Hydrogenation catalyst, preparation method and application thereof, and 1-phenethyl alcohol prepared by acetophenone liquid phase hydrogenation

Abstract

The invention relates to the technical field of catalytic hydrogenation, and discloses a hydrogenation catalyst and a preparation method and application thereof.The hydrogenation catalyst is used for preparing 1-phenethyl alcohol through acetophenone liquid-phase hydrogenation.The catalyst comprises a SiO2 carrier, an active component Cu, a modification element F and an oxide of metal M. Wherein the metal M is selected from at least one of group IIB metal, group VIB metal, group VIIB metal and group VIII metal; f is a fluorine element. The hydrogenation catalyst has good hydrogenation activity and long service life, and has the characteristic of long service life when being used for hydrogenation reaction, especially low-temperature liquid-phase hydrogenation reaction, for example, when being used for selectively hydrogenating acetophenone into 1-phenethyl alcohol, the hydrogenation catalyst has low-temperature acetophenone hydrogenation activity and high selectivity, and can be used for preparing 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol or 1-phenethyl alcohol. And meanwhile, the service life is long.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic hydrogenation, and in particular to a hydrogenation catalyst and a preparation method and application thereof, and preparation of 1-phenylethanol by liquid phase hydrogenation of acetophenone. Background Art

[0002] The selective hydrogenation of acetophenone (ACP) to α-methylbenzyl alcohol (MBA) has been studied on different metals. Common catalysts for acetophenone hydrogenation include precious metal catalysts with palladium, platinum, ruthenium, rhodium as active components, nickel-based catalysts and copper-based catalysts. Although the reaction conditions are mild, the selectivity of α-methylbenzyl alcohol is poor when using precious metal catalysts and nickel-based catalysts for acetophenone hydrogenation [Wang Youzhen, Qiao Minghua, Hu Huarong, Yan Shirun, Wang Weijiang, Fan Kangnian, Preparation and Characterization of Highly Selective Ni-Sn-B / SiO2 Amorphous Catalyst for Acetophenone Hydrogenation, Acta Chemica 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 have good low-temperature activity, strong selectivity for CO bonds and weak ability to form CC 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 / SiO2catalyst.[J]Applied Catalysis A:General 349(2008)100-109] The kinetics of acetophenone hydrogenation over Cu / SiO2 catalyst was studied. The results showed that when it was assumed that acetophenone was strongly adsorbed on the catalyst surface and phenylethanol was weakly adsorbed on the catalyst, the obtained kinetic model was consistent with the actual reaction results. Wang Bing et al. [Wang Bing, Qu Yanan, An Hao, Wang Jinkai, Guo Zhenmei, Lv Zhiguo. Preparation of high-performance nano Cu / SiO2 catalyst and its catalytic performance in hydrogenation of aromatic ketones. Journal of Qingdao University of Science and Technology (Natural Science Edition), Vol. 41, No. 3, June 2020, 48-55] The Cu / SiO2 catalyst prepared by the sol-gel method has a smaller particle size and good dispersion of active species compared with the co-precipitation method. Finally, the mechanism of acetophenone hydrogenation was explored. The synergistic effect of Cu0 and Cu+ improved the activity and stability of the catalyst. Sumitomo Chemical Company of Japan has reported in patents that Cu / SiO2 is used for acetophenone hydrogenation reaction [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 higher. At the same time, the addition of alkali or alkaline earth metals can effectively prevent the occurrence of α-methylbenzyl alcohol hydrogenolysis reaction.

[0003] The catalyst for preparing α-methylbenzyl alcohol from acetophenone is a hydrogenation catalyst, and the above reports do not involve the problem of catalyst deactivation under low-temperature reaction conditions. Summary of the invention

[0004] During high-temperature hydrogenation, the catalyst may become deactivated due to carbon deposition. However, the inventors have found that in the hydrogenation reaction, a side reaction of generating water is generally involved. For example, after acetophenone is hydrogenated to generate 1-phenylethanol, the hydrogenolysis of 1-phenylethanol to generate ethylbenzene and water is always inevitable. If the reaction is carried out at a lower temperature, the accumulation of water will also lead to catalyst deactivation. This is the main problem faced by hydrogenation catalysts.

