Aluminosilicate zeolite-hydrogenation metal component-alumina composite, method for preparing the composite, aluminosilicate zeolite-based catalyst, method for preparing the catalyst, use of the catalyst, and method for synthesizing cyclohexylbenzene

Abstract

A composite of silicon-aluminum molecular sieve, metal hydride component, and alumina, as well as its preparation and use, are disclosed. The composite includes a silicon-aluminum molecular sieve, alumina, and a metal hydride component. At least a part of the silicon-aluminum molecular sieve and at least a part of the alumina in the composite are bonded by chemical means. There is a characteristic spectral peak in the infrared spectrum of the composite at 860-900 cm -1 -1. When a hydroalkylation catalyst based on the composite is used in a reaction for preparing phenylcyclohexane by the hydroalkylation reaction of benzene, excessive hydrogenation of benzene caused by an overly long diffusion path can be avoided, the selectivity of cyclohexane as a by-product can be reduced, the utilization rate of benzene can be improved, and the energy consumption of reaction and separation can be reduced.

Description

Detailed Description of the Invention

[0001] 〔Technical Field〕 The present application relates to the technical field of catalysts, and specifically, to aluminosilicate zeolite - hydrogenation metal component - alumina composites suitable for use as catalyst active components, as well as their preparation and use.

[0002] 〔Background Art〕 Cyclohexylbenzene is an important chemical intermediate and can be used to prepare phenol and cyclohexanone by oxidation, and can also be used as an additive with a function of preventing overcharging for the electrolyte of lithium - ion secondary batteries. Due to its relatively high cetane number, cyclohexylbenzene can also be used as a blending component for the cetane number of gas oil.

[0003] WO001244A discloses a method for synthesizing cyclohexylbenzene by catalyzing the alkylation of benzene and cyclohexene using solid acid Y zeolite as a catalyst. However, the yield of cyclohexylbenzene in this method is less than 90%. CN104513122A discloses a method for synthesizing cyclohexylbenzene by the liquid - phase alkylation of benzene and cyclohexene. The method includes the step of alkylating a mixture of cyclohexene and cyclohexane with benzene using MWW zeolite as a catalyst, with a high cyclohexene conversion rate and a cyclohexylbenzene yield of over 90%.

[0004] CN108435234A discloses a method for preparing cyclohexylbenzene by catalyzing the alkylation of benzene and cyclohexene using a heteropolyacid as a catalyst. After the catalyst was reused 10 times, a cyclohexylbenzene yield reaching 96% and a cyclohexene conversion rate of 86% were achieved. The yield of cyclohexylbenzene in the method of alkylating benzene and cyclohexene is relatively high. However, since cyclohexene in industry is derived from the selective hydrogenation of benzene and it is difficult to separate cyclohexene and benzene due to their close boiling points, the price of cyclohexene is relatively high.

[0005] The hydroalkylation technology of benzene has the characteristics of simple and easily available raw materials and short process steps, so it is another ideal option for the production of cyclohexylbenzene. US4094918 discloses a four-component catalyst with 13X zeolite as a carrier, presenting excellent hydroalkylation performance. Since then, hydroalkylation catalysts with zeolite as an alkylation component have been widely developed. US5053571, US5146024, US6037513, and CN103261126A disclose the use of β-zeolite, X or Y zeolite, and MCM-22 zeolite as alkylation components in the hydroalkylation reaction, respectively. The reaction includes two steps, the hydrogenation of benzene to produce cyclohexene and the alkylation of cyclohexene by benzene, which are completed on the same catalyst. Therefore, if the coupling performance of the two reactions of hydrogenation and alkylation is improved, the by-products of these reactions can be effectively reduced.

[0006] In the prior art, the zeolite and the carrier used in the hydroalkylation catalyst are independent of each other. As a result, the hydrogenation and alkylation processes carried out on the catalyst cannot be well combined, leading to excessive hydrogenation of benzene and the production of a higher content of cyclohexane as a by-product. On the one hand, cyclohexane cannot be further utilized within the system, resulting in a waste of benzene resources. On the other hand, since the boiling points of benzene and cyclohexane are very close, separation is difficult, leading to an increase in the energy consumption of the reaction.

[0007] Therefore, there remains a need in the art for a catalyst that can achieve an aromatic hydroalkylation reaction with high conversion and selectivity.

[0008] 〔Summary of the Invention〕 For the purpose of overcoming the drawbacks of the prior art, the present application provides an aluminosilicate zeolite-hydrogenated metal component-alumina composite, as well as its preparation and use. The composite is particularly suitable as a catalytic active component of a hydroalkylation catalyst for catalyzing the aromatic hydroalkylation reaction.

[0009] To achieve the above object, in one aspect, the present application provides an aluminosilicate zeolite-hydrogenated metal component-alumina composite, comprising an aluminosilicate zeolite, an alumina, and a hydrogenated metal component, wherein at least a part of the aluminosilicate zeolite in the composite is chemically bonded to at least a part of the alumina, and the composite has an infrared spectrum presenting characteristic peaks within the range of 860-900 cm -1 of the composite.

[0010] In another aspect, 1) a step of subjecting hydrated alumina to a first calcination, treatment with an ammonium salt aqueous solution, and a second calcination in sequence to obtain an activated alumina substrate; 2) a step of supporting a hydrogenated metal component on the activated alumina substrate to obtain a modified activated alumina substrate; and 3) using the modified activated alumina substrate as a solid aluminum source, synthesizing an aluminosilicate zeolite by hydrothermal crystallization to obtain the composite; There is provided a method for preparing an aluminosilicate zeolite - metal hydrogenation component - alumina composite of the present application, comprising the above.

[0011] In another aspect, the present application provides an aluminosilicate zeolite - based catalyst comprising a binder and the aluminosilicate zeolite - metal hydrogenation component - alumina composite of the present application, having an aluminum content of 10 - 85% by weight (calculated as alumina), a silicon content of 10 - 85% by weight (calculated as silica), and a metal hydrogenation component content of 0.01 - 5% by weight (calculated as metal) based on the total mass of the catalyst.

[0012] In another aspect, I) providing the aluminosilicate zeolite - metal hydrogenation component - alumina composite of the present application, or preparing the aluminosilicate zeolite - metal hydrogenation component - alumina composite according to the method of the present application for preparing the aluminosilicate zeolite - metal hydrogenation component - alumina composite; and II) kneading and molding the aluminosilicate zeolite - metal hydrogenation component - alumina composite with a binder source, followed by calcination and optionally activation to obtain the catalyst; There is provided a method for preparing an aluminosilicate zeolite - based catalyst, comprising the above.

[0013] In another aspect, there is provided an aluminosilicate zeolite - based catalyst prepared according to the method of the present application for preparing an aluminosilicate zeolite - based catalyst.

[0014] In another aspect, there is provided the use of the aluminosilicate zeolite catalyst of the present application in an aromatic hydroalkylation reaction, which comprises contacting and reacting an aromatic feedstock and an alkylating agent with the aluminosilicate zeolite catalyst in the presence of hydrogen.

