Hydrogenation-acid catalyst dual-function catalyst, method for preparing the same, and its use.

Abstract

The catalyst comprises, based on the mass of the catalyst, 80 to 99.8% of a silicon-aluminum molecular sieve component, 0.2 to 2% of a metal component having hydrogenation activity supported on the molecular sieve, and 0 to 20% of a hydrocarbyl modifying component, the metal having hydrogenation activity being selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, and the hydrocarbyl modifying component being C 1-20 A hydrogenation-acid catalyst bifunctional catalyst having hydrocarbyl groups. The catalyst has two functions as a hydrogenation catalyst and an acid catalyst, and is suitable for the hydroalkylation reaction of benzene and the hydroisomerization reaction of alkanes. Furthermore, when the catalyst is used in the hydroalkylation reaction of benzene to produce cyclohexylbenzene, the catalyst has the characteristics of high benzene conversion, good product selectivity, and low production of the by-product cyclohexane.

Description

Detailed Description of the Invention

[0001] 〔Technical Field〕 This application relates to the field of catalysts, specifically to a hydrogenation-acid catalyst bifunctional catalyst, and its preparation method and its use.

[0002] 〔Background Art〕 Cyclohexylbenzene is an important chemical product and has important applications in the fields of liquid crystals and secondary batteries. Among them, cyclohexylbenzene liquid crystals have extremely high chemical stability, photochemical stability, and physical properties, and are one of the ideal materials for liquid crystal displays. In addition, cyclohexylbenzene can also be used as an additive component of the electrolyte of lithium-ion batteries. Since cyclohexylbenzene has a function of preventing overcharging, the safety of the battery can be effectively improved. Furthermore, by using cyclohexylbenzene as an intermediate and further performing peroxidation reaction and decomposition reaction, phenol and cyclohexanone, which are important chemical products that can be used in the production of phenolic resins, caprolactam, and nylon, can be obtained. Therefore, the preparation and production of cyclohexylbenzene have received extensive attention. The basic information of cyclohexylbenzene is as follows: colorless liquid, CAS number: 827-52-1, density 0.95 g / cm ,

[0003] , , ,

[0002] , 3 , ,

[0004] , , , 、boiling point 238~240 °C, melting point 5 °C, flash point 98 °C.

[0003] As the main preparation methods of cyclohexylbenzene that depend on raw materials, there are hexene alkylbenzene cyclization method, benzene hydroalkylation method, etc. Among them, the basic principle of the benzene hydroalkylation method is as follows. Using benzene and hydrogen as raw materials, a part of benzene is hydrogenated at the metal active center to obtain a six-membered cyclic olefin structure (such as cyclohexene), and further, an alkylation reaction is carried out with benzene at the position of the acidic active center to obtain a cyclohexylbenzene product. Therefore, in the production process of cyclohexylbenzene, a bifunctional catalyst having both a hydrogenation active center and an alkylation active center can be used.

[0004] Research on the hydroalkylation of benzene for the preparation of cyclohexylbenzene began in the 1980s. Currently developed catalysts mainly use metals supported on molecular sieves, and most of them suffer from low catalytic efficiency and low selectivity. For example, catalysts based on molecular sieves of the MCM-22 series (US2011 / 0015457A1, CN104105679A) have the problem of slow catalytic rates and high selectivity for the byproduct cyclohexane. Other catalysts, such as catalysts using HY molecular sieves treated with Ni-rare earth elements as a support (US4219689), have the problem of low benzene conversion rates and low yields of cyclohexylbenzene products. It has since been reported that molecular sieves supported with Pd / HY can be used as a catalyst to catalyze the hydroalkylation of benzene and prepare cyclohexylbenzene in a single step (Molecular Catalysis 2017, 442, 27-38). The initial conversion rate of benzene was 42.2%, the selectivity for cyclohexylbenzene remained at approximately 75%, and the selectivity for cyclohexane, a byproduct of excess hydrogenation, was high at approximately 20%. From this perspective, existing technologies have significant problems for practical industrial application, mainly due to the low selectivity of the product and the large amount of cyclohexane produced as a byproduct.

[0005] Similarly, other hydrogenation-solid acid binary catalytic reactions also face the problem of numerous by-products and reduced selectivity of the target product. For example, patent CN112934251A discloses a scheme using metal hydride-mordenite for n-heptane hydrogenation isomerization, where the selectivity of isoheptane is approximately 60%-70%. Conventional patents such as US5643440, US5302279, and US6190532 disclose schemes using noble metal-low acid molecular sieves as heavy oil isomerization catalysts. However, there is a general lack of positional control of the central sites of the hydrogenation and acid catalysts, and the optimal matching effect of the dual active sites is not demonstrated.

[0006] [Disclosure of the Invention] The object of this application is to provide a dual-function hydrogenation-acid catalyst, a method for preparing the same, and its applications. This catalyst has two functions, hydrogenation and acid catalysis, and is suitable for the hydroalkylation reaction of benzene and the hydroisomerization reaction of alkanes. Furthermore, when used in the hydroalkylation reaction of benzene to produce cyclohexylbenzene, this catalyst has the characteristics of a high benzene conversion rate, good product selectivity, and low levels of cyclohexane as a by-product.

[0007] To achieve the above objective, in one embodiment, the present invention provides a catalyst comprising, based on the mass of the catalyst, 80-99.8% silica-alumina molecular sieve component, 0.2-2% hydrogenation-active metal component supported on the molecular sieve, and 0-20% hydrocarbyl-modified component, wherein the hydrogenation-active metal is selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, and the hydrocarbyl-modified component is C 1-20 It is hydrocarbil.

[0008] In another embodiment, a method for preparing the catalyst of the present application is provided, comprising the following steps: (1) A step of providing an H-type silica-alumina molecular sieve; and (2) A step of obtaining a catalyst by supporting a hydrogenation-active metal on an H-type silica-alumina molecular sieve and optionally performing hydrocarbylation and / or reduction on the obtained product.

[0009] In another embodiment, the use of the catalyst of the present invention in a hydrocarbon hydrogenation reaction is provided, comprising the step of contacting and reacting a hydrocarbon raw material with the catalyst in the presence of hydrogen.

[0010] In another embodiment, the present application provides a one-step method for producing cyclohexylbenzene by hydrogenating benzene, the method comprising the step of contacting and reacting benzene with the catalyst of the present application in the presence of hydrogen to obtain cyclohexylbenzene.

[0011] In another embodiment, the present invention provides a method for alkane hydroisomerization, comprising the step of contacting and reacting a linear alkane with the catalyst of the present invention in the presence of hydrogen to obtain an isomerization product, wherein the linear alkane is a linear alkane with 8 or more carbon atoms.

[0012] The following are some of the advantageous effects of the catalyst of this invention compared to the prior art: 1. The catalyst of this invention possesses two functions: hydrogenation and acid catalysis. It can achieve the hydroalkylation reaction of benzene under mild reaction conditions, producing cyclohexylbenzene. Both the conversion rate of benzene and the selectivity of the main product, cyclohexylbenzene, are very high, and the stability of the reaction system is good. In particular, when an ATS structure silica-alumina molecular sieve is used as the molecular sieve component, the catalyst of this invention has a special pore structure and acidic properties. The catalyst of this invention has the remarkable effect of reducing the generation of by-products cyclohexane and dicyclohexylbenzene in the hydroalkylation reaction of benzene.

[0013] 2. The catalyst of this invention has a specific composition, and in particular, its active metal component is mainly concentrated in the molecular sieve's flow path. The outer surface has a low metal content, ensuring that the content of excess hydrogenation by-products (such as cyclohexane) is low. The outer surface of the catalyst is highly hydrophobic, so it has good affinity with various types of alkanes, aromatics, and other nonpolar substances, ensuring that the benzene conversion rate is maintained at a high level.

[0014] 3. When the catalyst of this invention is used in the isomerization reaction of linear alkanes, the metal is mainly dispersed in the molecular sieve channel, the spatial distance from the strongly acidic site is small, and the amount of acid on the outer surface is small. Therefore, in the alkane hydrogenation isomerization reaction, there are advantages such as a high substrate conversion rate and good selectivity of the hydrogenation isomerized product.

[0015] Other features and effects of the present invention will be described in the detailed description below.

[0016] [Brief explanation of the drawing] The following figures are used to provide a further understanding of the present application and constitute part of this specification. They are used to illustrate the present application together with the specific embodiments described below. However, they are not intended to limit the present application. Here, Figure 1 shows the XRD spectrum of the catalyst prepared in Production Example I-1; Figure 2 shows a TEM image of the catalyst prepared in manufacturing example I-1; Figure 3 shows an SEM image of the catalyst prepared in manufacturing example I-1; Figure 4 shows the XRD spectrum of the catalyst prepared in Production Example II-1; Figure 5 shows the infrared absorption spectrum of the catalyst prepared in Production Example II-1; Figure 6 shows the XRD spectrum of the catalyst prepared in Production Example II-3; Figure 7 shows the XRD spectrum of the catalyst prepared in Production Example III-1.

[0017] [Detailed description of the invention] The specific embodiments of this application will be described in detail below with reference to the drawings. Please understand that the specific embodiments described herein are used only to illustrate and explain the application and do not limit it in any way.

[0018] Any specific numerical value disclosed herein (including the endpoints of a numerical range) should be interpreted as including any value close to the exact value, such as any acceptable value within ±5% of the exact value, rather than being limited to the exact value itself. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of a range, combining an endpoint value with a specific numerical value within that range, or arbitrarily combining specific numerical values. Such new numerical ranges should also be considered as specifically disclosed herein.

[0019] In this specification, the so-called "silicon-aluminum ratio" or "silicon-aluminum molar ratio" refers to the molar ratio of silicon, calculated as SiO2, to aluminum, calculated as Al2O3, in a molecular sieve.

[0020] In this specification, w, m, s, vs, wm, ms, and s-vs in the XRD data of molecular sieves represent the relative intensity I / I0 of the diffraction peak at the corresponding 2θ angle relative to the strongest diffraction peak (i.e., the diffraction peak with the maximum intensity), calculated based on the intensity of the diffraction peaks, where I represents the peak intensity of the corresponding diffraction peak, I0 represents the peak intensity of the strongest diffraction peak, w means weak, m means medium, m and s mean strong, vs means very strong, wm means weak to medium, ms means medium to strong, and s-vs means strong to very strong. Such expressions are known to those skilled in the art. Generally, w represents less than 20, m represents 20 to 40, s represents 40 to 70, vs represents greater than 70, wm represents less than 40, ms represents 20 to 70, and s-vs represents greater than 40.

[0021] According to this invention, the interplanar spacing of each diffraction peak in the XRD diffraction spectrum of a molecular sieve can be calculated using Bragg's equation below, based on the 2θ value of the diffraction peak: λ = 2dsinθ (wherein λ is the wavelength of the incident wave, λ = 1.54 Å, d is the interplanar spacing, and θ is the angle between the incident light and the scattering plane).

[0022] In this specification, the term "pore volume" refers to the volume of pores per unit mass of the catalyst. The term "total pore volume" refers to the volume of all pores per unit mass of the catalyst. The term "micropore volume" refers to the volume of all micropores (generally, pores with a diameter of less than 2 nanometers) per unit mass of the catalyst.

[0023] In this specification, the term "specific surface area" refers to the total surface area per unit mass of a sample, including both the internal and external surface areas. Non-porous samples such as Portland cement and some clay mineral powders have only an external surface area. Porous samples such as asbestos fibers, diatomaceous earth, and molecular sieves have both an external and internal surface area. In porous samples, the surface area within micropores with a pore diameter of less than 2 nanometers constitutes the internal surface area. The external surface area is obtained by subtracting the internal surface area from the aforementioned surface area. The external surface area per unit mass of a sample is the external specific surface area. Therefore, in this specification, "external surface of the catalyst" refers to the surface of the catalyst excluding the internal surface of micropores with a pore diameter of less than 2 nanometers.