[0005] Based on this, the purpose of the present invention is to overcome the problem that the hydrogenation catalyst in the prior art is easily deactivated when used, especially when used under low-temperature hydrogenation conditions, and to provide a hydrogenation catalyst and its preparation method and application, and acetophenone liquid phase hydrogenation to prepare 1-phenylethanol. The hydrogenation catalyst has good hydrogenation activity and a long service life. When it is used in a hydrogenation reaction, especially a low-temperature liquid phase hydrogenation reaction, the catalyst has the characteristics of a 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 a long service life.

[0006] The first aspect of the present invention provides a hydrogenation catalyst, which includes: a SiO2 carrier, 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 metals, Group VIB metals, Group VⅡB metals and Group VIII metals; and F is a fluorine element.

[0007] The second aspect of the present invention provides a method for preparing the hydrogenation catalyst of the present invention, which comprises: (1) optionally molding and heat treating a kneaded product containing a copper source, a metal M source, a SiO2 source and a F source to obtain a catalyst precursor; (2) reducing the catalyst precursor obtained in step (1) to obtain the hydrogenation catalyst.

[0008] The third aspect of the present invention provides use of the catalyst of the present invention in a hydrogenation reaction.

[0009] A 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 of the present invention, contacting a raw material mixed liquid containing acetophenone with hydrogen to carry out a hydrogenation reaction to obtain a material containing 1-phenylethanol.

[0010] When the hydrogenation catalyst of the present invention is used for hydrogenation reaction, especially liquid phase hydrogenation reaction, the activity of the catalyst can be better improved, so that the hydrogenation reaction can be carried out at a lower temperature, and the possibility of dehydration side reaction and the possibility of water accumulation at the active center of the catalyst can be reduced, thereby improving the stability of the hydrogenation catalyst of the present invention during low temperature reaction. For example, when the hydrogenation catalyst of the present invention is used for preparing 1-phenylethanol by liquid phase hydrogenation of acetophenone, a high acetophenone conversion rate and 1-phenylethanol selectivity can be achieved, and the performance of the hydrogenation catalyst does not significantly decrease after stable operation for 3000 hours, and the catalyst can be better used in the industrial production of preparing 1-phenylethanol by hydrogenation of acetophenone. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is the hydroxyl infrared spectrum of the hydrogenation catalyst CM-1 in Example 1 and the hydrogenation catalyst cCM-1 in Comparative Example 1. DETAILED DESCRIPTION

[0012] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0013] The first aspect of the present invention provides a hydrogenation catalyst, which includes: a SiO2 carrier, 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 metals, Group VIB metals, Group VⅡB metals and Group VIII metals; and F is a fluorine element.

[0014] In the present invention, the hydrogenation catalyst of the present invention has good catalytic activity and selectivity of the target product after hydrogenation, especially under low-temperature hydrogenation reaction conditions, the hydrogenation catalyst of the present invention has the advantages of better hydrogenation activity, high selectivity of 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 embodiment, the oxide of the metal M can better cooperate with the active component to increase the catalytic activity of the catalyst, especially the catalytic activity and stability of the catalyst when used for low-temperature liquid phase hydrogenation reaction.

[0016] According to the present invention, in some preferred embodiments, the metal M is at least one of Zn, Mn, Co and Mo. By adopting the above embodiment, the synergistic effect of the oxide of the metal M and the active component can be further increased to increase the catalytic activity of the hydrogenation catalyst.