[0015] In yet another aspect, the present application provides a method for synthesizing cyclohexylbenzene, which comprises contacting and reacting benzene with the aluminosilicate zeolite catalyst of the present application in the presence of hydrogen to obtain cyclohexylbenzene.

[0016] Compared with the prior art, the aluminosilicate zeolite catalyst using the aluminosilicate zeolite-hydrogenated metal component-alumina composite of the present application as the catalytic active component has good catalytic activity and selectivity when used in an aromatic hydroalkylation reaction. In particular, when the catalyst is used in the hydroalkylation reaction of benzene to prepare cyclohexylbenzene, it can avoid excessive hydrogenation of benzene, reduce the selectivity of cyclohexane as a by-product, improve the utilization rate of benzene, and reduce the energy consumption of reaction and separation.

[0017] Additional features and advantages of the present application will be shown in detail in the following detailed description.

[0018] [Brief Description of the Drawings] The accompanying drawings, which are used to provide a further understanding of the present application and form a part of this specification, illustrate embodiments of the present application together with the following detailed description, but do not constitute a limitation to the present application. In the drawings, FIG. 1 is a graph showing the long-term operation results of the aluminosilicate zeolite catalyst obtained in Example 1 and Comparative Example 1 of the present application; FIG. 2 shows the infrared spectrum of the Y-Ru / Al2O3 composite obtained in Example 1; and, Figure 3 shows the infrared spectrum of the Y-Ru / Al2O3 composite obtained in Comparative Example 1.

[0019] [Detailed Description of the Invention] The following provides a detailed description of specific embodiments of the present application in conjunction with the accompanying drawings. It should be understood that the specific embodiments described herein are intended only to illustrate and explain the present application and are not intended to limit the present application.

[0020] It should be understood that any specific numerical values (including the endpoints of numerical ranges) disclosed herein are not limited to the exact numerical values, but also include values close to the exact values, for example, all possible values within ±5% of the exact value. Also, for the disclosed numerical ranges, one or more new numerical ranges can be obtained by any combination between the values of the endpoints of the range, between the values of the endpoints and the values of specific points within the range, and between the values of each specific point, and such new numerical ranges should also be considered as specifically disclosed herein.

[0021] Unless otherwise indicated, the terms used herein have the same meaning as generally understood by those skilled in the art. When a term is defined herein and its definition is different from the general understanding in the art, the definition herein shall prevail.

[0022] In the present application, the so-called "metal hydride component" refers to a metal, metal oxide, other metal compound, or a mixture thereof having hydrogenation activity.

[0023] In the present application, the composition of the aluminosilicate zeolite-metal hydride component-alumina composite and the aluminosilicate zeolite-based catalyst is determined by X-ray fluorescence (XRF) analysis and is consistent with the addition ratio of the relevant raw materials during preparation.

[0024] In this application, the crystallinity of the aluminosilicate zeolite-metal hydrogenation component-alumina composite and the aluminosilicate zeolite-based catalyst is measured by the X-ray diffraction (XRD) method, and the sample is dried at 120 °C for 2 hours before the test. The crystallinity of the sample is calculated from the peak area of the diffraction peaks with 2θ between 5 and 40° on the XRD spectrum.

[0025] In this application, the surface hydrogenation metal percentage content of the aluminosilicate zeolite-metal hydrogenation component-alumina composite is determined by the X-ray photoelectron spectroscopy (XPS) method. The total hydrogenation metal percentage content of the composite is determined by the X-ray fluorescence spectroscopy (XRF) method.

[0026] In this application, unless otherwise specified, any pressure is gauge pressure.

[0027] In this application, all things or matters not mentioned, except for the explicitly described content, can be directly applied to the known modes in the technical field without any change. Furthermore, any embodiments described in this specification may be freely combined with one or more other embodiments described in this specification, and the technical solutions or concepts formed thereby shall be regarded as part of the original disclosure or the original specification of this application, and shall not be regarded as new matters not disclosed or contemplated in this specification, unless such combination is clearly considered unreasonable by those skilled in the art.

[0028] All patents and non-patent documents mentioned in this specification, including but not limited to textbooks and magazine articles, are incorporated herein by reference in their entirety.

[0029] As described above, in the first aspect, the present application provides a aluminosilicate zeolite-metal hydride component-alumina composite, which comprises an aluminosilicate zeolite, alumina, and a metal hydride component, at least a part of the aluminosilicate zeolite in the composite is chemically bonded to at least a part of the alumina, and the composite has an infrared spectrum presenting characteristic peaks within the range of 860~900 cm -1 to provide a composite having an infrared spectrum presenting characteristic peaks within the range of.

[0030] In a preferred embodiment, the aluminosilicate zeolite is selected from zeolites having a pore structure of 10-membered rings or 12-membered rings, or combinations thereof, more preferably selected from β, Y, MCM-22, PSH-3, SSZ-25, MCM-49, MCM-56 zeolites, or combinations thereof, and particularly preferably selected from β, Y, MCM-22 zeolites, or combinations thereof.

[0031] In the present application, there is no particular limitation on the type of the hydrogenation active metal in the metal hydride component, and it may be various hydrogenation active metals conventionally used in the art. In a preferred embodiment, the metal hydride component is selected from metals from Group VIB and Group VIII of the periodic table, or combinations thereof, more preferably selected from Ru, Pd, Pt, Ni, Co, Mo, W, or combinations thereof, and particularly preferably contains one or more hydrogenation active metals selected from Pd, Ru, Ni, or combinations thereof. The adoption of the above-mentioned preferred hydrogenation active metals is beneficial to improving the overall performance of the catalyst.

[0032] In a preferred embodiment, the composite has a zeolite crystallinity of 50~75%, preferably 50~70%, as detected by XRD.

[0033] In a preferred embodiment, the complex has a silicon content (calculated as silica) of 5 to 65% by weight, preferably 15 to 50% by weight, an aluminum content (calculated as alumina) of 30 to 94.99% by weight, preferably 50 to 85%, and a metal hydride component content (calculated as metal) of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total mass of the complex.

[0034] In a preferred embodiment, the surface metal hydride content ratio of the complex measured by the XPS method accounts for 0.1 to 25%, preferably 5 to 20%, of the total metal hydride content ratio of the complex measured by the XRF method.

[0035] In a preferred embodiment, the complex of the present application 1) A step of subjecting hydrated alumina to first firing, treatment with an ammonium salt aqueous solution, and second firing in sequence to obtain an activated alumina substrate; 2) A step of supporting a metal hydride component on the activated alumina substrate to obtain a modified activated alumina substrate; And, 3) A step of using the modified activated alumina substrate as a solid aluminum source and synthesizing aluminosilicate zeolite by hydrothermal crystallization to obtain the complex. It is prepared by a method including the above steps.

[0036] More preferably, the features of each of steps 1) to 3) are as described in the following second aspect.