[0024] In this specification, “H-type silica-alumina molecular sieve” has the meaning commonly understood in the art, and in particular refers to a silica-alumina molecular sieve having an activated acidic moiety. This can usually be prepared directly using an acidic system, or by ammonium ion exchange and calcination of an alkali metal type silica-alumina molecular sieve, such as a Na-type silica-alumina molecular sieve.

[0025] In this application, unless otherwise specified, the amount and content of hydrogenation-active metal components are based on the metal.

[0026] Unless otherwise specified, terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and that definition differs from the common understanding in the art, the definition provided herein shall prevail.

[0027] In this application, unless expressly stated otherwise, matters not described herein are deemed to be the same as those known in the art without any modification. Furthermore, any embodiment described herein may be freely combined with one or more other embodiments described herein. Any technical solution or technical idea thus obtained shall be deemed to be part of the original disclosure or description herein and shall not be deemed to be novel matter not disclosed or anticipated herein unless such combination is clearly unreasonable to a person skilled in the art.

[0028] All patent documents and non-patent documents, including but not limited to textbooks and journal articles, referenced herein are incorporated herein in their entirety by reference.

[0029] As described above, in the first embodiment, the present invention provides a hydrogenation-acid catalyst with a dual function comprising, based on the mass of the catalyst, 80-99.8% silica-alumina molecular sieve component, 0.2-2% hydrogenation-active metal component supported on the molecular sieve, and 0-20% hydrocarbyl-modified component.

[0030] In the catalyst of the present invention, the hydrocarbyl-modified component is attached to the surface of the molecular sieve via covalent bonds, such as the covalent bonds of the hydrocarbyl-Si-O-molecular sieve. In certain embodiments, a silanation reagent can be used as a starting material, and the hydrocarbyl-modified component can be attached to the surface of the molecular sieve through the reaction of silicon-oxygen bonds linked to silicon with active hydroxyl groups on the surface of the molecular sieve.

[0031] In a preferred embodiment, the hydride-active metal is selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, and more preferably ruthenium, palladium, or a combination thereof.

[0032] In a preferred embodiment, the hydrocarbyl-modified component is C1-20 Hydrocarbyl, preferably C 1-10 The hydrocarbyl is more preferably selected from methyl, ethyl, propyl, isopropyl, butyl, phenyl, benzyl, phenethyl, or a combination thereof.

[0033] In preferred embodiments, the mass content of silica-alumina molecular sieves in the catalyst is 90-99.8% based on the mass of the catalyst, such as 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, etc. More preferably, the mass content of silica-alumina molecular sieves is 90-98%.

[0034] In preferred embodiments, the mass content of the hydrogenated metal in the catalyst is 0.2 to 1.5%, preferably 0.2 to 1.2%, more preferably 0.3 to 1.0%, based on the mass of the catalyst, such as 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc.

[0035] In preferred embodiments, the silica-alumina molecular sieve in the catalyst is selected from molecular sieves having an MWW structure, FAU structure, MOR structure, BEA structure, or ATS structure, or a combination thereof, and is preferably a molecular sieve having an ATS structure. Specific examples of molecular sieves having an MWW structure include SCM-1 molecular sieve and MCM-22 molecular sieve. Specific examples of molecular sieves having an FAU structure include X molecular sieve and Y molecular sieve. Specific examples of molecular sieves having an MOR structure include LZ-211 molecular sieve. Specific examples of molecular sieves having a BEA structure include β molecular sieve. In particular embodiments, the silica-alumina molecular sieve is an H-type silica-alumina molecular sieve.

[0036] In preferred embodiments, the silicon-aluminum ratio of the molecular sieves in the silica-alumina catalyst is 2 to 50, preferably 2 to 40, and more preferably 2 to 20.

[0037] In certain preferred embodiments, the molecular sieve in the catalyst is a silica-alumina molecular sieve having an ATS structure, and the X-ray diffraction spectrum of the catalyst exhibits the relative intensity characteristics of the diffraction peaks as shown in the table below:

[0038] [Table 1]

[0039] In a more preferred embodiment, the X-ray diffraction spectrum of the catalyst exhibits the relative intensity characteristics of the diffraction peaks shown in any of the rows in the following table:

[0040] [Table 2]

[0041] In a more preferred embodiment, the catalyst has a strip-like or rod-like crystal structure, with a crystal length of 0.3 to 3 μm and an aspect ratio of 2 to 20, preferably 5 to 20.

[0042] In this application, the catalyst may optionally undergo either a hydrocarbylation treatment or a reduction treatment, or both. Here, the hydrocarbylation treatment and the reduction treatment can be carried out during the preparation of the catalyst after supporting the hydrogenated metal, or before the use of the catalyst. When both the hydrocarbylation treatment and the reduction treatment are carried out, the reduction treatment can be carried out before or after the hydrocarbylation treatment, and it is preferable to carry it out after the hydrocarbylation treatment. In a preferred embodiment, the catalyst undergoes the reduction treatment. Furthermore, if the silica-alumina molecular sieve is a molecular sieve having an MWW, FAU, MOR, or BEA structure, it is preferable to subject the catalyst to a hydrocarbylation treatment.

[0043] In this application, the hydrogenating metal in the catalyst may exist in various forms, such as a metal element, oxide, chloride, nitrate, or a combination thereof. In a preferred embodiment, the hydrogenating metal exists mainly in the form of a metal element when the catalyst is subjected to reduction treatment. Preferably, in the catalyst, the particle size of the hydrogenating metal particles is 0.5 to 10 nm, and more preferably 1 to 5 nm.

[0044] In certain preferred embodiments, the silica-alumina molecular sieve in the catalyst is a molecular sieve having an ATS structure, particularly an ATS molecular sieve having the above-described XRD spectral characteristics, wherein the mass content of the silicon-aluminum molecular sieve is 80-99.8%, preferably 90-99.8%, based on the mass of the catalyst, the mass content of the hydrogenated active metal is 0.2-2%, preferably 0.2-1.5%, and the catalyst does not contain hydrocarbyl-modified components.

[0045] In other preferred embodiments, particularly when the silica-alumina molecular sieve is a molecular sieve having an MWW, FAU, MOR, or BEA structure, the mass content of the silica-alumina molecular sieve in the catalyst is 80-98%, preferably 90-98%, based on the mass of the catalyst; the mass content of the hydrogenated active metal is 0.2-1.5%, preferably 0.2-1.2%, more preferably 0.3-1.0%; and the mass content of the hydrocarbyl modified component is 1-20%, preferably 1-10%, more preferably 2-10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.

[0046] In a more preferred embodiment, the mass content of the hydrogenated metal on the outer surface of the catalyst relative to the elements on the outer surface, as measured by X-ray photoelectron spectroscopy (XPS), is 0.5% or less, preferably 0.4% or less, more preferably 0.01 to 0.35%, for example, 0.01 to 0.2%.

[0047] In a more preferred embodiment, the distribution coefficient of the hydrogenation active metal on the outer surface of the catalyst is 1 to 20%, preferably 1.5 to 18%, more preferably 1.5 to 12%, for example 1.5 to 10%.

[0048] In the present application, the distribution coefficient of the hydrogenation active metal on the outer surface of the catalyst is calculated by the following formula: Distribution coefficient of the hydrogenation active metal on the outer surface = (mass content of the hydrogenation active metal on the outer surface with respect to the elements on the outer surface of the catalyst * specific surface area of the outer surface of the catalyst) / (total mass content of the hydrogenation active metal contained in the catalyst * specific surface area of the catalyst) * 100%, Here, the mass content of the hydrogenation active metal on the outer surface with respect to the elements on the outer surface of the catalyst is measured by X-ray photoelectron spectroscopy (XPS), and the total mass content of the hydrogenation active metal contained in the catalyst can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0049] According to the present application, the ratio of the content of the hydrogenation active metal on the outer surface of the catalyst to the total amount of the hydrogenation active metal can be characterized by using the distribution coefficient of the hydrogenation active metal on the outer surface of the catalyst. Specifically, when the hydrogenation active metal in the catalyst is supported on the inner and outer surfaces of the molecular sieve using a simple impregnation method, the ratio of the content of the hydrogenation active metal on the outer surface to the total content of the hydrogenation active metal is not only proportional to the relative distribution of the hydrogenation active metal on the outer surface but also proportional to the ratio of the outer surface area of the catalyst.

[0050] In a preferred embodiment, the specific surface area of the catalyst is 200 to 800 m 2 / g, preferably 250 to 700 m 2 / g, for example 300 m 2 / g, 380 m 2 / g, 385 m<{ 2 / g, 410 m 2 / g, 490 m 2 / g or 500 m 2 / g.

[0051] In a preferred embodiment, the total pore volume of the catalyst is 0.15 cm³. 3 The amount is 0.18 to 1.0 cm² or more, preferably 0.18 to 1.0 cm². 3 / g, more preferably 0.2~1.0cm 3 This is expressed as / g, for example, 0.2~0.9cm 3 It is / g.

[0052] In a preferred embodiment, the pore volume of the catalyst is 0.05 to 0.30 cm³. 3 The density is / g, preferably 0.10-0.25cm 3 It is / g.

[0053] In a preferred embodiment, the total acid content of the catalyst is 400 to 1500 μmol·g -1 The concentration is preferably 600-1500 μmol·g -1 For example, 800 μmol·g -1 Therefore, 1250 μmol·g -1 Therefore, 1300 μmol·g -1 or 1500 μmol·g -1 That is the case.

[0054] In some preferred embodiments, for example, when the catalyst undergoes hydrocarbylation treatment (i.e., when the content of hydrocarbyl-modified components in the catalyst is 1-20%, preferably in the range of 1-10%), the relative acid equivalent of the outer surface of the catalyst is 15-50%, preferably 15-40%, for example, 20%, 30%, or 35%.

[0055] In certain preferred embodiments, for example, when the catalyst undergoes hydrocarbylation treatment, the acid content ratio of B acid / L acid in the catalyst is 0.2 to 8.0, preferably 0.4 to 6.0, and more preferably 3.0 to 6.0, for example 5.0 or 5.5.

[0056] In other preferred embodiments, for example, when the catalyst is based on ATS molecular sieves and has not undergone hydrocarbylation treatment, the acid content ratio of B acid / L acid in the catalyst is 3 to 10, preferably 5 to 7.

[0057] In a preferred embodiment, when hydrocarbylation treatment is performed but reduction treatment is not, the metal H2-TPR test reduction temperature of the catalyst is 470-500°C, preferably 480-500°C.

[0058] In a second embodiment, a method for preparing the catalyst of the present invention is provided, comprising the following steps: (1) A step of providing an H-type silica-alumina molecular sieve; and (2) A step of supporting a hydrogenation-active metal on an H-type silica-alumina molecular sieve, and optionally subjecting the resulting product to hydrocarbylation and / or reduction to obtain a catalyst.

[0059] In a preferred embodiment, the H-type silica-alumina molecule is selected from molecular sieves having an MWW, FAU, MOR, BEA, or ATS structure, or a combination thereof, and is preferably a molecular sieve having an ATS structure.

[0060] In some preferred embodiments, step (1) includes performing ammonium ion exchange and calcination on the raw materials of the silica-alumina molecular sieve in order to obtain an H-type silica-alumina molecular sieve.

[0061] In a more preferred embodiment, the silica-alumina molecular sieve raw material is selected from silica-alumina molecular sieves having an MWW, FAU, MOR, or BEA structure, or a combination thereof.