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

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

[0019] According to the present invention, in some more preferred embodiments, the metal M is Co and Mo; wherein, when Co and Mo are used simultaneously, there is no specific requirement for the ratio between the two, for example, based on Co and Mo as corresponding oxides, the mass ratio of Co to Mo 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 0.5-5wt%, preferably 1-3wt%. The above embodiment can reduce the possibility of dehydration side reaction in the hydrogenation reaction and reduce the possibility of water accumulation in the active center of the catalyst, thereby improving the stability of the hydrogenation catalyst, especially when used under low temperature liquid phase conditions.

[0021] According to the present invention, in some embodiments, in the hydrogenation catalyst: the content of the oxide of metal M is 0.5-15wt%, preferably 1-10wt%. The above embodiment can better improve the catalytic activity of the hydrogenation catalyst, especially the catalytic activity when used under low temperature liquid phase conditions.

[0022] According to the present invention, in some embodiments, the content of Cu in the hydrogenation catalyst is 30-75wt%, preferably 48-67wt%. The above embodiments can better improve the catalytic activity of the hydrogenation catalyst, especially the catalytic activity when used under low temperature liquid phase conditions.

[0023] According to the present invention, in some embodiments, in the hydrogenation catalyst, the content of the carrier is 5-69wt%, preferably 20-50wt%. With the above embodiment, the hydrogenation catalyst has better catalytic activity and stability.

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

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

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

[0027] In the present invention, the hydrogenation catalyst prepared by the preparation method of the present invention not only has good catalytic hydrogenation activity, but also can reduce the possibility of dehydration side reactions and the possibility of water accumulation in the active center of the catalyst when used, thereby improving the stability of the catalyst during low-temperature reactions.

[0028] According to the present invention, it can be understood that the kneaded material 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, wherein the kneading method and apparatus can be any method and apparatus in the art, such as kneading in a kneader, and the kneading time can be selected according to needs, such as kneading for 10-60 minutes.

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

[0030] According to the present invention, in some embodiments, the metal M source is selected from at least one of nitrates, hydrochlorides, metal acid salts and basic carbonates of metal M.

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

[0032] In the present invention, the silica sol is a dispersion of nano-scale silicon dioxide 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 the present invention, hydrofluoric acid with a concentration of 40 wt % is used as an example for illustrative description.

[0034] According to the present invention, in order to better form the kneaded product, in some embodiments, the kneaded product further contains water; the amount of the water can be selected according to needs, for example, the amount of the 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 the copper source, metal M source, SiO2 source and F source can be prepared into an aqueous solution of a certain concentration using water and kneaded, or at least one of the copper source, metal M source, SiO2 source and F source can be prepared into an aqueous solution of a certain concentration using part of water, and then added to the remaining water for kneading.

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

[0037] According to the present invention, as long as it can affect the purpose of the present invention, the amount of the extrusion aid is not particularly limited. 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, "optionally shaping" means that shaping may or may not be performed according to the desired shape of the final hydrogenation catalyst, preferably shaping is performed, and the shaping method may be a conventional shaping method in the art, such as extruding the kneaded product into thin strips in a twin-screw extruder, and the diameter of the thin strips may be 1.0-3.0 mm and the length may be 2-15 mm.

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

[0040] According to the present invention, as long as the purpose of the present invention can be achieved, the drying conditions are not particularly limited. 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: drying time is 5-20 hours.

[0042] According to the present invention, as long as the purpose of the present invention can be achieved, the calcination conditions are not particularly limited. 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: calcination time 2-10h.

[0044] According to the present invention, in some embodiments, the reduction process is: in the presence of hydrogen, the catalyst precursor undergoes a reduction reaction. Using the above embodiment, the prepared hydrogenation catalyst has better catalytic activity and stability.

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

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

[0047] According to the present invention, in some preferred embodiments, the reduction reaction conditions include: the reduction temperature is 160-270° C. By adopting the above embodiment, the prepared hydrogenation catalyst has better catalytic activity and stability.

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

[0049] The third aspect of the present invention provides use of the catalyst of the present invention in a hydrogenation reaction.