[0037] In the aluminosilicate zeolite-hydrogenation metal component-alumina composite of the present application, it is considered, without being limited to a specific theory, that most of the hydrogenation active metal is sandwiched between the zeolite and the alumina rather than being dispersed on the outer surface of the zeolite, which is more advantageous for improving the coupling of the hydrogenation reaction and the alkylation reaction. In particular, in the hydroalkylation reaction of benzene to produce cyclohexylbenzene, side reactions such as excessive hydrogenation of benzene caused by an overly long diffusion path can be avoided, thereby reducing the selectivity of cyclohexane as a by-product, improving the utilization rate of benzene, and reducing the energy consumption for reaction and separation.

[0038] In a second aspect, the present application 1) a step of subjecting hydrated alumina (such as pseudo-boehmite) to a first calcination, treatment with an aqueous ammonium salt solution, and a second calcination in sequence to obtain an activated alumina substrate; 2) a step of supporting a hydrogenation metal component on the activated alumina substrate to obtain a modified activated alumina substrate; and 3) a step of using the modified activated alumina substrate as a solid aluminum source and synthesizing an aluminosilicate zeolite by hydrothermal crystallization to obtain the composite; A method for preparing an aluminosilicate zeolite-hydrogenation metal component-alumina composite is provided, which includes the above steps.

[0039] In the method for preparing an aluminosilicate zeolite-hydrogenation metal component-alumina composite of the present application, such that most of the hydrogenation active metal is sandwiched between the zeolite and the alumina, and the zeolite is formed on the surface of the alumina on which the hydrogenation active metal is supported, a modified activated alumina supported with the hydrogenation metal component is used as a solid aluminum source, and the aluminosilicate zeolite is synthesized by hydrothermal crystallization. It is considered to be more advantageous for improving the combination of the hydrogenation and alkylation reactions, without being limited to a specific theory, particularly in the reaction of hydroalkylation of benzene for preparing cyclohexylbenzene. This can avoid excessive hydrogenation of benzene caused by an overly long diffusion path, thereby reducing the selectivity of cyclohexane as a by-product, improving the utilization rate of benzene, and reducing the energy consumption of the reaction and separation.

[0040] According to the present application, suitable hydrated aluminas include, but are not limited to, pseudoboehmite, alumina trihydrate, boehmite, amorphous aluminum hydroxide, or mixtures thereof, preferably pseudoboehmite.

[0041] In a preferred embodiment, the conditions of the first firing and the second firing in step 1) each independently include a firing temperature of 500 to 650 °C, preferably 550 to 600 °C, and / or a firing time of 0.5 to 5 hours, preferably 2 to 4.5 hours.

[0042] According to the present application, "treatment with an aqueous ammonium salt solution" is treatment with an acidic ammonium salt solution such as an ammonium chloride solution, an ammonium nitrate solution, or an ammonium sulfate solution. In a preferred embodiment, the conditions of the treatment with the aqueous ammonium salt solution in step 1) include a mass ratio of the hydrated alumina (based on the weight after firing at 550 °C for 5 hours), the ammonium salt, and water of 1:1 to 15:1 to 15, preferably 1:1 to 2:1 to 5, an exchange temperature of 25 to 100 °C, preferably 60 to 90 °C, and / or an exchange time of 0.5 to 5 hours, preferably 1 to 2 hours.

[0043] In the method of the present application, hydrated alumina is used as a raw material, and the hydrated alumina is subjected to calcination, treatment with an ammonium salt aqueous solution, and a secondary calcination treatment to synthesize an activated alumina substrate used as a raw material for preparing zeolite, thereby improving the crystallinity of the zeolite. It is considered to be more advantageous for the synergistic cooperation between the obtained zeolite and the metal component without being limited to a specific theory. Together, they can improve the performance of a catalyst using zeolite as an active component. In particular, in the reaction of preparing cyclohexylbenzene by hydroalkylation of benzene, the selectivity of cyclohexane as a by-product can be reduced more favorably.

[0044] In a preferred embodiment, the hydrogenation metal component is selected from metals of Group VIB and Group VIII of the periodic table, or a combination thereof. More preferably, it is selected from Ru, Pd, Pt, Ni, Co, Mo, W, or a combination thereof. Particularly preferably, it contains one or more hydrogenation active metals selected from Pd, Ru, Ni, or a combination thereof.

[0045] In a preferred embodiment, the step of loading in step (2) is achieved by impregnation, preferably by equal - volume impregnation. More preferably, the step of loading in step (2) is carried out by contacting the activated alumina substrate with an aqueous solution containing a soluble salt of the hydrogenation active metal at a contact temperature of 0 - 50 °C for a contact time of 0.5 - 12 hours. Here, the hydrogenation active metal is as described above and will not be described here.

[0046] In a preferred embodiment, step (3) is carried out by reacting the modified activated alumina substrate, a silicon source, an alkali source, optionally a structure directing agent or a template agent, and water under hydrothermal crystallization conditions to obtain the composite.

[0047] In a further preferred embodiment, the hydrothermal crystallization conditions include a hydrothermal crystallization temperature of 80 to 250 ° C, preferably 100 to 180 ° C, and / or a hydrothermal crystallization time of 20 to 60 hours, preferably 28 to 48 hours. In a further preferred embodiment, different reaction conditions are used for different target zeolites. For example, when the zeolite is a Y zeolite, the hydrothermal crystallization temperature may be, for example, 80 to 120 ° C, preferably 95 to 105 ° C, and the hydrothermal crystallization time may be, for example, 20 to 60 hours, preferably 28 to 36 hours.

[0048] In a further preferred embodiment, the silicon source is selected from water glass, silica sol, sodium silicate, or combinations thereof, the alkali source is selected from alkali metal hydroxides, aqueous ammonia, or combinations thereof, and the structure directing agent or template is selected from tetramethylammonium bromide, tetraethylammonium bromide, and hexamethyleneimine.

[0049] In a particular further preferred embodiment, the modified activated alumina substrate, silicon source, alkali source, any structure directing agent or template, and water are used in amounts calculated based on Na2O, Al2O3, SiO2, and H2O, with a molar ratio of Na2O:Al2O3:SiO2:H2O = 0.1 to 1.0:1:0.5 to 2.0:10 to 50, and the resulting aluminosilicate zeolite is a Y zeolite.

[0050] In a particular further preferred embodiment, the modified activated alumina substrate, silicon source, alkali source, any structure directing agent or template, and water are used in amounts calculated based on Na2O, Al2O3, SiO2, and H2O, and the template is calculated based on R, with a molar ratio of Na2O:Al2O3:SiO2:H2O:R = 0.1 to 3.0:1:10.0 to 100.0:300 to 800:10 to 40, and the resulting aluminosilicate zeolite is an MCM-22 zeolite.

