the hydrogen pressure is 1.0-5.0 MPa, preferably 1.5-4.0 MPa, including but not limited to 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, etc.

[0060] According to the present invention, in some embodiments, the conditions for the hydrogenation reaction include: the feed molar ratio of hydrogen to acetophenone is 1.0-20.0, preferably 1.2-15.0, including but not limited to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, etc.

[0061] According to the present invention, in some embodiments, the reaction temperature is 60-120°C, preferably 65-90°C, including but not limited to 70°C, 75°C, 80°C, 85°C, etc.

[0062] The present invention will be described in detail below through examples. The content of F element in the hydrogenation catalyst was obtained by XRF testing.

[0063] Example 1

[0064] Preparation of hydrogenation catalysts:

[0065] 103.6 g of basic copper carbonate, 13.7 g of ammonium molybdate, 4.9 g of ammonium fluoride, and 27.5 g of SiO2 powder were placed in a kneader, 10 g of citric acid and 5 g of guar gum powder were added, and 120 g of water was added. After kneading for 30 min, the mixture was extruded into thin strips with a diameter of 2 mm in an extruder. The strips were dried at 120 °C for 10 h and calcined at 350 °C for 4 h to obtain the catalyst precursor CMO-1.

[0066] CMO-1 was loaded into a fixed-bed reactor and reduced with hydrogen at a pressure of 0.5 MPa and a volume hourly space velocity (HHSV) of 500 h⁻¹. -1 The reduction temperature was 230℃ and the reduction time was 6 hours, resulting in hydrogenation catalyst CM-1.

[0067] In the hydrogenation catalyst CM-1, the mass fractions are: Cu 60 parts, MoO3 10 parts, F 2.5 parts, and SiO2 27.5 parts.

[0068] The infrared characterization of the hydroxyl group in the hydrogenation catalyst CM-1 is shown below. Figure 1 As shown.

[0069] Example 2

[0070] Preparation of hydrogenation catalysts:

[0071] 151.2 g of copper nitrate trihydrate, 18.3 g of zinc nitrate hexahydrate, 3.3 g of 40 wt% hydrofluoric acid, 25 g of 40 wt% silica sol AN-40, and 44 g of SiO2 powder were placed in a kneader, 20 g of citric acid and 10 g of guar gum powder were added, and 50 g of water was added. After kneading for 30 min, the mixture was extruded in an extruder to form thin strips with a diameter of 2 mm. The strips were dried at 80 °C for 20 h and calcined at 500 °C for 2 h to obtain the catalyst precursor CMO-2.

[0072] CMO-2 was loaded into a fixed-bed reactor and reduced with hydrogen at a pressure of 0.8 MPa and a volume hourly space velocity (HHSV) of 800 h⁻¹. -1 The reduction temperature was 180℃, and the reduction time was 9 hours, yielding hydrogenation catalyst CM-2.

[0073] In the hydrogenation catalyst CM-2, the mass fractions are: Cu 40 parts, ZnO 5.0 parts, F 1.0 parts, and SiO2 54 parts.

[0074] Example 3

[0075] Preparation of hydrogenation catalysts:

[0076] 120.9 g of basic copper carbonate, 29.4 g of cobalt nitrate hexahydrate, 6.8 g of ammonium fluoride, 30 g of 40% silica sol AN-40, and 7 g of SiO2 powder were placed in a kneader, 5 g of citric acid and 3 g of guar gum powder were added, and 20 g of water was added. After kneading for 20 min, the mixture was extruded in an extruder to form thin strips with a diameter of 2 mm. The strips were dried at 120 °C for 10 h and calcined at 300 °C for 4 h to obtain the catalyst precursor CMO-3.

[0077] CMO-3 was loaded into a fixed-bed reactor and reduced with hydrogen at a pressure of 0.3 MPa and a hydrogen volume hourly space velocity of 800 h⁻¹. -1 The reduction temperature was 200℃ and the reduction time was 5 hours, resulting in hydrogenation catalyst CM-3.

[0078] The hydrogenation catalyst CM-3 has the following mass fractions: Cu 70 parts, CoO 7.5 parts, F 3.5 parts, and SiO2 19 parts.

[0079] Example 4

[0080] Preparation of hydrogenation catalysts:

[0081] Following the method of Example 3, except that 37.8 g of 50 wt% manganese nitrate aqueous solution was used to replace 29.4 g of cobalt nitrate hexahydrate to obtain hydrogenation catalyst CM-4.