[0062] In certain specific embodiments, the ammonium ion exchange in step (1) is performed in an alkali metal type molecular sieve. + and K +Alkali metal or alkaline earth metal cations such as NH 4+ The ammonium ion exchange is performed at 20-60°C for 0.5-4 hours, one or more times. The ammonium salt used in the ammonium ion exchange is selected from one or more of ammonia, ammonium chloride, ammonium nitrate, and ammonium carbonate. The concentration of the ammonium salt is 0.1-1.0 mol / L. After ammonium ion exchange, the molecular sieves are dried and calcined at 60-120°C for 4-24 hours. The calcination temperature is 400-650°C, the calcination time is 1-12 hours, and the calcination atmosphere is oxygen or air, yielding H-type silica-alumina molecular sieves.

[0063] In another preferred embodiment, step (1) includes mixing a silicon source, an aluminum source, a fluorine source, an organic structure modifier, and water, and then performing a pretreatment by heating, followed by a crystallization treatment and calcination to obtain an H-type ATS silica-alumina molecular sieve.

[0064] In a more preferred embodiment, in step (1), an additive silicon source calculated as SiO2, an aluminum source calculated as Al2O3, and F - The molar ratio of the fluorine source, organic structural modifier, and water calculated as follows is 1:(0.02~0.2):(0.5~2):(0.25~1.5):(3~15), and preferably 1:(0.05~0.15):(0.5~1):(0.5~1):(5~10).

[0065] In a further preferred embodiment, in step (1), the silicon source is selected from silicic acid, silica gel, silica sol, tetraethyl silicate, sodium silicate, or a combination thereof; the aluminum source is selected from boehmite pseudo, aluminum isopropoxide, or a combination thereof; the fluorine source is hydrofluoric acid; and the organic structure-controlling agent is 4-pyrrolidinylpyridine. In this embodiment, 4-pyrrolidinylpyridine is used as the organic structure-controlling agent. There is no need to add a base during the reaction, and the resulting molecular sieve can be used as a catalyst without ammonium ion exchange.

[0066] In a more preferred embodiment, the heating pretreatment method in step (1) is rotary evaporation to remove moisture or open heating to remove moisture, and the treatment conditions for open heating are heating and stirring at 50 to 100°C, preferably 70 to 90°C.

[0067] In a more preferred embodiment, after the raw material mixture is heated and pretreated in step (1), the molar ratio of the silicon source (calculated as SiO2) to water during crystallization is 1:(1 to 10), preferably 1:(1.5 to 6.5).

[0068] In a more preferred embodiment, the crystallization conditions in step (1) include a crystallization temperature of 120 to 200°C, preferably 150 to 200°C, and a crystallization time of 7 to 21 days, preferably 7 to 15 days.

[0069] In a further preferred embodiment, in step (1), crystallization can be carried out by any method conventionally known in the art, such as mixing a silicon source, an aluminum source, a fluorine source, an organic structure-determining agent, and water in predetermined ratios, and then heating the resulting mixture under crystallization conditions to crystallize it.

[0070] In a more preferred embodiment, after the crystallization step is completed in step (1), the product can be obtained from the mixture by any conventionally known separation method and calcination treatment. Examples of separation methods include filtering, washing, and drying the mixture. Here, filtering, washing, and drying can be carried out by any conventionally known method in the art. For example, as filtration, the mixture of products obtained may be simply filtered by suction. Washing includes, for example, washing with deionized water and / or ethanol. The drying temperature includes, for example, 40 to 250°C, preferably 60 to 150°C, and the drying time includes, for example, 8 to 30 hours, preferably 10 to 20 hours. This drying may be carried out under atmospheric pressure or under reduced pressure.

[0071] In a further preferred embodiment, in step (1), the firing can be carried out by any method conventionally known in the art. For example, the firing temperature is generally 300 to 800°C, preferably 400 to 650°C, and the firing time is generally 1 to 12 hours, preferably 2 to 6 hours. Furthermore, the firing is generally carried out in an oxygen-containing atmosphere, such as in an air or oxygen atmosphere.

[0072] According to the present invention, in step (2), the hydrogenated metal can be supported on an H-type silica-alumina molecular sieve by conventional means (such as impregnation). In a preferred embodiment, in step (2), a solution of the hydrogenated metal source is added to the H-type silica-alumina molecular sieve, and then dried to support the hydrogenated metal on the H-type silica-alumina molecular sieve.

[0073] In a further preferred embodiment, in step (2), the hydrogenation-active metal source is selected from soluble compounds of the metal, preferably from chlorides, nitrates, or combinations thereof of the metal. Taking ruthenium as an example, the solution of the hydrogenation-active metal source may be a ruthenium-containing solution prepared from ruthenium nitrate or ruthenium chloride.

[0074] In a more preferred embodiment, in step (2), the concentration of the solution of the hydrogenated metal source is 1.5 to 50 g / L, preferably 2 to 45 g / L, based on the mass of the hydrogenated metal.

[0075] In a more preferred embodiment, in step (2), a solution of the hydrogenation-activated metal source is added dropwise to the H-type silica-alumina molecular sieve of step (1). The present invention does not particularly limit the dropwise addition conditions. For example, after dropwise addition at room temperature, mixing can be performed for 1 to 10 hours.

[0076] In a more preferred embodiment, in step (2), the mass ratio of the hydrogenated metal in the solution of the hydrogenated metal source to the H-type silica-alumina molecular sieve of step (1) is 0.002 to 0.015:1, for example, 0.005 to 0.02:1.

[0077] In a more preferred embodiment, drying in step (2) can be carried out by a conventional method such as oven drying. The drying conditions preferably include a drying temperature of 40 to 90°C and a drying time of 4 to 12 hours.

[0078] According to the present invention, in step (2), after supporting the hydrogenated metal on an H-type silica-alumina molecular sieve, the obtained product can be optionally subjected to either a hydrocarbylation treatment or a reduction treatment, or both. When both hydrocarbylation and reduction treatments are performed, the reduction treatment can be performed before or after the hydrocarbylation treatment, preferably after the hydrocarbylation treatment.

[0079] In a preferred embodiment, step (2) includes reducing the product after supporting the hydride-active metal. More preferably, the reduction can be carried out using a reducing gas, preferably hydrogen reduction, and the reduction conditions are preferably a reduction temperature of 300 to 550°C, a reduction time of 3 to 6 hours, and a volume space velocity of the reducing gas of 40 to 200 h. -1 This includes being.

[0080] In preferred embodiments, particularly when the H-type silica-alumina molecular sieve is a molecular sieve having an MWW, FAU, MOR, or BEA structure, step (2) includes hydrocarbylation of the product after the hydrogenation-active metal has been supported. Preferably, the product after the hydrogenation-active metal has been subjected to reduction first, and then hydrocarbylation.

[0081] In a more preferred embodiment, the hydrocarbylation treatment of step (2) includes, preferably, reducing the product supported with the hydrogenated metal, and then mixing and reacting it with a hydrocarbylation reagent in a solvent.

[0082] In a more preferred embodiment, the hydrocarbylating reagent is methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, tolylsilanetriol, diphenylsilanediol, or a combination thereof, preferably selected from dimethyldimethoxysilane, diethyldimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, tolylsilanetriol, or a combination thereof. More preferably, the solvent used for the hydrocarbylating treatment is selected from ethanol, toluene, or a combination thereof.

[0083] In a more preferred embodiment, in the hydrocarbylation treatment, the mass ratio of the product supported by the hydrogenated metal, the hydrocarbylation reagent, and the solvent is 1:(0.05~0.45):(5~55), preferably 1:(0.06~0.40):(6~50), for example, 1:(0.10~0.33):(8~50), or 1:(0.12~0.35):(7.5~52).

[0084] In a further preferred embodiment, the hydrocarbylation treatment includes reaction conditions such as a reaction temperature of 40 to 110°C, preferably 70 to 110°C, and a reaction time of 6 to 48 hours, preferably 8 to 24 hours.

[0085] In certain more preferred embodiments, after hydrocarbylation, the reaction product obtained is separated (e.g., by filtration), washed, and dried. According to the present invention, separation, washing, and drying can be carried out by any method conventionally known in the art. For example, filtration may simply be by suction filtration of the mixture of products obtained. An example of washing is washing with deionized water and / or ethanol. An example of drying temperature is 40 to 250°C, preferably 60 to 150°C. An example of drying time is 8 to 30 hours, preferably 10 to 20 hours. Drying may be carried out under atmospheric pressure or under reduced pressure.

[0086] In a third embodiment, a hydrogenation-acid catalyst with dual function, prepared by the method of the present invention, is provided.

[0087] In specific embodiments, the various characteristics of the hydrogenation-acid catalyst dual-function catalyst obtained by the method of the present invention are as described in the first aspect of the present invention and will not be described again here.

[0088] In a fourth embodiment, the use of the catalyst of the present invention in a hydrocarbon hydrogenation reaction is provided, comprising the step of contacting and reacting a hydrocarbon raw material with the catalyst in the presence of hydrogen.

[0089] In preferred embodiments, the hydrogenation reaction of hydrocarbons is selected from the hydroalkylation reaction of benzene and the hydroisomerization reaction of alkanes.

[0090] In a fifth embodiment, the present application provides a one-step method for producing cyclohexylbenzene by hydrogenating benzene. This method comprises contacting and reacting benzene with a catalyst described herein in the presence of hydrogen to obtain cyclohexylbenzene.

[0091] In preferred embodiments, the reaction conditions include: a mass ratio of benzene to catalyst of 8 to 40, preferably 10 to 40; a reaction temperature of 100 to 220°C, preferably 120 to 200°C; a reaction time of 2 to 8 hours, preferably 2.5 to 6 hours; and a hydrogen pressure of 0.8 to 2.5 MPa, preferably 1.0 to 2.5 MPa.

[0092] In a sixth embodiment, the present application provides a method for hydroisomerizing an alkane. This method comprises contacting and reacting a linear alkane with the catalyst of the present application in the presence of hydrogen to obtain an isomerization product, wherein the linear alkane is a linear alkane of C8 or more, such as n-heptane or n-decane, preferably a linear alkane of C8 to C20, and more preferably a linear alkane of C8 to C12.

[0093] In preferred embodiments, the reaction conditions include: a mass ratio of linear alkane to catalyst of 10 to 100, preferably 10 to 50; a reaction temperature of 250 to 400°C, preferably 300 to 400°C; a reaction time of 3 to 10 hours, preferably 4 to 10 hours; and a hydrogen pressure of 2.5 to 5.0 MPa, preferably 3.0 to 4.0 MPa.

[0094] In certain preferred embodiments, the following technical solutions are provided: A1. A catalyst for producing cyclohexylbenzene having an approximate chemical composition represented by the formula "xM·ySiO2·zAl2O3"; In the formula, M is a metallic element selected from one or more of the metals ruthenium, platinum, palladium, copper, and nickel; In the chemical composition of the formula, 0.001 ≤ x / y ≤ 0.02 and 8 ≤ y / z ≤ 80.

[0095] A2. The catalyst according to item A1, characterized in that the mass content of the metal M is 0.2% to 2% based on the mass of the catalyst.

[0096] A3. The catalyst described in item A1, characterized by having the X-ray diffraction pattern shown in the table below:

[0097] [Table 3]

[0098] A4. The catalyst according to item A1 or A3, further comprising the X-ray diffraction patterns shown in the table below.

[0099] [Table 4]

[0100] A5. Total acid content is 500-1500 μmol·g -1 The concentration is preferably 800-1500 μmol·g -1 The catalyst according to item A1, characterized in that the acid content ratio of acid B / acid L is 3 to 10, preferably 5 to 7.

[0101] A6. The catalyst according to item A1, characterized in that the crystals have a strip-like or rod-like form, the length of the crystals is 0.3 to 3 μm, and the aspect ratio is 2 to 20.