[0051] In a specific more preferred embodiment, the modified activated alumina substrate, silicon source, alkali source, any structure-directing agent or templating agent, and water are in amounts calculated based on Na2O, Al2O3, SiO2, and H2O, and the templating agent is calculated based on R, and they are used in a molar ratio of Na2O:Al2O3:SiO2:H2O:R = 0.01 to 2:1:20.0 to 100.0:100 to 500:5 to 30, and the resulting aluminosilicate zeolite is β-zeolite.

[0052] In the present application, after hydrothermal crystallization, the aluminosilicate zeolite-metal hydrogenation component-alumina composite can be obtained by a process of washing with deionized water and then drying. The drying process may be carried out under normal pressure or reduced pressure, and the drying temperature may be 40 to 250 °C, preferably 60 to 150 °C. The drying time may be 8 to 36 hours, preferably 12 to 24 hours.

[0053] In a third aspect, the present application provides an aluminosilicate zeolite-based catalyst comprising a binder and the aluminosilicate zeolite-metal hydrogenation component-alumina composite of the present application, having an aluminum content of 10 to 85% by weight, preferably 15 to 80% by weight (calculated as alumina), a silicon content of 10 to 85% by weight, preferably 15 to 80% by weight (calculated as silica), and a metal hydrogenation component content of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total mass of the catalyst.

[0054] In the present application, there is no particular limitation on the binder, and it may be one conventionally used for catalyst preparation in the art. In a preferred embodiment, the binder is an inorganic oxide, preferably selected from oxides of elements of Group IIA, Group IVB, Group IIIA, and Group IVA of the periodic table, or combinations thereof, more preferably selected from alumina, silica, titania, or combinations thereof. The use of the above-mentioned preferred binder is advantageous for improving the overall performance of the catalyst.

[0055] In the present application, there is no particular limitation on the shape of the aluminosilicate zeolite-based catalyst, and it may be in any physical form such as powder, granules, or molded articles such as pallet-shaped, strip-shaped, or trilobal-shaped.

[0056] In the aluminosilicate zeolite-based catalyst of the present application, it is considered, without being limited to a specific theory, that most of the hydrogenation active metal is sandwiched between the aluminosilicate zeolite and alumina rather than being dispersed on the outer surface of the zeolite, which is more advantageous for improving the combination of the hydrogenation reaction and the alkylation reaction. Thereby, the reactivity and selectivity of the catalyst in the hydroalkylation reaction of aromatics, particularly the hydroalkylation reaction of benzene to produce cyclohexylbenzene, are improved.

[0057] In the fourth aspect, I) a step of providing an aluminosilicate zeolite-hydrogenation metal component-alumina composite according to the first aspect of the present application, or a step of preparing the aluminosilicate zeolite-hydrogenation metal component-alumina composite according to the method of the second aspect of the present application; and, II) a step of kneading and molding the aluminosilicate zeolite-hydrogenation metal component-alumina composite with a binder source, followed by firing and optionally activation to obtain the catalyst; A method for preparing an aluminosilicate zeolite-based catalyst is provided, which includes the above steps.

[0058] In the present application, there is no particular limitation on the binder source, and it may be one conventionally used in catalyst preparation in the art. In a preferred embodiment, the binder source is an inorganic oxide or something that can be converted into an inorganic oxide under firing conditions, and the inorganic oxide is preferably selected from oxides of elements from Group IIA, Group IVB, Group IIIA, and Group IVA of the periodic table, or combinations thereof, more preferably selected from alumina, silica, or combinations thereof. For example, the binder source may be alumina.

[0059] In step II), the kneading and forming steps may be carried out by a conventional method in the art such as extrusion molding, but are not strictly limited in the present application.

[0060] In a preferred embodiment, after the kneading and forming steps, the obtained molded article is dried. The drying step may be carried out in a conventional manner in the art. Preferably, the drying conditions include a temperature of 40 to 250°C, preferably 60 to 150°C, and a drying time of 8 to 30 hours, preferably 10 to 20 hours. The drying step may be carried out under normal pressure or reduced pressure.

[0061] In step II), the firing may be carried out in a conventional manner in the art. In a preferred embodiment, the firing conditions include a firing temperature of 300 to 650°C, preferably 400 to 600°C, and / or a firing time of 1 to 10 hours, preferably 3 to 6 hours. The firing is carried out in an oxygen-containing atmosphere such as air or an oxygen atmosphere.

[0062] In a preferred embodiment, the activation in step II) includes subjecting the formed solid after firing in step II) to ammonium exchange and reduction in sequence.

[0063] In a more preferred embodiment, the conditions for ammonium exchange include a mass ratio of the formed solid, the ammonium salt, and water of 1:1 to 15:1 to 15, an exchange temperature of 25 to 100°C, preferably 60 to 90°C, and an exchange time of 0.5 to 5 hours, preferably 1 to 2 hours. More preferably, after ammonium exchange, a step of washing with deionized water and then drying is carried out. The drying step may be carried out under normal pressure or reduced pressure, and the drying temperature may be 40 to 250°C, preferably 60 to 150°C. The drying time may be 8 to 36 hours, preferably 12 to 24 hours.

[0064] In a more preferred embodiment, the reduction conditions are as follows: under a hydrogen atmosphere, a reduction temperature of 100 to 500 °C, preferably 190 to 400 °C, a reduction time of 0.5 to 12 hours, preferably 3 to 5 hours, and a hydrogen volumetric space velocity of 100 to 600 h -1 , preferably 300 to 400 h -1 to perform the reduction.

[0065] According to the present application, the aluminosilicate zeolite-based catalyst may be prepared in any physical form such as powder, granules, or shaped articles such as pellets, strips, or trilobate forms. In the present application, there is no particular limitation on the physical form, and thus, the physical form may be obtained in any conventional manner known in the art.

[0066] In a fifth aspect, there is provided an aluminosilicate zeolite-based catalyst prepared according to the method of the present application for preparing an aluminosilicate zeolite-based catalyst.

[0067] In a sixth aspect, there is provided the use of the aluminosilicate zeolite-based catalyst according to the third or fifth aspect of the present application in an aromatic hydroalkylation reaction.

[0068] In a seventh aspect, the present application provides a method for aromatic hydroalkylation, which includes a step of contacting an aromatic feedstock and an alkylating agent with the aluminosilicate zeolite-based catalyst according to the third or fifth aspect of the present application in the presence of hydrogen to perform a hydroalkylation reaction.

[0069] In a preferred embodiment, the aromatic feedstock is selected from benzene, toluene, xylene, or a combination thereof.

[0070] In a preferred embodiment, the hydroalkylation reaction conditions include a reaction temperature of 80 to 200 °C, a reaction pressure of 0.1 to 2.0 MPa, a molar ratio of hydrogen to benzene of 0.1 to 20.0, and a mass space velocity of benzene of 0.1 to 2.0 h -1 .

[0071] In an eighth aspect, there is provided a method for synthesizing cyclohexylbenzene, which includes a step of contacting benzene with an aluminosilicate zeolite catalyst according to the third or fifth aspect of the present application in the presence of hydrogen and reacting them to obtain cyclohexylbenzene.