[0050] The catalyst of the present invention has better catalytic activity and stability when used for hydrogenation reaction.

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

[0052] Liquid phase hydrogenation reactions are generally carried out at relatively low temperatures. The hydrogenation catalyst of the present invention not only has a high catalytic activity during low temperature liquid phase hydrogenation reactions, but also can reduce the possibility of dehydration side reactions and the possibility of water accumulation at the active center of the catalyst, thereby improving the stability of the catalyst during low temperature reactions.

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

[0054] A 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 of the present invention, contacting a raw material mixed liquid containing acetophenone with hydrogen to carry out a hydrogenation reaction to obtain a material containing 1-phenylethanol.

[0055] In the present invention, the hydrogenation catalyst of the present invention is used for preparing 1-phenylethanol by liquid-phase hydrogenation of acetophenone, and a high conversion rate of acetophenone and selectivity of 1-phenylethanol can be achieved; and when the catalyst is stably operated for 3000 hours, the conversion rate of acetophenone and the selectivity of 1-phenylethanol do not decrease significantly, and the hydrogenation catalyst of the present invention can be well used in the industrial production of preparing 1-phenylethanol by liquid-phase hydrogenation of acetophenone.

[0056] According to the present invention, the raw material mixture containing acetophenone refers to a raw material mixture of acetophenone and a solvent. The present invention has no particular limitation on the type of the solvent. For example, the solvent in the raw material mixture may be an alkanol; wherein the alkanol is preferably a C1-C5 alkyl alcohol, further methanol and / or ethanol.

[0057] According to the present invention, the concentration of acetophenone in the raw material mixed solution containing acetophenone is not particularly limited, for example, the raw material mixed solution has a concentration of 10-50 wt % of acetophenone.

[0058] According to the present invention, for the conditions of the hydrogenation reaction, those skilled in the art can select conditions that are conducive to the hydrogenation reaction as needed. In some embodiments, the conditions of the hydrogenation reaction include: the mass space velocity of acetophenone in the raw material mixture is 0.1-1.0h -1 , preferably 0.3-0.6h -1 , including but not limited to 0.35h -1 、0.4h -1 , 0.45h -1 、0.5h -1、0.55h -1 wait.

[0059] According to the present invention, in some embodiments, the conditions of 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 of the hydrogenation reaction include: a feed molar ratio of hydrogen to acetophenone of 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, wherein the content of F element in the hydrogenation catalyst is obtained by XRF testing.

[0063] Example 1

[0064] Preparation of hydrogenation catalyst:

[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 sesbania 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, dried at 120 ° C for 10 h, and calcined at 350 ° C for 4 h to obtain catalyst precursor CMO-1;

[0066] CMO-1 was loaded into a fixed bed reactor and reduced with hydrogen at a hydrogen pressure of 0.5 MPa and a hydrogen volume space velocity of 500 h -1 The reduction temperature was 230°C and the reduction time was 6 hours, and the obtained hydrogenation catalyst was CM-1.

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

[0068] The infrared characterization image of the hydroxyl group of hydrogenation catalyst CM-1 is as follows Figure 1 shown.

[0069] Example 2

[0070] Preparation of hydrogenation catalyst:

[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 sesbania powder were added, and 50 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, dried at 80°C for 20 h, and calcined at 500°C for 2 h to obtain a catalyst precursor CMO-2.

[0072] CMO-2 was loaded into a fixed bed reactor and reduced with hydrogen at a hydrogen pressure of 0.8 MPa and a hydrogen volume space velocity of 800 h -1 , the reduction temperature was 180°C, the reduction time was 9 hours, and the hydrogenation catalyst CM-2 was obtained.

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

[0074] Example 3

[0075] Preparation of hydrogenation catalyst:

[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 sesbania powder were added, and 20 g of water was added. After kneading for 20 min, it was extruded into a thin strip with a diameter of 2 mm in an extruder, dried at 120°C for 10 h, and calcined at 300°C for 4 h to obtain a catalyst precursor CMO-3;

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

[0078] In the hydrogenation catalyst CM-3, the mass proportions are: Cu is 70 parts, CoO is 7.5 parts, F is 3.5 parts, and SiO2 is 19 parts.