[0082] In the hydrogenation catalyst CM-4, the mass fractions are: Cu 70 parts, MnO 7.5 parts, F 3.5 parts, and SiO2 19 parts.

[0083] Example 5

[0084] The method of Example 1 was followed, except that the 12.3 g of ammonium molybdate was replaced with a mixture of 6.2 g of ammonium molybdate and 19.4 g of cobalt nitrate hexahydrate. The resulting catalyst was designated as CM-5, and its mass fractions were: 60 parts Cu, 5.0 parts MoO3, 5.0 parts CoO, 2.5 parts F, and 27.5 parts SiO2.

[0085] Example 6

[0086] The method of Example 1 was followed, except that the 4.9 g of ammonium fluoride was replaced with 20 g of ammonium fluoride. The resulting catalyst was designated CM-6 and its mass fractions were: Cu 59 parts, MoO3 10 parts, F 4.5 parts, and SiO2 26.5 parts.

[0087] Example 7

[0088] 20g of hydrogenation catalyst CM-1 (3-6mm in length) was packed into a 12mm stainless steel reactor and reacted at 65℃ with a hydrogen pressure of 2.0MPa. The acetophenone feedstock was a 30wt% acetophenone ethanol solution, and the acetophenone space velocity was 0.3h⁻¹. -1 The molar ratio of hydrogen to acetophenone was 2.0. After 24 hours of reaction, the conversion rate of acetophenone was 92.0%, the selectivity of 1-phenylethanol was 99.6%, and the selectivity of ethylbenzene was 0.4%.

[0089] Example 8

[0090] The hydrogenation catalyst CM-2 was evaluated using the same method as in Example 7, and the conversion of acetophenone was 75.3%, the selectivity for 1-phenylethanol was 98.5%, and the selectivity for ethylbenzene was 1.5%.

[0091] Example 9

[0092] The hydrogenation catalyst CM-3 was evaluated using the same method as in Example 7, and the conversion of acetophenone was 73.2%, the selectivity for 1-phenylethanol was 98.7%, and the selectivity for ethylbenzene was 1.3%.

[0093] Example 10

[0094] The hydrogenation catalyst CM-4 was evaluated using the same method as in Example 7, and the conversion of acetophenone was 67.8%, the selectivity for 1-phenylethanol was 99.9%, and the selectivity for ethylbenzene was 0.1%.

[0095] Example 11

[0096] The hydrogenation catalyst CM-5 was evaluated using the same method as in Example 7, and the conversion of acetophenone was 93.0%, the selectivity for 1-phenylethanol was 99.7%, and the selectivity for ethylbenzene was 0.3%.

[0097] Example 12

[0098] The hydrogenation catalyst CM-6 was evaluated using the same method as in Example 7, resulting in a conversion of acetophenone of 65.0%, a selectivity of 1-phenylethanol of 98.5%, and a selectivity of ethylbenzene of 1.5%.

[0099] Example 13

[0100] 20g of hydrogenation catalyst CM-1 (3-6mm in length) was packed into a 12mm stainless steel reactor and reacted at 70℃ with a hydrogen pressure of 2.0MPa. The acetophenone feedstock was a 30wt% acetophenone ethanol solution, and the acetophenone space velocity was 0.3h⁻¹. -1 The molar ratio of hydrogen to acetophenone was 3.0. After 24 hours of reaction, the conversion rate of acetophenone was 93.6%, the selectivity of 1-phenylethanol was 99.5%, and the selectivity of ethylbenzene was 0.5%.

[0101] Example 14

[0102] 20g of hydrogenation catalyst CM-1 (3-6mm in length) was packed into a 12mm stainless steel reactor and reacted at 85℃ with a hydrogen pressure of 1.5MPa. The acetophenone feedstock was a 30wt% acetophenone ethanol solution, and the acetophenone space velocity was 0.4h⁻¹. -1 The molar ratio of hydrogen to acetophenone was 15. After 24 hours of reaction, the conversion rate of acetophenone was 95.0%, the selectivity of 1-phenylethanol was 98.5%, and the selectivity of ethylbenzene was 1.5%.