[0072] In a preferred embodiment, the reaction conditions include a reaction temperature of 80 to 200 °C, a reaction pressure of 0.1 to 2.0 MPa, a molar ratio of hydrogen to benzene of 0.1 to 20.0, and a mass space velocity of benzene of 0.1 to 2.0 h -1 -1.

[0073] 〔Example〕 The present application will be described in more detail below with reference to examples, but the present application is not limited thereto.

[0074] The equipment and test methods used in the following examples and comparative examples are as follows.

[0075] To measure the pyridine infrared spectrum of a sample, a Nicolet iS10 infrared spectrometer from Thermo Fisher was used. During the measurement, the sample was dried under an infrared lamp for 30 minutes, mixed with potassium bromide at a ratio of 1:50, and then pressed into a tablet for measurement. Before and after the measurement, the background of carbon dioxide was subtracted.

[0076] The model of the X-ray fluorescence analyzer (XRF) is the Axios mAX type X-ray fluorescence analyzer from PANalytical in the Netherlands, and the non-standard quantitative method was used for quantitative analysis.

[0077] The model of the X-ray photoelectron spectroscopy (XPS) was the K-Alpha type X-ray photoelectron spectrometer of Thermo Fisher Scientific in the United States, which had an optimum resolution of less than 30 μm, an optimum energy resolution of less than 0.5 eV (full width at half maximum), and a C1s energy resolution of less than 0.85 eV. AlKα target (hν = 1486.68 eV), ion source energy range of 100 - 3 keV, maximum beam current of 4 μA, and the optimum vacuum in the analysis chamber of 5×10 -9 mbar were used. In the measurement, the surface was not subjected to sputtering treatment.

[0078] X-ray diffraction analysis (XRD): The sample was subjected to phase analysis using the powder XRD method, and the relative crystallinity and the ratio of skeletal silicon to aluminum were calculated. The apparatus used was the D / max-1400 type X-ray powder diffractometer of Rigaku Corporation in Japan. Cu-Kα radiation (wavelength 1.541 Å), tube current of 40 mA, tube voltage of 40 kV, and the scanning angle range for phase analysis of 5 - 50° were used.

[0079] In the following examples and comparative examples, the starting materials and reagents used were all commercially available substances with reagent-grade purity, unless otherwise specified.

[0080] In the following examples, the preparation of the aluminosilicate zeolite - metal hydride component - alumina composite was as follows, but was not limited to the embodiments described below.

[0081] <Y Zeolite - Metal Hydride Component - Alumina Composite> 67.2 g of water glass was taken, charged into a beaker, and the temperature inside the beaker was heated to 50 °C by using a water bath. 52 g of a directing agent was added and the mixture was stirred uniformly. Then, 12 g of sodium hydroxide was added to adjust the pH value of the system to over 10. Following sufficient stirring until uniform, 88 g of water and 50 g of a modified activated alumina substrate were added and the mixture was stirred for 60 minutes. Then, the mixture was charged into a reaction kettle, crystallized at 100 °C for 20 hours, and then the product was filtered, washed, and dried at 120 °C for 12 hours to obtain a sample of Y - metal hydride component - alumina composite. Here, the directing agent was prepared by stirring 55.8 g of water glass and 56.8 g of sodium aluminate solution at room temperature and reacting for 24 hours.

[0082] <MCM - 22 zeolite - metal hydride component - alumina composite> 293 g of silica sol was taken, charged into a beaker, and the temperature inside the beaker was heated to 50 °C by using a water bath. 144 g of a hexamethyleneamine templating agent and 5.6 g of crystal seeds were added and the mixture was stirred uniformly. Then, 10 g of sodium hydroxide was added to adjust the pH value of the system to over 10. Following sufficient stirring until uniform, 970 g of water and 50 g of a modified activated alumina substrate were added and the mixture was stirred for 60 minutes. Then, the mixture was charged into a reaction kettle, crystallized at 100 °C for 28 hours, and then the product was filtered, washed, and dried at 120 °C for 12 hours to obtain a sample of MCM - 22 - metal hydride component - alumina composite.

[0083] <β zeolite - metal hydride component - alumina composite> Take 443 g of deionized water, place it in a beaker, add 32.6 g of sodium hydroxide, adjust the pH value of the system to over 10, continuously stir the mixture until it is completely dissolved. Heat the temperature inside the beaker to 50 °C by using a water bath. Add 50 g of modified activated alumina substrate, 960 g of tetraethylammonium hydroxide, and 520 g of tetraethylammonium bromide (TEA), and stir the mixture for 0.5 hour. Then, add 2445 g of 40% silica sol, continuously stir the mixture for 1 hour, and place it in a crystallization kettle. Under stirring, perform crystallization at a crystallization temperature of 150 °C for a crystallization time of 40 hours. Then, filter, wash the product, and dry it at 120 °C for 12 hours to obtain a sample of β-metal hydride component-alumina composite.

[0084] <Mixed zeolite-metal hydride component-alumina composite> By using the method for synthesizing zeolite as described above, perform the crystallization of zeolite independently, then mix the obtained crystallized product, stir it sufficiently, then filter, wash it, and dry it at 120 °C for 12 hours to obtain a mixed zeolite-metal hydride component-alumina composite.

[0085] <Example 1> (1) Take 200 g of hydrated alumina and calcine it at 600 °C for 5 hours. Then, take 100 g of the calcined powder and 100 g of ammonium nitrate, add them into 500 g of deionized water, and treat the mixture at 60 °C for 2 hours. Then, wash the product with deionized water, dry it at 120 °C for 12 hours, and subsequently perform calcination at 550 °C for 5 hours to obtain activated alumina.

[0086] (2) Take 96 g of activated alumina as a carrier and impregnate it isovolumetrically with 3 g of Ru. Dry the impregnated mixture at 120 °C for 12 hours and calcine it at 550 °C for 5 hours to obtain Ru / Al2O3.

[0087] (3) 50 g of Ru / Al₂O₃ was taken as the substrate, and Y zeolite was synthesized according to the method described above, resulting in a Y-Ru / Al₂O₃ composite. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0088] (4) 50 g of the Y-Ru / Al₂O₃ composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the obtained formed solid and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst A. Based on the charge amount, Catalyst A contains 1.5 wt% of Ru, 50.5 wt% of the composite, and 49.5 wt% of the binder, and its elemental analysis results are shown in Table 2.

[0089] Catalyst A was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3, and the results of the long-term operation are shown in Figure 1.

[0090] Figure 2 shows the infrared spectrum of the Y-Ru / Al₂O₃ composite obtained in Example 1. It presents a characteristic peak at 863 cm -1 within the range of 860 - 900 cm -1 , indicating the presence of a chemical bond between the zeolite and alumina.

[0091] <Example 2> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Subsequently, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added into 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then, the product was washed with deionized water, dried at 120 °C for 12 hours, and subsequently calcined at 550 °C for 5 hours to obtain activated alumina.