[0079] Example 4

[0080] Preparation of hydrogenation catalyst:

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

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

[0083] Example 5

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

[0085] Example 6

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

[0087] Example 7

[0088] 20 g of hydrogenation catalyst CM-1 (length 3-6 mm) was loaded into a 12 mm stainless steel reactor and reacted at 65 °C with a hydrogen pressure of 2.0 MPa. The acetophenone raw material was a 30 wt% acetophenone ethanol solution and the acetophenone space velocity was 0.3 h -1 The molar ratio of hydrogen to acetophenone was 2.0. Samples were taken after 24 hours of reaction, and 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 in the same manner as in Example 7, and the conversion rate of acetophenone obtained was 75.3%, the selectivity of 1-phenylethanol was 98.5%, and the selectivity of ethylbenzene was 1.5%.

[0091] Example 9

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

[0093] Example 10

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

[0095] Embodiment 11

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

[0097] Example 12

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

[0099] Embodiment 13

[0100] 20 g of hydrogenation catalyst CM-1 (length 3-6 mm) was loaded into a 12 mm stainless steel reactor and reacted at 70 °C with a hydrogen pressure of 2.0 MPa. The acetophenone raw material was a 30 wt% acetophenone ethanol solution and the acetophenone space velocity was 0.3 h -1 The molar ratio of hydrogen to acetophenone was 3.0. Samples were taken after 24 hours of reaction, and 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] Embodiment 14

[0102] 20 g of hydrogenation catalyst CM-1 (length 3-6 mm) was loaded into a 12 mm stainless steel reactor and reacted at 85 °C with a hydrogen pressure of 1.5 MPa. The acetophenone raw material was a 30 wt% acetophenone ethanol solution and the acetophenone space velocity was 0.4 h -1 The molar ratio of hydrogen to acetophenone was 15, and samples were taken 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] Embodiment 15

[0104] 20 g of hydrogenation catalyst CM-1 (length 3-6 mm) was loaded into a 12 mm stainless steel reactor and reacted at 90 °C with a hydrogen pressure of 3.0 MPa. The acetophenone raw material was a 30 wt% acetophenone ethanol solution and the acetophenone space velocity was 0.6 h -1 The molar ratio of hydrogen to acetophenone was 5, and samples were taken 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] 20 g of hydrogenation catalyst CM-1 (length 3-6 mm) was loaded into a 12 mm stainless steel reactor and reacted at 60 °C with a hydrogen pressure of 4.0 MPa. The acetophenone raw material was a 30 wt% acetophenone ethanol solution and the acetophenone space velocity was 0.2 h -1 The molar ratio of hydrogen to acetophenone was 1.5. Samples were taken after 24 hours of reaction, and 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] Embodiment 17

[0108] The life of catalyst CM-1 was evaluated in the same manner as in Example 7. The results are shown in Table 1.

[0109] Comparative Example 1

[0110] Preparation of hydrogenation catalyst:

[0111] The method of Example 1 was followed, except that ammonium fluoride was not added, and the obtained hydrogenation catalyst was cCM-1.

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

[0113] The catalyst life of the hydrogenation catalyst cCM-1 was evaluated in the same manner as in Example 7. The results are shown in Table 1.

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

[0115] Comparative Example 2

[0116] Preparation of hydrogenation catalyst:

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

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

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

[0120] Table 1

[0121]

[0122]

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

[0124] pass Figure 1 It can be seen that the hydrogenation catalyst CM-1 has a peak at 3746 cm -1 The hydroxyl absorption peak at is significantly weakened compared with that of the hydrogenation catalyst cCM-1, which indicates 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 are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydrogenation catalyst, characterized in that The catalyst comprises: a SiO2 carrier, an active component Cu, a modification element F and an oxide of a metal M; Wherein, the metal M is selected from at least one of Group IIB metals, Group VIB metals, Group VIIB metals and Group VIII metals; and F is fluorine.