[0103] Example 15

[0104] 20g of hydrogenation catalyst CM-1 (3-6mm in length) was packed into a 12mm stainless steel reactor and reacted at 90℃ with a hydrogen pressure of 3.0MPa. The acetophenone feedstock was a 30wt% acetophenone ethanol solution, and the acetophenone space velocity was 0.6h⁻¹. -1 The molar ratio of hydrogen to acetophenone was 5. After 24 hours of reaction, the conversion rate of acetophenone was 98.0%, the selectivity of 1-phenylethanol was 97.3%, and the selectivity of ethylbenzene was 2.7%.

[0105] Example 16

[0106] 20g of hydrogenation catalyst CM-1 (3-6mm in length) was packed into a 12mm stainless steel reactor and reacted at 60℃ with a hydrogen pressure of 4.0MPa. The acetophenone feedstock was a 30wt% acetophenone ethanol solution, and the acetophenone space velocity was 0.2h⁻¹. -1 The molar ratio of hydrogen to acetophenone was 1.5. After 24 hours of reaction, the conversion rate of acetophenone was 89.2%, the selectivity of 1-phenylethanol was 99.9%, and the selectivity of ethylbenzene was 0.1%.

[0107] Example 17

[0108] The lifetime of catalyst CM-1 was evaluated using the same method as in Example 7, and the results are shown in Table 1.

[0109] Comparative Example 1

[0110] Preparation of hydrogenation catalysts:

[0111] Following the method of Example 1, except that ammonium fluoride was not added, the resulting hydrogenation catalyst was cCM-1.

[0112] In the hydrogenation catalyst cCM-1, the mass fractions are: Cu 61.5 parts, MoO 10 parts, and SiO2 28.5 parts.

[0113] The hydrogenation catalyst cCM-1 was evaluated for its lifetime using the same method as in Example 7, and the results are shown in Table 1.

[0114] The infrared characterization of the hydroxyl group in the hydrogenation catalyst cCM-1 is shown below. Figure 1 As shown.

[0115] Comparative Example 2

[0116] Preparation of hydrogenation catalysts:

[0117] Following the method of Example 3, except that 48.1 g of magnesium nitrate hexahydrate was used instead of 29.4 g of cobalt nitrate hexahydrate to obtain the hydrogenation catalyst cCM-2.

[0118] In the hydrogenation catalyst cCM-2, the mass fractions are: Cu 70 parts, MgO 7.5 parts, F 3.5 parts, and SiO2 19 parts.

[0119] The hydrogenation catalyst cCM-2 was evaluated using the same method as in Example 7, and the conversion of acetophenone was 53.2%, the selectivity for 1-phenylethanol was 98.9%, and the selectivity for ethylbenzene was 1.1%.

[0120] Table 1

[0121]

[0122]

[0123] As can be seen from the results of the examples and Table 1, the hydrogenation catalyst of the present invention for the hydrogenation of acetophenone to 1-phenylethanol not only has good catalytic activity and selectivity for 1-phenylethanol, but also has good stability.

[0124] pass Figure 1 It can be seen that the hydrogenation catalyst CM-1 is at 3746 cm⁻¹ -1 The hydroxyl absorption peak at the catalyst surface is significantly weaker compared to that of hydrogenation catalyst cCM-1, indicating that the modification of F significantly reduces the concentration of silanol groups on the surface of the hydrogenation catalyst.

[0125] 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 liquid-phase hydrogenation catalyst for ketone compounds, characterized in that, The hydrogenation catalyst comprises: a SiO2 carrier, an active component Cu, a modifying element F, and an oxide of a metal M; The metal M is selected from at least one of Zn, Mn, Co, Cr, Mo, and Ni; and F is fluorine element. The preparation method of the hydrogenation catalyst comprises: (1) kneadates of a copper source, a metal M source, a SiO2 source, and a F source are formed and heat-treated to obtain a catalyst precursor; (2) the catalyst precursor obtained in step (1) is reduced to obtain the hydrogenation catalyst.

2. The hydrogenation catalyst of claim 1, wherein, The metal M is selected from at least one of Zn, Mn, Co, and Mo.

3. The hydrogenation catalyst according to claim 1 or 2, wherein, The metal M is Co and / or Mo.

4. The hydrogenation catalyst according to claim 1 or 2, wherein, in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is 100 wt%, the content of the oxide of the metal M is 0.5-15 wt%; and / or the content of Cu is 30-75 wt%; and / or the content of the carrier is 5-69 wt%.