[0102] A7. The specific surface area of ​​the catalyst is 200-600 m². 2 The amount is / g, preferably 250-500m 2 It is characterized by having a concentration of / g; the pore volume of the catalyst is 0.05~0.30 cm³. 3 The density is / g, preferably 0.10-0.25cm 3 The catalyst described in item A1, characterized by being / g.

[0103] A8. A method for preparing a catalyst for producing cyclohexylbenzene as described in any one of items A1 to A7, which includes the following steps: (1) A silicon source, an aluminum source, a fluorine source, an organic structural modifier, and water are mixed, pretreated by heating, and then crystallized and calcined to obtain sample B; (2) Add a solution containing metal M to sample B from step (1), dry and reduce to prepare a catalyst.

[0104] A9. In step (1), the added silicon source calculated as SiO2, the aluminum source calculated as Al2O3, and F - The preparation method described in item A8, characterized in that the molar ratio of the fluorine source calculated as such, the organic structure modifier, and water is 1:(0.02-0.2):(0.5-2):(0.25-1.5):(3-15), and preferably 1:(0.05-0.15):(0.5-1):(0.5-1):(5-10).

[0105] A10. The preparation method according to item A8 or A9, characterized in that in step (1), the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl silicate, and sodium silicate; the aluminum source is selected from at least one of pseudoboehmite and aluminum isopropoxide; the fluorine source in step (1) is hydrofluoric acid; and the organic structure-determining agent is 4-pyrrolidinylpyridine.

[0106] A11. The preparation method according to item A8 or A9, characterized in that, in step (1), the molar ratio of the silicon source calculated as SiO2 in the raw material mixture after heating and pretreatment to water during crystallization is 1:(1~10), preferably 1:(1.5~6.5).

[0107] A12. The preparation method according to item A8 or A9, characterized in that in step (1), the crystallization conditions include a temperature of 120 to 200°C and a time of 7 to 21 days, preferably a temperature of 150 to 200°C and a time of 7 to 15 days.

[0108] A13. The preparation method according to item A8 or A9, characterized in that in step (2), the concentration of the solution containing metal M is 2 to 50 g / L.

[0109] A14. A one-step method for producing cyclohexylbenzene by hydrogenating benzene using one of the catalysts described in items A1 to A7.

[0110] A15. The method according to item A14, characterized by using hydrogen as a hydrogen source for producing cyclohexylbenzene and comprising a catalytic reaction between a starting material benzene and a catalyst; where the mass ratio of the starting material benzene to the catalyst is 8 to 40; the reaction temperature is 100 to 220°C; the reaction time is 2 to 8 hours; and the hydrogen pressure is 0.8 to 2.5 MPa.

[0111] B1. A catalyst for producing cyclohexylbenzene, characterized by comprising a molecular sieve, an active metal M, and a hydrocarbyl modifying group; Here, the active metal M is selected from one or more of ruthenium, platinum, palladium, copper, and nickel; Here, the hydrocarbyl modifying group is selected from at least one C1-C4 alkyl group; Here, based on the mass of the catalyst, the mass content of the active metal M is 0.2% to 1.5%, the mass content of the metal M on the outer surface relative to the elements on the outer surface of the catalyst is 0.4% or less, and the partition coefficient of the metal M on the outer surface is 1.2% to 20%.

[0112] B2. The catalyst according to item B1, characterized in that the mass content of the metal M is 0.2% to 1.2% based on the mass of the catalyst.

[0113] B3. The catalyst according to item B1, characterized in that the mass content of the hydrocarbyl modifying group is 1% to 10% based on the mass of the catalyst.

[0114] B4. The catalyst according to item B1, characterized in that the molecular sieve in the catalyst is selected from at least one of MWW, FAU, MOR, BEA, and ATS molecular sieves; the molecular sieve in the catalyst accounts for 90% to 98% of the catalyst mass; and the silicon / aluminum ratio is 2 to 50, preferably 4 to 40.

[0115] B5. Catalyst specific surface area is 380-800 m² 2 The value is / g, preferably 400-700m 2 The total pore volume of the catalyst is 0.15 cm³ / g; 3 The amount is 0.2 to 0.9 cm² or more, preferably 0.2 to 0.9 cm². 3 The catalyst described in item B1, characterized by being / g.

[0116] B6. A method for preparing a catalyst for producing cyclohexylbenzene as described in any one of items B1 to B5, comprising the following steps: (i) A process of obtaining H-type molecular sieves by calcining ammonium ion-exchanged molecular sieve raw materials; (ii) A step in which a solution containing metal M is added to the H-type molecular sieve from step (1), and the mixture is dried and reduced to obtain a catalyst precursor; (iii) A step of preparing a catalyst by mixing and reacting a catalyst precursor, an alkylating reagent, and a solvent, followed by filtration, washing, and drying.

[0117] The preparation method described in item B6, characterized in that in step (i), the concentration of the solution containing metal M is 2 to 50 g / L.

[0118] The preparation method according to item B6, characterized in that in step (ii), the alkylating reagent is selected from one or more of methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, propyltrimethoxysilane, and isopropyltrimethoxysilane, preferably selected from one or more of dimethyldimethoxysilane, diethyldimethoxysilane, and isopropyltrimethoxysilane; and the solvent is at least one of ethanol or toluene.

[0119] The preparation method according to item B6, characterized in that in step (iii) B9, the mass ratio of the catalyst precursor, alkylating reagent, and solvent added is 1:(0.05~0.40):(5~50).

[0120] B10. A one-step method for producing cyclohexylbenzene by hydrogenating benzene using one of the catalysts described in items B1 to B5.

[0121] C1. The process involves a catalytic reaction between the starting material benzene and a catalyst, using hydrogen as the hydrogen source to produce cyclohexylbenzene; the catalyst comprises a molecular sieve, an active metal M, and a hydrocarbyl modifying group; Here, the active metal M is selected from one or more of ruthenium, platinum, palladium, copper, and nickel; Here, the hydrocarbyl modifying group is selected from at least one of phenyl, benzyl, and phenethyl; Here, the total acid content of the catalyst is 400-1500 μmol·g. -1 A one-step method for producing cyclohexylbenzene by hydrogenating benzene, wherein the relative acid equivalent on the outer surface of the catalyst is 15-35%.

[0122] C2. The method according to item C1, characterized in that the metal M is preferably a ruthenium and / or palladium metallic element.

[0123] C3. The method according to item C1, characterized in that the mass content of the hydrocarbyl modifying group is 2% to 20% based on the mass of the catalyst.

[0124] C4. The method according to item C1, characterized in that the molecular sieve in the catalyst is selected from at least one of MWW, FAU, MOR, BEA, and ATS molecular sieves; the molecular sieve in the catalyst accounts for 80% to 95% of the catalyst mass; and the molar ratio of silicon to aluminum is 2 to 50, preferably 4 to 40.

[0125] C5. The specific surface area of ​​the catalyst is 385-500 m². 2 The value is / g, preferably 410-490m 2 It is characterized by having a concentration of / g; the total pore volume of the catalyst is 0.18 cm³. 3 The amount is 0.18 to 1.0 cm² or more, preferably 0.18 to 1.0 cm². 3 The method according to item C1, characterized in that it is / g.

[0126] C6. The method according to item C1, characterized in that the catalyst preparation method includes the following steps: (A) A step of preparing a catalyst precursor by mixing a solution containing metal M with an H-type molecular sieve, drying and reducing it; (B) A step of preparing a catalyst by mixing and reacting a catalyst precursor, an arylation reagent, and a solvent, followed by filtration, washing, and drying.

[0127] The method according to item C6, characterized in that in step (A), the concentration of the solution containing metal M is 1.5 to 45 g / L.

[0128] The method according to item C6, characterized in that in step (B), the arylation reagent is selected from one or more of phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, tolylsilanetriol, and diphenylsilanediol; and the solvent is at least one of ethanol or toluene.

[0129] The method according to item C6, characterized in that in step (B) C9, the mass ratio of the added catalyst precursor, arylation reagent, and solvent is 1:(0.06~0.45):(6~55).

[0130] C10. The method according to item C1, characterized in that, in the above reaction, the mass ratio of the starting material benzene to the catalyst is 8 to 40, the reaction temperature is 100 to 220°C, the reaction time is 2 to 8 hours, and the hydrogen pressure is 0.8 to 2.5 MPa.

[0131] [Examples] The technical solutions of the present invention will be described in more detail by the following embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0132] In the following examples and comparative examples, unless otherwise specified, all reagents and raw materials used are commercially available and of analytical grade purity.

[0133] In the following examples and comparative examples, experimental methods for which specific conditions are not given should be selected according to conventional methods and conditions, or according to the product's instructions.

[0134] In the present invention, including the following examples and comparative examples, the structure of the sample is determined by X-ray diffraction (XRD) spectroscopy, and the XRD spectrum is determined by an X-ray powder diffractometer. The type of X-ray powder diffractometer used is a Panalytical X PERPRO X-ray powder diffractometer. The following conditions were used to analyze the physical phase of the sample: CuKα source (λ=1.54Å), nickel filter, 2θ scanning range 2~50°, operating voltage 40kV, current 40mA, scanning speed 10° / min.

[0135] In this application, including the following examples and comparative examples, the scanning electron microscope (SEM) used was an S-4800II field emission scanning electron microscope. The method for measuring the crystal particle size of the sample is as follows: A randomly selected field of view is used to observe molecular sieves at a magnification of 10,000x using a scanning electron microscope. The average of the sum of the particle sizes of all crystals within the field of view is calculated, and this operation is repeated a total of 10 times. The average of the sum of these 10 average values ​​is taken as the crystal particle size.

[0136] In the present application, including the following examples and comparative examples, the size of the sample was measured as follows: Using a transmission electron microscope (G2F30 transmission electron microscope, manufactured by FEI, Netherlands, operating voltage 300kV), the observation field was randomly selected, and the molecular sieve was observed at a magnification of 100,000 times. The average of the sum of the sizes of all particles in the observation field was calculated, and this operation was repeated a total of 10 times. The average of the sum of the average values ​​from these 10 times was used as the particle size.

[0137] In this application, including the following examples and comparative examples, the acid content and type of acid in the sample were measured using pyridine adsorption infrared spectroscopy (Nicolet Model 710 spectrometer). The specific procedure was as follows: a. Sample pretreatment. The sample (approximately 30 mg) was pressed into a thin disc with a diameter of 13 mm and placed in the infrared sample chamber. The sample was then pretreated at 400°C for 1 hour under vacuum cell conditions. After the sample chamber cooled to room temperature, the infrared data of the sample was scanned as background. b. Pyridine adsorption. At room temperature and under vacuum conditions, pyridine vapor was introduced back into the original position until adsorption reached equilibrium. The adsorption time was 1 hour. c. Pyridine desorption. After adsorption was complete, the chamber was evacuated at 100°C until the internal pressure no longer changed. The desorption time was 40 minutes, and the infrared absorption spectra were scanned and recorded. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption infrared absorption spectrum. Based on this spectrum, the acid content of the sample was calculated:

[0138]

number

[0139] In the formula, r and w are the diameter (cm) and mass (g) of the catalyst thin plate, and A is the integrated absorbance value at a given wavenumber peak based on a scanning pyridine adsorption infrared absorption spectrum. IMEC is the integrated molar decay coefficient, and IMEC L 2.22, IMEC B It is 1.67. 1545cm -1 The nearby peak is acid B, at 1455 cm. -1 The peak in the vicinity represents L-acid.