[0092] (2) 99 g of activated alumina was taken as a carrier and impregnated with 1 g of Pd in an equal volume. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Pd / Al2O3.

[0093] (3) 50 g of Pd / Al2O3 was taken as a substrate, and Y zeolite was synthesized according to the method described above, resulting in a Y-Pd / Al2O3 composite. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0094] (4) Next, 50 g of the Y-Pd / Al2O3 composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst B. Based on the loading amount, Catalyst B contains 0.5 wt% of Pd, 50.5 wt% of the composite, and 49.5 wt% of the binder, and its elemental analysis results are shown in Table 2.

[0095] Catalyst B was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0096] The infrared spectrum of the Y-Pd / Al2O3 composite obtained in Example 2 was the same as that in Example 1.

[0097] <Example 3> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Subsequently, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added into 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then, the product was washed with deionized water, dried at 120 °C for 12 hours, and subsequently calcined at 550 °C for 5 hours to obtain activated alumina.

[0098] (2) 95 g of activated alumina was taken as a carrier and impregnated isovolumetrically with 5 g of Ni. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ni / Al2O3.

[0099] (3) 50 g of Ni / Al2O3 was taken as a substrate, and Y zeolite was synthesized according to the method described above, resulting in a Y-Ni / Al2O3 composite. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0100] (4) Next, 50 g of the Y-Ni / Al2O3 composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst C. Based on the loading amount, Catalyst C contains 2.5 wt% of Ni, 50.5 wt% of the composite, and 49.5 wt% of the binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0101] The catalyst C was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 0.45 h -1 , the feed rate of benzene was 0.075 g / min, and the feed rate of hydrogen was 10.9 mL / min. The reaction temperature was 150 °C and the reaction pressure was 0.12 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0102] The infrared spectrum of the Y-Ni / Al2O3 composite obtained in Example 3 was the same as that in Example 1.

[0103] <Example 4> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Then, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added into 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Thereafter, the product was washed with deionized water, dried at 120 °C for 12 hours, and subsequently calcined at 550 °C for 5 hours to obtain activated alumina.

[0104] (2) 96 g of activated alumina was taken as a carrier and impregnated isovolumetrically with 3 g of Ru. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ru / Al2O3.

[0105] (3) 50 g of Ru / Al2O3 was taken as a substrate, and β-zeolite was synthesized according to the method described above, and as a result, a β-Ru / Al2O3 composite was obtained. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0106] (4) Next, 50 g of the β-Ru / Al2O3 composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst D. Based on the charge amount, Catalyst D contains 1.5 wt% of Ru, 50.5 wt% of the composite, and 49.5 wt% of the binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0107] Catalyst D was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0108] The infrared spectrum of the β-Ru / Al2O3 composite obtained in Example 4 was the same as that in Example 1.

[0109] <Example 5> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Then, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added into 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Thereafter, the product was washed with deionized water and dried at 120 °C for 12 hours, followed by calcination at 550 °C for 5 hours to obtain activated alumina.

[0110] (2) 99 g of activated alumina was taken as a carrier and impregnated with 1 g of Pd in an equal volume. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Pd / Al2O3.

[0111] (3) 50 g of Pd / Al₂O₃ was taken as the substrate, and β-zeolite was synthesized according to the method described above, resulting in a β-Pd / Al₂O₃ composite. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0112] (4) Next, 50 g of the β-Pd / Al₂O₃ composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added to 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst E. Based on the loading amount, Catalyst E contains 0.5 wt% of Pd, 50.5 wt% of the composite, and 49.5 wt% of the binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0113] Catalyst E was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0114] The infrared spectrum of the β-Pd / Al₂O₃ composite obtained in Example 5 was the same as that in Example 1.

[0115] <Example 6> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Then, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added to 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Thereafter, the product was washed with deionized water and dried at 120 °C for 12 hours, followed by calcination at 550 °C for 5 hours to obtain activated alumina.

[0116] (2) 95 g of activated alumina was used as a carrier and impregnated isovolumetrically with 5 g of Ni. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ni / Al2O3.

[0117] (3) 50 g of Ni / Al2O3 was used as a substrate and β-zeolite was synthesized according to the method described above, resulting in a β-Ni / Al2O3 composite. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0118] (4) Next, 50 g of the β-Ni / Al2O3 composite was taken and mixed with 70 g of alumina. The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added to 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volumetric space velocity of 300 h -1 to obtain Catalyst F. Based on the loading amount, Catalyst F contains 2.5 wt% Ni, 50.5 wt% composite, and 49.5 wt% binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0119] Catalyst F was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 0.45 h -1 , the feed rate of benzene was 0.075 g / min, and the feed rate of hydrogen was 10.9 mL / min. The reaction temperature was 150 °C and the reaction pressure was 0.12 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0120] The infrared spectrum of the β-Ni / Al2O3 composite obtained in Example 6 was the same as that in Example 1.

[0121] <Example 7> (1) 200 g of hydrated alumina was taken and calcined at 600 °C for 5 hours. Subsequently, 100 g of the calcined powder and 100 g of ammonium nitrate were taken and added into 500 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then, the product was washed with deionized water and dried at 120 °C for 12 hours. Subsequently, the ammonium zeolite was calcined at 550 °C for 5 hours to obtain activated alumina.

[0122] (2) 96 g of activated alumina was taken as a support and impregnated isovolumetrically with 3 g of Ru. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ru / Al2O3.

[0123] (3) 50 g of Ru / Al2O3 was taken as a substrate, and MCM-22 zeolite was synthesized according to the method described above to obtain an MCM-22-Ru / Al2O3 composite as a result. The crystallinity and elemental analysis results of the composite are shown in Table 1.

[0124] (4) Subsequently, 50 g of the MCM-22-Ru / Al2O3 composite was taken and mixed with 70 g of a binder (alumina). The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a formed solid. 30 g of the formed solid and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then, the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst G. Based on the charge amount, Catalyst G contains 1.5 wt% of Ru, 50.5 wt% of the composite, and 49.5 wt% of the binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0125] Catalyst G was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1, the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0126] The infrared spectrum of the MCM-22-Ru / Al2O3 composite obtained in Example 7 was the same as that in Example 1.

[0127] <Example 8> Using 25 g of the Y-Ru / Al2O3 composite obtained in step (3) of Example 1 and 25 g of the β-Ru / Al2O3 composite obtained in step (3) of Example 4, and mixing with 70 g of a binder (alumina), a catalyst H was obtained by referring to step (4) of Example 1 except that other conditions remained the same. Based on the charge amount, catalyst H contained 1.5 wt% Ru, 50.5 wt% composite, and 49.5 wt% binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0128] Catalyst H was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0129] <Example 9> In step (4), 50 g of the Y-Ru / Al2O3 composite was taken and mixed with 22.5 g of a binder (alumina), and a catalyst I was obtained by referring to Example 1 except that other conditions remained the same. Based on the charge amount, catalyst I contained 2.3 wt% Ru, 76 wt% composite, and 24 wt% binder, and the elemental analysis results of the catalyst are shown in Table 2.