5. The hydrogenation catalyst according to claim 4, wherein, in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is 100 wt%, the content of the oxide of the metal M is 1-10 wt%; and / or the content of Cu is 48-67 wt%; and / or the content of the carrier is 20-50 wt%. In the preparation method of the hydrogenation catalyst, the copper source is selected from at least one of nitrate, hydrochloride, and basic carbonate of copper; and / or the metal M source is selected from at least one of nitrate, hydrochloride, and basic carbonate of the metal M; and / or the SiO2 source is selected from silica powder and / or silica sol; and / or the F source is selected from HF and / or ammonium fluoride. In the preparation method of the hydrogenation catalyst, the kneadates further contain water, and / or the kneadates further contain a extrusion aid; and / or the amount of the extrusion aid is 1%-20% of the mass of the copper source. The amount of the water is 5%-150% of the mass of the copper source; and / or the extrusion aid is selected from at least one of citric acid, sesbania powder, and graphite powder. The extrusion aid is citric acid and / or sesbania powder. In the preparation method of the hydrogenation catalyst, the heat treatment process comprises drying and calcination. The drying conditions comprise: a drying temperature of 80-150°C; and / or a drying time of 5-20h; and / or The calcination conditions comprise: a calcination temperature of 300-500°C; and / or a calcination time of 2-10h. In the preparation method of the hydrogenation catalyst, the reduction process is that the catalyst precursor is subjected to a reduction reaction in the presence of hydrogen. The reduction reaction conditions comprise: The pressure of hydrogen is 0.1-1MPa; and / or 6. The hydrogenation catalyst of claim 1 or 2, wherein, The reduction temperature is 160-270°C; and / or The reduction time is 2-10h.

14. Use of the hydrogenation catalyst according to any one of claims 1-13 in liquid-phase hydrogenation of ketone compounds. The method comprises:

7. The hydrogenation catalyst of claim 1 or 2, wherein, ​ ​ ​ 8. The hydrogenation catalyst of claim 7, wherein, ​ ​ 9. The hydrogenation catalyst of claim 8, wherein, ​ 10. The hydrogenation catalyst of claim 1 or 2, wherein, ​ 11. The hydrogenation catalyst of claim 10, wherein, ​ ​ 12. The hydrogenation catalyst of claim 1 or 2, wherein, ​ 13. The hydrogenation catalyst of claim 12, wherein, ​ ​ The gas hourly space velocity of hydrogen is 200-1000 h -1 ; and / or ​ ​ ​ 15. A process for the production of 1-phenylethanol by liquid phase hydrogenation of acetophenone, characterized in that, ​ The raw material mixture containing acetophenone is contacted with hydrogen in the presence of the hydrogenation catalyst according to any one of claims 1-13 to obtain a material containing 1-phenylethanol.

16. The method of claim 15, wherein, the solvent in the raw material mixture is a C1-C5 alkyl alcohol; and / or the conditions of the hydrogenation reaction include: The mass space velocity of the acetophenone in the raw material mixture is 0.1-1.0 h -1 ; and / or the hydrogen pressure is 1.0-5.0 MPa; and / or the feed molar ratio of hydrogen to acetophenone is 1.0-20.0; and / or the reaction temperature is 60-120°C.

17. The method of claim 16, wherein, the solvent in the raw material mixture is a C1-C5 alkyl alcohol; and / or the conditions of the hydrogenation reaction include: The mass space velocity of the acetophenone in the raw material mixture is 0.3-0.6 h -1 ; and / or the hydrogen pressure is 1.5-4.0 MPa; and / or the feed molar ratio of hydrogen to acetophenone is 1.2-15.0; and / or the reaction temperature is 65-90°C.

18. The method of claim 16 or 17, wherein, the solvent in the raw material mixture is methanol and / or ethanol. the solvent in the raw material mixture is a C1-C5 alkyl alcohol; and / or the conditions of the hydrogenation reaction include: the hydrogen pressure is 1.0-5.0 MPa; and / or the feed molar ratio of hydrogen to acetophenone is 1.0-20.0; and / or the reaction temperature is 60-120°C. the solvent in the raw material mixture is a C1-C5 alkyl alcohol; and / or the conditions of the hydrogenation reaction include: the hydrogen pressure is 1.5-4.0 MPa; and / or the feed molar ratio of hydrogen to acetophenone is 1.2-15.0; and / or the reaction temperature is 65-90°C. the solvent in the raw material mixture is methanol and / or ethanol.

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