[0140] In this application, including the following examples and comparative examples, the relative acid equivalent properties of the catalyst's outer surface were measured using the thermal decomposition of triisopropylbenzene, a "probe reaction." Specifically, a chromatography column sample was prepared by mixing 50 mg of catalyst with 100 mg of quartz sand. Then, 1 μL of triisopropylbenzene solution was injected at once into a gas chromatograph (GC, Agilent 7890B) at 250°C. The relative acid content and activity of the catalyst's outer surface were then evaluated by comparing the yield of cyclohexene in the chromatogram with the structure of an unhydrocarbylated "metal molecular sieve." The specific calculation method is as follows: Relative acid equivalent of the outer surface = (Amount of propylene produced by the hydrocarbylated group / (Amount of triisopropylbenzene added to the hydrocarbylated group × 3)) / (Amount of propylene produced by the unhydrocarbylated group / (Amount of triisopropylbenzene added to the unhydrocarbylated group × 3)) × 100%.

[0141] In this application, including the following examples and comparative examples, the total pore volume, micropore volume, total specific surface area, and specific surface area of ​​the outer surface of the sample are measured by the nitrogen physicoadsorption-desorption method (BET method): the nitrogen physicoadsorption-desorption isotherm of the molecular sieve is measured using a physicoadsorption device (e.g., Micromeretic ASAP2020M physicoadsorption device), and the values ​​are calculated using the BET formula and the t-plot formula.

[0142] In this application, including the following examples and comparative examples, the inductively coupled plasma atomic emission spectrometer (ICP) used is the Varian 725-ES. The analytical sample was dissolved in hydrofluoric acid, and the elemental content (moles) of the hydrogenated metal (hereinafter referred to as "metal M") in the sample was detected and converted to determine the mass content.

[0143] In the present application, including the following examples and comparative examples, the mass content of metal M on the outer surface of the catalyst relative to the elements on the outer surface of the catalyst is determined by X-ray photoelectron spectroscopy (XPS), which is a test of the elemental state of the catalyst surface. The X-ray photoelectron spectrometer used is an ESCA LAB-250 X-ray photoelectron spectrometer manufactured by Thermo Company, with Al Ka ​​= 1486.6 eV as the X-ray source, a voltage of 12 kV, a current of 20 mA, a detection thickness of 3 nm, and C1s = 284.6 eV as the internal standard for correcting the measured elemental signals.

[0144] In this application, including the following examples and comparative examples, the distribution coefficient of metal M on the outer surface of the catalyst is calculated by the following formula: The partition coefficient of metal M = (mass content of metal M on the outer surface of the catalyst relative to the elements on the outer surface of the catalyst × specific surface area of ​​the outer surface of the catalyst) / (total mass content of metal M in the catalyst × specific surface area of ​​the catalyst) × 100%.

[0145] In this application, including the following examples and comparative examples, the metal reduction temperature is determined by the H2-TPR test (hydrogen temperature programmed reduction). The TPR tester is an AMI-3300 temperature programmed absorption apparatus from Altamira Instruments. The test method involves filling the sample, purging it with argon at 300°C for 1 hour, and then cooling it to 50°C. A 10% H2-Ar mixed gas is introduced at a total flow rate of 30 mL / min, and the temperature is increased to 900°C at a rate of 10°C / min. The H2 consumption curve is measured, and the peak temperature of the curve is recorded as the reduction temperature of the sample.

[0146] In this application, including the following examples and comparative examples, the mass content of hydrocarbyl-modified components is measured using thermogravimetric-mass spectrometry (TG-MS) mass loss ratio, and the type of hydrocarbyl modification is confirmed by mass spectrometry. The analytical instrument used is a Netzsch STA449F3-QMS403 model. Thermogravimetric measurements of the samples at 25 to 1000°C were performed at a heating rate of 10°C / min.

[0147] In this application, including the following examples and comparative examples, the infrared absorption spectra of catalysts were measured using a Fourier transform infrared spectrometer (FTIR). The analyzer was a Thermo Fisher Scientific Nicolet 5700 model. The test range was wavenumber 400–4000 cm⁻¹. -1 The absorption spectrum was obtained at this point.

[0148] In this application, including the following examples and comparative examples, the reaction product cyclohexylbenzene was characterized by gas chromatography-mass spectrometry (GC-MS), and the yield of the product cyclohexylbenzene and the conversion rate of the reaction substrate were analyzed by gas chromatography (GC). The GC / MS instrument was an Agilent 7890A from Agilent, USA, with an HP-5 nonpolar capillary column (30 m, 0.53 mm). The gas chromatograph was an Agilent 7890B, with a flame ionization detector (FID), and an SE-54 capillary column (30 m, 0.53 mm).

[0149] The formulas for calculating the yield and selectivity of the product, cyclohexylbenzene, are as follows: Yield of the product, cyclohexylbenzene (%) = (moles of cyclohexylbenzene produced by the reaction × 2) / (moles of benzene, the reaction substrate) × 100%.

[0150] The selectivity (%) for the product, cyclohexylbenzene, is calculated as follows: (Number of moles of cyclohexylbenzene produced by the reaction × 2) / (Number of moles of benzene reacted) × 100%.

[0151] Similarly, in the present application, including the following examples and comparative examples, the yield and selectivity of the isomerization product in the n-decane hydrogenation isomerization reaction are as follows: Yield of isomerization product (%) = (Number of moles of isomerization product produced by the reaction) / (Number of moles of n-decane, the reaction substrate) × 100%.

[0152] Selectivity of isomerized product (%) = (Number of moles of isomerized product produced in the reaction) / (Number of moles of n-decane reacted) × 100%.

[0153] (Preparation Example 1-1) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0154] 1.2 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0155] The XRD spectral data of the catalyst is shown in Table I-1. The XRD spectrum of the catalyst is shown in Figure 1. TEM and SEM images of the catalyst are shown in Figures 2 and 3, respectively. In the catalyst composition, n(SiO2):n(Al2O3)=10, the mass fraction of Ru was 0.3%, and the chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0156] According to the SEM in Figure 3, the crystals in the catalyst were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0157] [Table 5]

[0158] (Preparation example I-2) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0159] 2.5 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0160] Table I-2 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst is the same as in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=10, the mass fraction of Ru was 0.6%, and the chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0041 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0161] The SEM image of the catalyst is the same as in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0162] [Table 6]

[0163] (Preparation example I-3) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0164] 6 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0165] Table I-3 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=10, and the mass fraction of Ru was 1.5%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0104 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0166] The SEM image of the catalyst was similar to that shown in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0167] [Table 7]

[0168] (Preparation example I-4) Mix 4g of deionized water, 1.1g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.75g of hydrofluoric acid uniformly to form a mixture with the ratio 1SiO2:0.1Al2O3:1.5F - A component with the composition :29H2O:0.75OSDA was obtained. Pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:4.5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0169] 1.2 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0170] Table I-4 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=10, and the mass fraction of Ru was 0.3%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0171] The SEM image of the catalyst is the same as in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4 to 2.0 μm and an aspect ratio of 2 to 15.

[0172] [Table 8]

[0173] (Preparation example I-5) Mix 4g of deionized water, 1.5g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 1g of hydrofluoric acid uniformly to form 1SiO2:0.1Al2O3:2F - A component with the composition :30H2O:1OSDA was obtained. Pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:4.5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0174] 1.2 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0175] Table I-5 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=10, and the mass fraction of Ru was 0.3%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0176] The SEM image of the catalyst was similar to that shown in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.5–2.5 μm and an aspect ratio of 3–20.

[0177] [Table 9]

[0178] (Preparation example I-6) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0179] 1.2 mL of 2.7 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0180] Table I-6 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=10, and the mass fraction of Pd was 0.3%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=10. The properties of the obtained catalyst are shown in Table I-13.

[0181] The SEM image of the catalyst was similar to that shown in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0182] [Table 10]

[0183] (Preparation example I-7) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.21g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.05Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0184] 1.2 mL of 3.2 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0185] Table I-7 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=20, and the mass fraction of Ru was 0.3%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=20. The properties of the obtained catalyst are shown in Table I-13.

[0186] The SEM image of the catalyst was similar to that shown in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–12.

[0187] [Table 11]

[0188] (Preparation example I-8) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.08g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.02Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0189] 1.2 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0190] Table I-8 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was the same as that shown in Figure 1. In the catalyst composition, n(SiO2):n(Al2O3)=50, and the mass fraction of Ru was 0.3%. The chemical composition of the catalyst was expressed as "xM·ySiO2·zAl2O3", with x / y=0.0021 and y / z=50. The properties of the obtained catalyst are shown in Table I-13.

[0191] The SEM image of the catalyst was similar to that shown in Figure 3. In this catalyst, the crystals were in the form of long bands, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–12.

[0192] [Table 12]

[0193] (Preparation example I-9) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0194] 1.2 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 450°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain a catalyst precursor. 0.3 g of dimethyldimethoxysilane, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed and refluxed at 75°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst. The properties of the obtained catalyst are shown in Table I-13.

[0195] Table I-9 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was similar to that of Figure 1. The SEM of the catalyst was similar to that of Figure 3. The crystals in the catalyst were long and band-like, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0196] [Table 13]

[0197] (Preparation example I-10) Mix 4g of deionized water, 1.5g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 1g of hydrofluoric acid uniformly to form 1SiO2:0.1Al2O3:2F - A component with the composition :30H2O:1OSDA was obtained. Pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:4.5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0198] 2.5 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 450°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain a catalyst precursor. 0.3 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed and refluxed at 75°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst. The properties of the obtained catalyst are shown in Table I-13.

[0199] Table I-10 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was similar to that of Figure 1. The SEM of the catalyst was similar to that of Figure 3. The crystals in the catalyst were long and band-like, with a crystal length of 0.5–2.5 μm and an aspect ratio of 3–20.

[0200] [Table 14]

[0201] (Preparation example I-11) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0202] 1.2 mL of a 2.7 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 450°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain a catalyst precursor. 0.3 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed, refluxed at 75°C for 24 hours, centrifuged with water, washed, and dried at 80°C for 12 hours to obtain the catalyst. The properties of the obtained catalyst are shown in Table I-13.

[0203] Table I-11 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was similar to that of Figure 1. The SEM of the catalyst was similar to that of Figure 3. The crystals in the catalyst were long and band-like, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–10.

[0204] [Table 15]

[0205] (Preparation example I-12) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.21g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.05Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain the desired H-type silica-alumina molecular sieve (ATS structure).

[0206] 1.2 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 450°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain a catalyst precursor. 0.3 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed and refluxed at 75°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst. The properties of the obtained catalyst are shown in Table I-13.

[0207] Table I-12 shows the XRD spectral data of the catalyst. The XRD spectrum of the catalyst was similar to that of Figure 1. The SEM of the catalyst was similar to that of Figure 3. The crystals in the catalyst were long and band-like, with a crystal length of 0.4–1.5 μm and an aspect ratio of 2–12.

[0208] [Table 16]

[0209] (Example I-1) 0.25 g of the catalyst synthesized in Preparation Example I-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0210] (Example I-2) 0.25 g of the catalyst synthesized in Preparation Example I-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.6 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0211] (Example I-3) 0.25 g of the catalyst synthesized in Preparation Example I-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 2.0 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0212] (Example I-4) 0.25 g of the catalyst synthesized in Preparation Example I-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0213] (Example I-5) 0.25 g of the catalyst synthesized in Preparation Example I-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 200°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0214] (Example I-6) 0.25 g of the catalyst synthesized in Preparation Example I-2 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0215] (Example I-7) 0.25 g of the catalyst synthesized in Preparation Example I-3 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0216] (Example I-8) 0.25 g of the catalyst synthesized in Preparation Example I-4 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0217] (Example I-9) 0.25 g of the catalyst synthesized in Preparation Example I-5 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0218] (Example I-10) 0.25 g of the catalyst synthesized in Preparation Example I-6 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0219] (Example I-11) 0.25 g of the catalyst synthesized in Preparation Example I-7 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0220] (Example I-12) 0.25 g of the catalyst synthesized in Preparation Example I-9 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0221] (Example I-13) 0.25 g of the catalyst synthesized in Preparation Example I-9 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.6 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0222] (Example I-14) 0.25 g of the catalyst synthesized in Preparation Example I-9 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 2.0 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0223] (Example I-15) 0.25 g of the catalyst synthesized in Preparation Example I-9 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0224] (Example I-16) 0.25 g of the catalyst synthesized in Preparation Example I-9 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system was then heated to 200°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0225] (Example I-17) 0.25 g of the catalyst synthesized in Preparation Example I-10 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table I-14.