2. The hydrogenation catalyst according to claim 1, wherein The metal M is selected from at least one of Zn, Mn, Co, Cr, Mo and Ni, preferably at least one of Zn, Mn, Co and Mo, and more preferably Co and / or Mo.

3. The hydrogenation catalyst according to claim 1 or 2, wherein In the hydrogenation catalyst: The content of F is 0.5-5wt%, preferably 1-3wt%; and / or The content of the oxide of metal M is 0.5-15wt%, preferably 1-10wt%; and / or The content of Cu is 30-75wt%, preferably 48-67wt%; and / or The content of the carrier is 5-69wt%, preferably 20-50wt%.

4. A method for preparing the hydrogenation catalyst according to any one of claims 1 to 3, characterized in that: The preparation method comprises: (1) a kneaded product containing a copper source, a metal M source, a SiO2 source and a 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.

5. The preparation method according to claim 4, wherein The copper source is selected from at least one of copper nitrate, copper hydrochloride and copper basic carbonate; and / or The metal M source is selected from at least one of nitrates, hydrochlorides, metal acid salts and basic carbonates of metal M; and / or The SiO2 source is selected from silicon dioxide powder and / or silica sol; and / or The F source is selected from HF and / or ammonium fluoride.

6. The preparation method according to claim 4 or 5, wherein: The kneaded product further contains water, and preferably the amount of the water is 5%-150% of the mass of the copper source; and / or The kneaded material also contains an extrusion aid; Preferably, the extrusion aid is selected from at least one of citric acid, sesbania powder and graphite powder, preferably citric acid and / or sesbania powder; and / or The amount of the extrusion aid is 1%-20% of the mass of the copper source.

7. The preparation method according to any one of claims 4 to 6, wherein: The heat treatment process includes drying and roasting; Preferably, the drying conditions include: a drying temperature of 80-150° C.; and / or a drying time of 5-20 h; and / or The calcination conditions include: a calcination temperature of 300-500° C.; and / or a calcination time of 2-10 hours.

8. The preparation method according to claim 4-7, wherein: The reduction process is as follows: in the presence of hydrogen, the catalyst precursor undergoes a reduction reaction; Preferably, the conditions for the reduction reaction include: The pressure of hydrogen is 0.1-1 MPa; and / or The gas hourly space velocity of hydrogen is 200-1000h -1 ; and / or The reduction temperature is 160-270°C; and / or The reduction time is 2-10h.

9. Use of the hydrogenation catalyst according to any one of claims 1 to 3 in a hydrogenation reaction; Preferably, the hydrogenation catalyst is used in a liquid phase hydrogenation reaction; More preferably, the hydrogenation catalyst is used in liquid phase hydrogenation of ketone compounds.

10. A method for preparing 1-phenylethanol by liquid phase hydrogenation of acetophenone, characterized in that: The method includes: In the presence of the hydrogenation catalyst according to any one of claims 1 to 3, the raw material mixed liquid containing acetophenone is contacted with hydrogen to carry out a hydrogenation reaction to obtain a material containing 1-phenylethanol; Preferably, The solvent in the raw material mixture is an alkanol, preferably a C1-C5 alkyl alcohol, more preferably methanol and / or ethanol; and / or The conditions of the hydrogenation reaction include: The mass space velocity of acetophenone in the raw material mixture is 0.1-1.0h -1 , preferably 0.3-0.6h -1 ; and / or The hydrogen pressure is 1.0-5.0 MPa, preferably 1.5-4.0 MPa; and / or The feed molar ratio of hydrogen to acetophenone is 1.0-20.0, preferably 1.2-15.0; and / or The reaction temperature is 60-120°C, preferably 65-90°C.

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