[0130] Catalyst I was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0131] <Example 10> A catalyst was prepared with reference to Example 1, except that 70 g of porous silica gel was used as a binder to obtain Catalyst J. Based on the charged amount, Catalyst J contained 1.5 wt% of Ru, 43.4 wt% of the composite, and 56.5 wt% of the binder. The elemental analysis results of the catalyst are shown in Table 2.

[0132] Catalyst J was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0133]

Table 1

[0134]

Table 2

[0135] <Comparative Example 1> 98.5 g of Y zeolite was taken as a carrier and impregnated isovolumetrically with 1.5 g of Ru. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ru / Y. Then 50 g of Ru / Y was taken and mixed with 70 g of hydrated alumina. The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a Y-Ru / Al2O3 composite. 30 g of the Y-Ru / Al2O3 composite and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst K.

[0136] Catalyst K was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 The molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3, and the results of the long-term operation are shown in Figure 1.

[0137] Figure 3 shows the infrared spectrum of the Y-Ru / Al2O3 composite obtained in Comparative Example 1. It does not exhibit characteristic peaks in the range of 860 - 900 cm -1 indicating that zeolite and alumina are physically mixed and there is no chemical bond between them.

[0138] <Comparative Example 2> 99.5 g of Y zeolite was used as a carrier and impregnated with 0.5 g of Pd in an equal volume. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Pd / Y. Then 50 g of Pd / Y was taken and mixed with 70 g of hydrated alumina. The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain the Y-Pd / Al2O3 composite. 30 g of the Y-Pd / Al2O3 composite and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volume space velocity of 300 h -1 to obtain Catalyst L.

[0139] Catalyst L was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 The molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0140] The infrared spectrum of the Y-Pd / Al2O3 composite obtained in Comparative Example 2 is in the range of 860 - 900 cm -1did not exhibit a characteristic peak within the range.

[0141] <Comparative Example 3> 90 g of Y zeolite was taken as a carrier and impregnated isovolumetrically with 10 g of Ni. The impregnated mixture was dried at 120 °C for 12 hours and calcined at 550 °C for 5 hours to obtain Ni / Y. Then 50 g of Ni / Y was taken and mixed with 70 g of hydrated alumina. The mixture was kneaded and formed into strips, dried at 120 °C for 12 hours, and then calcined at 600 °C for 5 hours to obtain a Y-Ni / Al2O3 composite. 30 g of the Y-Ni / Al2O3 composite and 30 g of ammonium nitrate were taken and added into 300 g of deionized water, and the mixture was treated at 60 °C for 2 hours. Then the product was washed with deionized water and dried at 120 °C for 12 hours to obtain ammonium zeolite. The ammonium zeolite was calcined at 550 °C for 5 hours, and then the obtained sample was reduced at 230 °C for 3 hours at a hydrogen volumetric space velocity of 300 h -1 to obtain Catalyst M.

[0142] Catalyst M was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0143] The infrared spectrum of the Y-Ni / Al2O3 composite obtained in Comparative Example 3 did not exhibit a characteristic peak within the range of 860 - 900 cm -1 did not exhibit a characteristic peak within the range.

[0144] <Comparative Example 4> (1) 50 g of modified alumina was taken and mixed with 8.1 g of RuCl3 (37% Ru), 32.6 g of sodium hydroxide, 760 g of tetraethylammonium bromide, and 1050 g of macroporous silica gel. The mixture was thoroughly ground for 8 minutes and placed in a reaction kettle at 150 °C for 40 hours for crystallization to obtain a Ru / zeolite-alumina mixture.

[0145] (2) Referring to step (4) of Example 1, 50 g of the Ru / zeolite-alumina mixture was taken, mixed with 70 g of the binder (alumina), and with other conditions remaining the same, Catalyst O was obtained.

[0146] Catalyst O was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0147] <Comparative Example 5> (1) (Referring to Example 1) A specific amount of metal salt was dissolved in water to obtain an aqueous metal salt solution. The aqueous metal salt solution and the activated alumina obtained in step (1) of Example 1 were used respectively instead of the water and the modified activated alumina substrate used in the method for synthesizing the Y zeolite-metal hydrogenation component-alumina composite as described above to obtain a composite.

[0148] (2) Referring to step (4) of Example 1, 50 g of the composite obtained in step (1) was taken, mixed with 70 g of the binder (alumina), and with other conditions remaining the same, Catalyst P was obtained.

[0149] Catalyst P was evaluated for the hydroalkylation reaction. The mass space velocity of benzene was 1.0 h -1 , the molar ratio of hydrogen to benzene was 2, the reaction temperature was 150 °C, and the reaction pressure was 0.10 MPa. The results of the reaction after 32 hours are shown in Table 3.

[0150]

Table 3

[0151] As can be seen from the data shown in Table 3, compared with the catalysts of Comparative Examples 1 to 5, the catalysts obtained in Examples 1 to 10 not only exhibit higher yields and selectivities of cyclohexylbenzene as the main product, but also present a higher conversion rate of benzene, while the selectivities and yields of cyclohexane as by-products are significantly decreased.

[0152] As can be seen from the long-term operation results of the catalysts obtained in Example 1 and Comparative Example 1 of the present application shown in FIG. 1, the catalyst of the present application can maintain high activity without decline during long-term operation. On the other hand, compared with the catalyst of Comparative Example 1, the catalyst of the present application presents a higher conversion rate of benzene and a high selectivity of cyclohexylbenzene as the main product.

[0153] The preferred embodiments of the present application have been described in detail above with reference to the accompanying drawings. However, the present application is not limited to the specific details of the above embodiments. Within the scope of the technical idea of the present application, various simple modifications may be made to the technical solutions of the present application, and all these simple modifications are within the protection scope of the present application.

[0154] Furthermore, it should be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present application does not otherwise explain various possible combinations.

[0155] In addition, unless it is contrary to the spirit of the present application, various different embodiments of the present application may be combined with each other in any manner. Such combinations should also be regarded as the disclosure of the present application.

Brief Description of the Drawings

[0156]

Figure 1

Figure 2

Figure 3

Claims

1. An aluminosilicate zeolite-hydrogenation metal component-alumina composite, comprising an aluminosilicate zeolite, alumina, and a hydrogenation metal component; At least a portion of the aluminosilicate zeolite in the composite is chemically bonded to at least a portion of the alumina, and the composite has a molecular weight of 860 to 900 cm －１ The complex has an infrared spectrum exhibiting characteristic peaks in the range of

2. The aluminosilicate zeolite is selected from zeolites having a pore structure of 10-membered rings or 12-membered rings, or a combination thereof, preferably selected from β, Y, MCM-22, PSH-3, SSZ-25, MCM-49, MCM-56 zeolite, or a combination thereof, more preferably selected from β, Y, MCM-22 zeolite, or a combination thereof. and / or The hydrogenation metal component comprises one or more hydrogenation active metals selected from metals of Groups VIB and VIII of the Periodic Table, or combinations thereof, preferably selected from Ru, Pd, Pt, Ni, Co, Mo, W, or combinations thereof, more preferably selected from Pd, Ru, Ni, or combinations thereof; The composite of claim 1.