[0226] (Example I-18) After adding 0.25 g of the catalyst synthesized in Preparation Example I-11 to a high-pressure reactor, 8 g of benzene was added to the reactor, and the system was filled with hydrogen to make the pressure in the system 1.2 MPa. Then, the temperature of the system was raised to 150 °C, and the reaction was terminated after 4 hours. The evaluation data was summarized in Table I-14.

[0227] (Example I-19) After adding 0.25 g of the catalyst synthesized in Preparation Example I-12 to a high-pressure reactor, 8 g of benzene was added to the reactor, and the system was filled with hydrogen to make the pressure in the system 1.2 MPa. Then, the temperature of the system was raised to 150 °C, and the reaction was terminated after 4 hours. The evaluation data was summarized in Table I-14.

[0228] [Table 17]

[0229] [Table 18]

[0230] (Comparative Example I-1) <1. Preparation of Catalyst> A catalyst was prepared referring to Preparation Example I-1, except that the H-type silica-alumina molecular sieve was changed to an H-type Y molecular sieve (FAU structure) with n(Si):n(Al) = 10.

[0231] 1.2 mL of a 3.2 g / L ruthenium chloride solution was added dropwise onto 1 g of the above molecular sieve. After drying at 80 °C for 2 hours, it was reduced in a fixed-bed reactor at 350 °C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0232] <2. Evaluation of Catalyst> The evaluation method of the catalyst is as shown in Example I-1. The composition of the catalyst and the evaluation results are shown in Table I-15.

[0233] (Comparative Example I-2) 1. Preparation of Catalyst The catalyst was prepared in accordance with Preparation Example I-1, except that the H-type silica-alumina molecular sieve was changed to an H-type Y molecular sieve (FAU structure) with n(Si):n(Al)=20.

[0234] 1.2 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of the above molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0235] 2. Catalyst evaluation: The catalyst evaluation method is shown in Example I-1. The catalyst composition and evaluation results are shown in Table I-15.

[0236] (Comparative example I-3) 1. Preparation of the catalyst The catalyst was prepared according to Preparation Example I-1, except that the H-type silica-alumina molecular sieve was changed to an H-type MCM-22 molecular sieve (MWW structure) with n(Si):n(Al)=20.

[0237] 1.2 mL of a 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of the above molecular sieve. After drying at 80°C for 2 hours, the mixture was reduced in a fixed-bed reactor at 350°C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0238] 2. Catalyst evaluation: The catalyst evaluation method is shown in Example I-1. The catalyst composition and evaluation results are shown in Table I-15.

[0239] (Comparative example I-4) 1. Preparation of the catalyst The catalyst was prepared in accordance with Preparation Example I-1, except that the H-type silica-alumina molecular sieve was changed to an H-type MCM-22 molecular sieve (MWW structure) with n(Si):n(Al)=30.

[0240] A 1.2 mL ruthenium chloride solution with a concentration of 3.2 g / L was added dropwise onto 1 g of the above molecular sieve. After drying at 80 °C for 2 hours, it was reduced in a fixed-bed reactor at 350 °C with a hydrogen flow rate of 10 mL / min for 3 hours to obtain the required catalyst.

[0241] 2. Evaluation of the catalyst: The evaluation method of the catalyst is shown in Example I-1. The composition and evaluation results of the catalyst are shown in Table I-15.

[0242] [Table 19]

[0243] (Example I-20) The catalyst prepared in Preparation Example I-1 was subjected to a total of 6 repeated washings and dryings and then used in the following reaction. The reaction conditions of Example I-1 were directly adopted for the evaluation of the catalyst. That is, 8 g of benzene was added to a high-pressure reactor, filled with hydrogen to make the pressure in the system 1.2 MPa. Then, the temperature of the system was raised to 150 °C, and the reaction was terminated after 4 hours. The evaluation results of the catalyst are shown in Table I-16.

[0244] [Table 20]

[0245] (Example I-21) The catalyst prepared in Preparation Example I-9 was subjected to a total of 6 repeated washings and dryings and then used in the following reaction. The reaction conditions of Example I-12 were directly adopted for the evaluation of the catalyst. That is, 8 g of benzene was added to a high-pressure reactor, filled with hydrogen to make the pressure in the system 1.2 MPa. Then, the temperature of the system was raised to 150 °C, and the reaction was terminated after 4 hours. The evaluation results of the catalyst are shown in Table I-17.

[0246] [Table 21]

[0247] (Preparation Example II-1) Na-type MCM-22 molecular sieves (MWW structure) with a silicon-to-aluminum molar ratio of 25:1 were subjected to ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice, and the resulting samples were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0248] 1.5 mL of 3.2 g / L ruthenium chloride solution (solution concentration based on elemental ruthenium, the same applies hereafter) was added dropwise to 1 g of H-type silica-alumina molecular sieve. Ruthenium-supported molecular sieve was then obtained by drying at 80°C for 2 hours. An H2-TPR test was performed on this ruthenium-supported molecular sieve, and the reduction temperature was found to be 451°C.

[0249] 0.2 g of methyltrimethoxysilane, a ruthenium-supported molecular sieve, and 10 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. After adding water and centrifuging, the mixture was washed and dried at 80°C for 12 hours to obtain a hydrocarbylated molecular sieve. An H2-TPR test was performed on the obtained hydrocarbylated molecular sieve, and the reduction temperature was 476°C. This result indicates that the active metal M supported on the hydrocarbylated molecular sieve is mainly distributed in the channels of the molecular sieve.

[0250] Subsequently, hydrocarbylated molecular sieves were incubated in a fixed-bed reactor at 450°C with a hydrogen volume space velocity of 50 hF. -1 The mixture was reduced for 3 hours to obtain the desired catalyst.

[0251] The XRD spectrum of the obtained catalyst is shown in Figure 4. XRD indicates that the catalyst as a whole maintains an MWW molecular sieve structure. The infrared absorption spectrum of the obtained catalyst is shown in Figure 5. Wavenumber 2950 cm⁻¹ -1A Si-C absorption peak can be seen in the vicinity. Furthermore, TG-MS testing determined that the hydrocarbyl is methyl, and its content is as shown in Table II-1. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are as shown in Table II-1.

[0252] (Preparation Example II-2) Na-type MCM-22 molecular sieves (MWW structure) with a silicon-to-aluminum molar ratio of 25:1 were subjected to ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0253] 1.5 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 50 hF. -1 The mixture was reduced for 3 hours to obtain a catalyst precursor. 0.3 g of dimethyldimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst.

[0254] The XRD spectrum of the obtained catalyst is the same as in Figure 1. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid content), metal M content, and outer surface metal M content of the catalyst are as shown in II-1.

[0255] (Preparation Example II-3) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 were subjected to ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0256] 1 g of H-type silica-alumina molecular sieve was added dropwise to 2.5 mL of a 3.2 g / L ruthenium chloride solution. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The mixture was reduced for 3 hours to obtain a catalyst precursor. 0.3 g of ethyltrimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst.

[0257] The XRD spectrum of the obtained catalyst is shown in Figure 6. The catalyst as a whole maintains a FAU molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table II-1.

[0258] (Preparation Example II-4) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 5:1 were subjected to ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0259] 1.5 mL of 2.6 g / L palladium chloride solution (solution concentration based on palladium element; the same applies hereafter) was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, it was incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 h. -1The catalyst precursor was obtained by reduction for 3 hours. 0.2 g of isopropyltrimethoxysilane, 1 g of the catalyst precursor, and 10 mL of toluene solvent were mixed, refluxed at 110°C for 24 hours, then water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0260] X-ray diffraction revealed that the catalyst as a whole maintains a FAU molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table II-1.

[0261] (Preparation Example II-5) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 5:1 were subjected to ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice, and the resulting samples were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0262] 1.5 mL of a nickel nitrate (6.0 g / L) - copper nitrate (3.0 g / L) mixed solution (solution concentration depends on the metal element; the same applies hereafter) was added dropwise to 1 g of H-type silica-alumina molecular sieve. After drying at 80°C for 2 hours, the mixture was incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 h. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.2 g of isopropyltrimethoxysilane, 1 g of the catalyst precursor, and 10 mL of toluene solvent were mixed, refluxed at 110°C for 24 hours, then water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0263] X-ray diffraction revealed that the catalyst as a whole maintains a FAU molecular sieve structure. The specific surface area, pore volume, acidity properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table II-1.

[0264] (Preparation Example II-6) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - After obtaining a component with the composition :29H2O:0.5OSDA, pretreatment was performed by open heating at 80°C to obtain a block mixture. After pretreatment by heating the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and calcined at 550°C for 6 hours to obtain an H-type silica-alumina molecular sieve (ATS structure).

[0265] 1.5 mL of 3.2 g / L ruthenium chloride solution was added dropwise to 1 g of H-type ATS molecular sieve. After drying at 80°C for 2 hours, it was incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 50 hF. -1 The mixture was reduced for 3 hours to obtain a catalyst precursor. 0.2 g of isopropyltrimethoxysilane, 1 g of the catalyst precursor, and 10 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst.

[0266] X-ray diffraction revealed that the catalyst as a whole maintains an ATS molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table II-1.

[0267] (Preparation Example II-7) The catalyst was prepared according to Preparation Example II-1, except that the raw material was changed to a Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 50:1. The remaining steps were not changed. The characteristics of the catalyst are shown in Table II-1.

[0268] The XRD spectrum of the obtained catalyst is the same as that shown in Figure 1. The specific surface area, pore volume, acid properties (including total acid content and acid content on the outer surface), metal M content, and metal M content on the outer surface of the catalyst are shown in Table II-1.

[0269] (Examples II-1 to II-4) 0.25 g of the catalyst synthesized in Preparation Example II-1 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor and hydrogen was added. The reaction was terminated after 4 hours. The specific evaluation conditions and evaluation data are shown in Table II-2.

[0270] (Example II-5) 0.25 g of the catalyst synthesized in Preparation Example II-2 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table 2.

[0271] (Example II-6) 0.25 g of the catalyst synthesized in Preparation Example II-3 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table II-2.

[0272] (Example II-7) 0.25 g of the catalyst synthesized in Preparation Example II-4 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table II-2.

[0273] (Example II-8) 0.25 g of the catalyst synthesized in Preparation Example II-5 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table II-2.

[0274] (Example II-9) 0.25 g of the catalyst synthesized in Preparation Example II-6 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table II-2.

[0275] (Example II-10) 0.25 g of the catalyst synthesized in Preparation Example II-7 was added to a high-pressure reactor, then 8 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table II-2.

[0276] (Comparative Example II-1) <1. Preparation of the catalyst> The catalyst was prepared in accordance with Preparation Example II-1, except that the treatment step with methyltrimethoxysilane was omitted. The properties of the obtained catalyst are shown in Table II-1.

[0277] <2. Catalyst Evaluation> The catalyst evaluation method is as shown in Example II-5. The catalyst evaluation results are shown in Table II-2.

[0278] (Comparative Example II-2) <1. Preparation of the catalyst> The catalyst was prepared according to Preparation Example II-1, except that the amount of ruthenium chloride solution of the same concentration added was increased to 8 mL, i.e., only the metal content in the catalyst was increased. The characteristics of the catalyst are shown in Table II-1.

[0279] <2. Catalyst Evaluation> The catalyst evaluation method was the same as in Example II-5, and the catalyst evaluation results are shown in Table II-2.

[0280] (Comparative Example II-3) <1. Preparation of the catalyst> Except for increasing the amount of dimethyldimethoxysilane from 0.3g to 1.0g, the catalyst was prepared according to Preparation Example II-2, with no changes to the remaining steps. The characteristics of the catalyst are shown in Table II-1.

[0281] <2. Catalyst Evaluation> The catalyst evaluation method was the same as in Example II-5, and the catalyst evaluation results are shown in Table II-2.

[0282] (Comparative Example II-4) The catalyst obtained in Preparation Example II-1 was evaluated by referring to the method of Preparation Example II-5, with the only change being the hydrogen partial pressure in the reaction conditions, which was changed to 4.0 MPa. The results of the catalyst evaluation are shown in Table II-2.

[0283] [Table 22]

[0284] [Table 23]

[0285] (Example II-10) The catalyst prepared in Preparation Example II-1 was washed and dried before being added to the next reaction, and was cycled a total of six times. Catalyst evaluation included adding 8 g of benzene to a high-pressure reactor and charging it with hydrogen to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours. The catalyst evaluation results are shown in Table II-3.

[0286] [Table 24]

[0287] (Preparation Example III-1) (1) Preparation of H-type MWW molecular sieves MCM-22 molecular sieves (MWW structure) with a silicon-to-aluminum molar ratio of 20:1 were subjected to ammonium ion exchange at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0288] (2) Preparation of catalyst 0.5 mL of 8 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve with a silicon-aluminum ratio of 20:1. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 500°C with a hydrogen volume space rate of 80 hF. -1 The mixture was reduced for 2 hours to obtain a catalyst precursor. 0.3 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed and refluxed at 75°C for 24 hours. After adding water, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0289] The XRD spectrum of the obtained catalyst is shown in Figure 7. The catalyst as a whole maintains an MWW molecular sieve structure. The specific surface area, pore volume, acidity (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0290] (Preparation Example III-2) (1) Preparation of H-type MWW molecular sieves The preparation process was the same as in Preparation Example III-1, except that a Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 25:1 was used.

[0291] (2) Preparation of catalyst 1 mL of 8 g / L ruthenium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve with a silicon-aluminum ratio of 25:1. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 500°C with a hydrogen volume space rate of 80 hF. -1The catalyst precursor was obtained by reduction for 3 hours. 0.2 g of tolyltrimethoxysilane, 1 g of the catalyst precursor, and 20 ml of toluene solvent were mixed, refluxed at 110°C for 24 hours, then water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0292] The XRD spectrum of the obtained catalyst is the same as that shown in Figure 7. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid content), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0293] (Preparation Example III-3) (1) Preparation of H-type MOR molecular sieves The preparation process was the same as in Preparation Example III-1, except that a Na-type mordenite (MOR structure) with a silicon-aluminum molar ratio of 10:1 was used.

[0294] (2) Preparation of catalyst 0.5 mL of 8 g / L ruthenium chloride solution was added dropwise to 1 g of H-type MOR molecular sieve with a silicon-to-aluminum ratio of 10:1. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 500°C with a hydrogen volume space rate of 150 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.3 g of phenylsilanetriol, 1 g of the catalyst precursor, and 30 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0295] The resulting catalyst maintained an overall MOR molecular sieve structure. The specific surface area, pore volume, acidity (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0296] (Preparation Example III-4) (1) Preparation of H-type MOR molecular sieves The preparation process was the same as in Preparation Example III-1, except that a Na-type mordenite (MOR structure) with a silicon-aluminum molar ratio of 15:1 was used.

[0297] (2) Preparation of catalyst 0.5 mL of 8 g / L palladium chloride solution was added dropwise to 1 g of H-type MOR molecular sieve with a silicon-to-aluminum ratio of 15:1. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 500°C with a hydrogen volume space rate of 80 hF. -1 The mixture was reduced for 3 hours to obtain a catalyst precursor. 0.2 g of diphenylsilanediol, 1 g of the catalyst precursor, and 20 mL of ethanol solvent were mixed and refluxed at 75°C for 24 hours, then water was added and the mixture was centrifuged. After washing, the mixture was dried at 80°C for 12 hours to obtain the catalyst.

[0298] The resulting catalyst retained an overall MOR molecular sieve structure. The specific surface area, pore volume, acidity (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0299] (Preparation Example III-5) Mix 4g of deionized water, 0.75g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol, and 0.5g of hydrofluoric acid uniformly to form a mixture of 1SiO2:0.1Al2O3:1F - A component with the composition :29H2O:0.5OSDA was obtained. Subsequently, pretreatment was performed by open heating at 80°C to obtain a block mixture. After heating and pretreatment of the raw material mixture, the molar ratio of silicon source (calculated as SiO2) to water during crystallization was set to 1:5, and crystallization was carried out in a crystallization kettle at 170°C for 15 days. After removing the product, it was washed three times with deionized water, dried, and then calcined at 550°C for 6 hours to obtain H-type ATS molecular sieves.

[0300] 0.5 mL of 8 g / L ruthenium chloride solution was added dropwise to 1 g of H-type ATS molecular sieve. After drying at 80°C for 2 hours, it was incubated in a fixed-bed reactor at 500°C with a hydrogen volume space rate of 80 hF. -1The catalyst precursor was obtained by reduction for 3 hours. 0.2 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 10 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0301] The resulting catalyst retains an ATS molecular sieve structure overall. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0302] (Preparation Example III-6) The catalyst was prepared by referring to Preparation Example III-1, with no changes to the process other than changing the raw material to a Na-type MCM-22 molecular sieve (MWW structure) with a silicon-aluminum molar ratio of 50:1.

[0303] The XRD spectrum of the obtained catalyst was the same as that shown in Figure 7. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table III-1.

[0304] (Examples III-1 to III-3) 0.25 g of the catalyst synthesized in Preparation Example III-1 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor and hydrogen was added. The reaction was terminated after 4 hours. The specific evaluation conditions and evaluation data are shown in Table III-2.

[0305] (Example III-4) 0.25 g of the catalyst synthesized in Preparation Example III-2 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.0 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table III-2.

[0306] (Example III-5) 0.25 g of the catalyst synthesized in Preparation Example III-3 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.0 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table III-2.

[0307] (Example III-6) 0.25 g of the catalyst synthesized in Preparation Example III-4 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.0 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table III-2.

[0308] (Example III-7) 0.25 g of the catalyst synthesized in Preparation Example III-5 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.0 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table III-2.

[0309] (Example III-8) 0.25 g of the catalyst synthesized in Preparation Example III-6 was added to a high-pressure reactor, then 10 g of benzene was added to the reactor, and hydrogen was added to bring the system pressure to 1.0 MPa. The system temperature was then raised to 180°C, and the reaction was terminated after 4 hours. The evaluation data is summarized in Table III-2.

[0310] (Comparative Example III-1) <1. Preparation of the catalyst> The catalyst was prepared in accordance with Preparation Example III-1, except that the treatment with phenyltrimethoxysilane was omitted.

[0311] <2. Catalyst Evaluation> The catalyst evaluation method was the same as in Example III-4, and the catalyst evaluation results are shown in Table III-2.

[0312] <Comparative example III-2> (1. Preparation of the catalyst) The catalyst was prepared in accordance with Preparation Example III-1, except that the amount of ruthenium chloride solution of the same concentration added was increased to 8 mL, that is, only the metal content in the catalyst was increased.

[0313] (2. Evaluation of catalysts) The catalyst evaluation method was the same as in Example III-4, and the catalyst evaluation results are shown in Table III-2.

[0314] (Comparative Example III-3) <1. Preparation of the catalyst> The catalyst was prepared in accordance with Preparation Example III-1, except that the addition of "0.3 g of phenyltrimethoxysilane" in the arylation step was changed to the addition of "0.8 g of phenyltrimethoxysilane".

[0315] (2. Evaluation of catalysts) The catalyst evaluation method was the same as in Example III-4, and the catalyst evaluation results are shown in Table III-2.

[0316] (Comparative Example III-4) The catalyst obtained in Preparation Example III-1 was evaluated according to the method of Preparation Example III-4, with no other changes except for changing the hydrogen partial pressure in the reaction conditions to 4.0 MPa. The results of the catalyst evaluation are shown in Table III-2.

[0317] [Table 25]

[0318] [Table 26]

[0319] (Example III-9) The catalyst prepared in Preparation Example III-1 was washed and dried a total of six times before being used in the next reaction. For catalyst evaluation, 8 g of benzene was added to a high-pressure reactor, and hydrogen was added to bring the system pressure to 1.2 MPa. The system temperature was then raised to 150°C, and the reaction was terminated after 4 hours.

[0320] [Table 27]

[0321] (Preparation example IV-1) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 and a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0322] 4.0 mL of 3.0 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.2 g of methyltrimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0323] The XRD spectrum of the obtained catalyst is the same as that shown in Figure 7. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0324] (Preparation example IV-2) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 and a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0325] 1 g of H-type silica-alumina molecular sieve was added dropwise to 4.0 mL of a 3.0 g / L palladium chloride solution. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.3 g of dimethyldimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0326] XRD analysis revealed that the obtained catalyst as a whole retains a FAU molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0327] (Preparation example IV-3) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 were subjected to ammonium ion exchange at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0328] 4.0 mL of 2.5 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. The mixture was dried at 80°C for 2 hours and then incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.3 g of dimethyldimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0329] XRD analysis revealed that the obtained catalyst as a whole retains a FAU molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0330] (Preparation example IV-4) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 5:1 were washed by ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation. The ammonium ion exchange was repeated twice, and the resulting samples were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0331] 1 g of H-type silica-alumina molecular sieve was added dropwise to 4.0 mL of a 3.0 g / L palladium chloride solution. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.3 g of dimethyldimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0332] XRD analysis revealed that the obtained catalyst as a whole retains a FAU molecular sieve structure. The specific surface area, pore volume, acidity properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0333] (Preparation example IV-5) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 were washed by ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0334] 1 g of H-type silica-alumina molecular sieve was added dropwise to 4.0 mL of a 3.0 g / L palladium chloride solution. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.3 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0335] XRD analysis revealed that the obtained catalyst as a whole retains a FAU molecular sieve structure. The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0336] (Example IV-1) 0.25 g of the catalyst synthesized in Preparation Example IV-1 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0337] (Example IV-2) 0.25 g of the catalyst synthesized in Preparation Example IV-1 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.5 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0338] (Example IV-3) 0.25 g of the catalyst synthesized in Preparation Example IV-1 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 380°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0339] (Example IV-4) 0.25 g of the catalyst synthesized in Preparation Example IV-2 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0340] (Example IV-5) 0.25 g of the catalyst synthesized in Preparation Example IV-3 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0341] (Example IV-6) 0.25 g of the catalyst synthesized in Preparation Example IV-4 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0342] (Example IV-7) 0.25 g of the catalyst synthesized in Preparation Example IV-5 was added to a high-pressure reactor, then 10 g of n-decane was added to the reactor, and hydrogen was added to bring the system pressure to 3.0 MPa. Subsequently, the system temperature was raised to 350°C, and the reaction was terminated after 3 hours. The evaluation data is summarized in Table IV-2.

[0343] (Comparative Example IV-1) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 were washed by ammonium ion exchange with a 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 45°C for 2 hours, followed by centrifugation. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0344] 4.0 mL of 3.0 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The reduction process was carried out for 3 hours to obtain the necessary catalyst.

[0345] The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0346] The catalyst evaluation method is shown in Example IV-1. The catalyst composition and evaluation results are shown in Table IV-2.

[0347] (Comparative example IV-2) Na-type Y molecular sieves (FAU structure) with a silicon-to-aluminum molar ratio of 10:1 were subjected to ammonium ion exchange at 45°C for 2 hours, followed by centrifugation and washing. The samples obtained by repeating ammonium ion exchange twice were dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.