3. 2. The composite of claim 1, wherein the composite has a zeolite crystallinity of 50-75%, preferably 50-70%, as detected by XRD.

4. The composite comprises, based on the total mass of the composite, a silicon content (calculated as silica) of 5 to 65% by weight, preferably 15 to 50% by weight; an aluminum content (calculated as alumina) of 30 to 94.99% by weight, preferably 50 to 85%; a hydrogenation metal component content (calculated as metal) of 0.01 to 5 wt. %, preferably 0.1 to 3 wt. %; 2. The composite of claim 1, having:

5. 2. The composite of claim 1, wherein the surface metal hydride fraction content of the composite measured by XPS method accounts for 0.1-25%, preferably 5-20%, of the total metal hydride fraction content of the composite measured by XRF method.

6. 1) subjecting hydrated alumina to a first calcination, treatment with an aqueous ammonium salt solution, and a second calcination in sequence to obtain an activated alumina substrate; 2) supporting a hydrogenation metal component on the activated alumina substrate to obtain a modified activated alumina substrate; and, 3) synthesizing an aluminosilicate zeolite by hydrothermal crystallization using the modified activated alumina substrate as a solid aluminum source to obtain the composite; 2. The complex of claim 1, prepared by a method comprising:

7. 1) subjecting hydrated alumina to a first calcination, treatment with an aqueous ammonium salt solution, and a second calcination in sequence to obtain an activated alumina substrate; 2) supporting a hydrogenation metal component on the activated alumina substrate to obtain a modified activated alumina substrate; and, 3) synthesizing an aluminosilicate zeolite by hydrothermal crystallization using the modified activated alumina substrate as a solid aluminum source to obtain the composite; 10. A method for preparing the aluminosilicate zeolite-hydrogenation metal component-alumina composite of claim 1, comprising:

8. In step 1), The conditions for the first firing and the second firing each independently include a firing temperature of 500 to 650°C and / or a firing time of 0.5 to 5 hours; and / or The conditions for the treatment with the aqueous ammonium salt solution are: a mass ratio of the hydrated alumina to the ammonium salt to water (based on weight after calcination at 550° C. for 5 hours) of 1:1-15:1-15, preferably 1:1-2:1-5; an exchange temperature of 25 to 100°C, preferably 60 to 90°C; and / or an exchange time of 0.5 to 5 hours, preferably 1 to 2 hours; Including, The method of claim 7.

9. The hydrogenation metal component comprises one or more hydrogenation active metals selected from metals of Groups VIB and VIII of the Periodic Table, or combinations thereof, preferably selected from Ru, Pd, Pt, Ni, Co, Mo, W, or combinations thereof, more preferably selected from Pd, Ru, Ni, or combinations thereof; and / or The loading step in step (2) is achieved by impregnation, preferably by isovolumetric impregnation; Preferably, the supporting step in step (2) is carried out by contacting the activated alumina substrate with an aqueous solution containing a soluble salt of the hydrogenation active metal at a contact temperature of 0 to 50°C for a contact time of 0.5 to 12 hours. The method of claim 7.

10. step (3) is carried out by reacting the modified activated alumina substrate, a silicon source, an alkali source, optionally a structure-directing or templating agent, and water under hydrothermal crystallization conditions to obtain the composite; Preferably, the hydrothermal crystallization conditions include a hydrothermal crystallization temperature of 80 to 250°C, preferably 100 to 180°C, and / or a hydrothermal crystallization time of 20 to 60 hours, preferably 28 to 48 hours; More preferably, the silicon source is selected from water glass, silica sol, sodium silicate, or a combination thereof, the alkali source is selected from alkali metal hydroxides, aqueous ammonia, or a combination thereof, and the structure directing or templating agent is selected from tetramethylammonium bromide, tetraethylammonium bromide, and hexamethyleneimine.

11. An aluminosilicate zeolite-based catalyst comprising a binder and the aluminosilicate zeolite-hydrogenation metal component-alumina composite of claim 1, Based on the total mass of the catalyst, an aluminum content (calculated as alumina) of 10 to 85% by weight, preferably 15 to 80% by weight; a silicon content (calculated as silica) of 10 to 85% by weight, preferably 15 to 80% by weight; a hydrogenation metal component content (calculated as metal) of 0.01 to 5 wt. %, preferably 0.1 to 3 wt. %; A catalyst having

12. the binder is an inorganic oxide, Preferably, the oxides are selected from oxides of elements of groups IIA, IVB, IIIA, and IVA of the periodic table, or combinations thereof; 12. The catalyst of claim 11, more preferably selected from alumina, silica, titania, or a combination thereof.

13. I) providing an aluminosilicate zeolite-hydrogenation metal component-alumina composite according to any one of claims 1 to 6 or preparing said aluminosilicate zeolite-hydrogenation metal component-alumina composite according to any one of claims 7 to 10; and, II) kneading and shaping the aluminosilicate zeolite-hydrogenation metal component-alumina composite with a binder source, followed by calcination and optional activation to obtain a catalyst; 1. A method for preparing an aluminosilicate zeolite catalyst, comprising:

14. The firing conditions in step II) include a firing temperature of 300 to 650°C and / or a firing time of 1 to 10 hours; and / or The activation in step II) comprises sequentially subjecting the shaped solid after calcination in step II) to ammonium exchange and reduction, preferably The ammonium exchange conditions include a mass ratio of the shaped solid, ammonium salt, and water of 1:1 to 15:1 to 15, an exchange temperature of 25 to 100°C, and an exchange time of 0.5 to 5 hours. and / or The reduction conditions are a hydrogen atmosphere, a reduction temperature of 100 to 500°C, a reduction time of 0.5 to 12 hours, and a reduction time of 100 to 600 hours. －１ and performing the reduction at a hydrogen volumetric space velocity of The method of claim 13.

15. 14. An aluminosilicate zeolite catalyst prepared by the method of claim 13.

16. 13. Use of the aluminosilicate zeolite catalyst according to claim 11 or 12 in aromatic hydroalkylation reactions, comprising:

10. A method for producing an aromatic hydrocarbon feedstock comprising contacting and reacting an aromatic feedstock and an alkylating agent with said aluminosilicate zeolite catalyst in the presence of hydrogen.

17. contacting and reacting benzene with the aluminosilicate zeolite catalyst of claim 11 or 12 in the presence of hydrogen to obtain cyclohexylbenzene; Preferably, the reaction conditions are a reaction temperature of 80 to 200°C, a reaction pressure of 0.1 to 2.0 MPa, a molar ratio of hydrogen to benzene of 0.1 to 20.0, and a reaction time of 0.1 to 2.0 h. －１ and a mass hourly space velocity of benzene of 1000 kJ / min.

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