[0348] 4.0 mL of 3.0 g / L palladium chloride solution was added dropwise to 1 g of H-type silica-alumina molecular sieve. The mixture was then dried at 80°C for 2 hours and incubated in a fixed-bed reactor at 450°C with a hydrogen volume space rate of 100 hF. -1 The catalyst precursor was obtained by reduction for 3 hours. 0.8 g of phenyltrimethoxysilane, 1 g of the catalyst precursor, and 15 mL of toluene solvent were mixed and refluxed at 110°C for 24 hours. Then, water was added, the mixture was centrifuged, washed, and dried at 80°C for 12 hours to obtain the catalyst.

[0349] The specific surface area, pore volume, acid properties (including total acid content and outer surface acid equivalent), metal M content, and outer surface metal M content of the catalyst are shown in Table IV-1.

[0350] The catalyst evaluation method is shown in Example IV-1. The catalyst composition and evaluation results are shown in Table IV-2.

[0351] [Table 28]

[0352] [Table 29]

[0353] Preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific embodiments described above. Within the scope of the technical idea of ​​the present invention, many simple modifications can be made to the technical solutions of the present invention, including various combinations of technical features in any other suitable embodiment. These simple modifications and combinations should also be considered part of the disclosure of the present invention, and all of them are within the scope of protection of the present invention.

[0354] In addition, it should be noted that each of the specific technical features described in the above-mentioned embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described further in this application.

[0355] Furthermore, as long as the present invention does not deviate from the spirit of the present invention, it is possible to arbitrarily combine various different embodiments, and such combinations should also be considered as part of the scope of the present invention. [Brief explanation of the drawing]

[0356] [Figure 1] Figure 1 shows the XRD spectrum of the catalyst prepared in Production Example I-1. [Figure 2] Figure 2 shows a TEM image of the catalyst prepared in manufacturing example I-1. [Figure 3] Figure 3 shows an SEM image of the catalyst prepared in manufacturing example I-1. [Figure 4] Figure 4 shows the XRD spectrum of the catalyst prepared in Production Example II-1. [Figure 5]Figure 5 shows the infrared absorption spectrum of the catalyst prepared in Production Example II-1. [Figure 6] Figure 6 shows the XRD spectrum of the catalyst prepared in Production Example II-3. [Figure 7] Figure 7 shows the XRD spectrum of the catalyst prepared in Production Example III-1.

Claims

1. A hydrogenation-acid catalyst for use in a benzene hydroalkylation reaction or an alkane hydroisomerization reaction, comprising, based on the mass of the catalyst, 80 to 99.8% of a silica-alumina molecular sieve component, 0.2 to 2% of a hydrogenation-active metal component supported on a molecular sieve, and 0 to 20% of a hydrocarbyl modification component, wherein the hydrogenation-active metal is selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, and the hydrocarbyl modification component is C １－２０ It is hydrocarbil, The silica-alumina molecular sieve is selected from molecular sieves having MWW, FAU, MOR, BEA, or ATS structures, or combinations thereof, and when the silica-alumina molecular sieve has an MWW, FAU, MOR, or BEA structure, the mass content of the hydrocarbyl-modified component is 1 to 20%; A catalyst having a mass content of hydrogenated metals on its outer surface relative to elements on the outer surface, as measured by X-ray photoelectron spectroscopy (XPS), of 0.5% or less, and a partition coefficient of hydrogenated metals on the outer surface of the catalyst of 1 to 20%.

2. The catalyst according to claim 1, wherein the hydrogenation-active metal is selected from ruthenium, palladium, or a combination thereof, and the hydrocarbyl-modifying component is selected from methyl, ethyl, propyl, isopropyl, butyl, phenyl, benzyl, phenethyl, or a combination thereof.

3. The catalyst according to claim 1, wherein the silicon-aluminum ratio of the silica-alumina molecular sieve is 2 to 50.

4. The catalyst according to claim 1, wherein the silica-alumina molecular sieve is a silica-alumina molecular sieve having an ATS structure, and the X-ray diffraction spectrum of the catalyst exhibits the relative intensity characteristics of the diffraction peaks shown in the table below: Table 1 In the table, s represents values ​​between 40 and 70, vs represents values ​​greater than 70, and m-s represents values ​​between 20 and 70.

5. The catalyst according to claim 4, wherein the X-ray diffraction spectrum of the catalyst exhibits the relative intensity characteristics of the diffraction peaks shown in any of the columns of the table below: Table 2 In the table, m represents a value between 20 and 40, and w-m represents a value less than 40.

6. The catalyst contains, based on the mass of the catalyst, 80-98% silica-alumina molecular sieve components, 0.2-2% hydrogenation-active metal components, and 1-20% hydrocarbyl-modified components, and the mass content of the hydrogenation-active metal on the outer surface relative to the elements on the outer surface of the catalyst, as measured by X-ray photoelectron spectroscopy (XPS), is 0.4% or less; The catalyst according to claim 1, wherein the partition coefficient of hydrogenated active metals on the outer surface of the catalyst is 1.5 to 18%.

7. The catalyst according to claim 1, wherein the catalyst contains 90 to 98% of the silica-alumina molecular sieve component, 0.2 to 1.5% of the hydrogenation-active metal component, and 1 to 10% of the hydrocarbyl-modified component, based on the mass of the catalyst.

8. The catalyst has the following characteristics: The specific surface area of ​​the catalyst is 200 to 800 m². ２ / g; The total pore volume of the catalyst is 0.15 cm³. ３ It must be at least / g; The micropore volume of the catalyst is 0.05 to 0.30 cm³. ３ / g, and the micropores refer to pores with a diameter of less than 2 nm; The total acid content of the catalyst is 400 to 1500 μmol·g －１ Being; The relative acid equivalent on the outer surface of the catalyst is 15-50%; Catalyst metal H ２ - The TPR test reduction temperature must be between 470 and 500°C; The ratio of the acid content of the catalyst's B acid to L acid is 0.2 to 8.0; In the catalyst, the crystals have a strip-like or rod-like form, the length of the crystals is 0.3 to 3 μm, and the aspect ratio is 2 to 20; The catalyst according to claim 1, having one or more of the above.

9. The catalyst has the following characteristics: The specific surface area of ​​the catalyst must be between 250 and 700 m² / g; The total pore volume of the catalyst must be 0.18 to 1.0 cm³ / g; The catalyst has a micropore volume of 0.10 to 0.25 cm³ / g, where the micropores refer to pores with a diameter of less than 2 nm; The total acid content of the catalyst must be between 600 and 1500 μmol·g⁻¹; The relative acid equivalent on the outer surface of the catalyst is 15-40%; The catalyst's metal H₂-TPR test reduction temperature must be 480-500°C; The ratio of the acid content of the catalyst's B acid to L acid is 0.4 to 6.0; In the catalyst, the crystals have a strip-like or rod-like form, the length of the crystals is 0.3 to 3 μm, and the aspect ratio is 5 to 20; The catalyst according to claim 1, having one or more of the above.

10. The following steps: (1) A step of providing an H-type silica-alumina molecular sieve; and (2) A method for preparing a catalyst according to claim 1, comprising the step of supporting a hydrogenated metal on the H-type silica-alumina molecular sieve and optionally performing hydrocarbylation and / or reduction on the obtained product, A method comprising measuring by X-ray photoelectron spectroscopy (XPS) test, wherein the mass content of the hydrogenated metal on the outer surface of the catalyst relative to the elements on the outer surface is 0.5% or less, and the partition coefficient of the hydrogenated metal on the outer surface of the catalyst is 1 to 20%.

11. Step (1) includes a step of obtaining H-type silica-alumina molecular sieves by performing ammonium ion exchange and calcination on the raw materials for silica-alumina molecular sieves. The raw material for the silica-alumina molecular sieve is selected from silica-alumina molecular sieves having MWW, FAU, MOR, or BEA structures, or combinations thereof. The method according to claim 10.

12. Step (1) comprises mixing a silicon source, an aluminum source, a fluorine source, an organic structure-regulating agent, and water, followed by pre-heating treatment, crystallization treatment, and calcination to obtain an H-type ATS silica-alumina molecular sieve, wherein the silicon source is selected from silicic acid, silica gel, silica sol, tetraethyl silicate, sodium silicate, or a combination thereof; the aluminum source is selected from boehmite, aluminum isopropoxide, or a combination thereof; the fluorine source is hydrofluoric acid; and the organic structure-regulating agent is 4-pyrrolidinylpyridine; Process (1) has the following characteristics: SiO ２ The added silicon source calculated as, Al ２ O ３ The aluminum source calculated as, F － The fluorine source calculated as, and the molar ratio of the organic structure directing agent, water is 1:(0.02 - 0.2):(0.5 - 2):(0.25 - 1.5):(3 - 15); In the crystallization process, SiO ２ The molar ratio of the silicon source to water, calculated as follows, is 1:(1 to 10); and, The crystallization conditions include a crystallization temperature of 120 to 200°C and a crystallization time of 7 to 21 days; The method according to claim 10, comprising one or more of the above.

13. In step (2), a solution of the hydrogenation-activated metal source is added to an H-type silica-alumina molecular sieve and dried to support the hydrogenation-activated metal on the H-type silica-alumina molecular sieve. Process (2) has the following characteristics: The hydrogenation-active metal source is selected from metal chlorides, nitrates, or combinations thereof; The concentration of the solution containing the hydrogenated metal source shall be 1.5 to 50 g / L, based on the mass of the hydrogenated metal. The solution of the hydrogenation-activated metal source is added dropwise to the H-type silica-alumina molecular sieve; and, The mass ratio of the hydrogenating metal to the H-type silica-alumina molecular sieve in the hydrogenating metal source solution shall be 0.002 to 0.015:1; The method according to claim 10, comprising one or more of the above.

14. The hydrocarbylation treatment includes reacting a product supported with a hydrogenated metal with a hydrocarbylation reagent in a solvent, The hydrocarbylating reagent is selected from methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, tolylsilanetriol, diphenylsilanediol, or a combination thereof; Hydrocarbylation treatment has the following characteristics: The solvent must be ethanol, toluene, or a combination thereof; The mass ratio of the product, which is supported by the hydrogenated metal, the hydrocarbylation reagent, and the solvent, is 1:(0.05-0.45):(5-55); The reaction conditions for the hydrocarbylation treatment include a reaction temperature of 40 to 110°C and a reaction time of 6 to 48 hours; The method according to claim 10, comprising one or more of the above.

15. The reduction is carried out using a reducing gas, and the conditions for the reduction are: a reduction temperature of 300 to 450°C, a reduction time of 3 to 6 hours, and a volume space velocity of the reducing gas of 40 to 200 h. －１ The method according to claim 10, which includes being

16. The process includes the step of contacting and reacting the hydrogenation-acid catalyst binary catalyst described in claim 1 with benzene in the presence of hydrogen to obtain cyclohexylbenzene; A one-step method for hydrogenating benzene to produce cyclohexylbenzene, comprising the reaction conditions being: a mass ratio of benzene to catalyst of 8 to 40; a reaction temperature of 100 to 220°C; a reaction time of 2 to 8 hours; and a hydrogen pressure of 0.8 to 2.5 MPa.

17. This method involves contacting and reacting a linear alkane with the hydrogenation-acid catalyst binary functional catalyst described in claim 1 in the presence of hydrogen to obtain an isomerized product; The aforementioned linear alkane is a linear alkane of C8 to C20; A method for hydrogenation isomerization of an alkane, comprising the following reaction conditions: the mass ratio of the linear alkane to the catalyst is 10 to 100; the reaction temperature is 250 to 400°C; the reaction time is 3 to 10 hours; and the hydrogen pressure is 2.5 to 5.0 MPa.

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