CN116020541A

CN116020541A - Catalyst for producing cyclohexylbenzene and preparation method and application thereof

Info

Publication number: CN116020541A
Application number: CN202111250651.2A
Authority: CN
Inventors: 蓝大为; 杨为民; 王振东; 梁俊; 李相呈; 王闻年
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2021-10-26
Filing date: 2021-10-26
Publication date: 2023-04-28

Abstract

The invention discloses a catalyst for producing cyclohexylbenzene, a preparation method thereof and application thereof in benzene hydroalkylation to produce cyclohexylbenzene. Wherein the catalyst has the formula "xM.ySiO ₂ ·zAl ₂ O ₃ "schematic chemical composition shown; wherein M is a metal element selected from one or more of ruthenium, platinum, palladium, copper and nickel metals; in the chemical composition, x/y is more than or equal to 0.001 and less than or equal to 0.02,8 and y/z is more than or equal to 80. The catalyst of the invention is used for producing cyclohexylbenzene by benzene hydroalkylation, and has the characteristics of high benzene conversion rate, good product selectivity and the like.

Description

Catalyst for producing cyclohexylbenzene and preparation method and application thereof

Technical Field

The invention relates to the technical field of chemical industry, in particular to a catalyst for producing cyclohexylbenzene, a preparation method thereof and a method for producing cyclohexylbenzene by using the catalyst in a benzene hydroalkylation one-step method.

Background

Cyclohexylbenzene is an important chemical product and has important application in the fields of liquid crystal and rechargeable batteries. The cyclohexylbenzene liquid crystal has extremely high chemical stability, photochemical stability and excellent physical properties, and is one of ideal materials for liquid crystal displays. The cyclohexylbenzene can be also used as an additive component in the electrolyte of the lithium ion battery, has the function of overcharge prevention and can effectively improve the safety of the battery. In addition, the important chemical products phenol and cyclohexanone can be prepared by taking the cyclohexylbenzene as an intermediate through further peroxidation and decomposition reaction, and further the cyclohexylbenzene can be used for producing phenolic resin, caprolactam and nylon, so the preparation and production of the cyclohexylbenzene are of great interest. The cyclohexylphenyl group information is as follows: colorless liquid with CAS number 827-52-1 and density of 0.95g/cm ³ The boiling point is 238-240 ℃, the melting point is 5 ℃, and the flash point is 98 ℃.

The main method for preparing the cyclohexylbenzene comprises the following steps of: benzene and cyclohexene alkylation process and benzene hydroalkylation process. The basic principle of the benzene hydroalkylation method is as follows: benzene and hydrogen are used as raw materials, part of benzene is hydrogenated at a metal active center to obtain a 6-membered cycloolefin structure (such as cyclohexene and the like), and the 6-membered cycloolefin structure is further alkylated with benzene at an acid active center to obtain a cyclohexylbenzene product. Therefore, a dual-function catalyst having both a hydrogenation center and an alkylation active center can be used in a cyclohexylbenzene production process.

Benzene hydroalkylation to cyclohexylbenzene was first studied in the eighties of the last century. Currently, most of the developed catalysts have problems of low catalytic efficiency and low selectivity. Such as catalysts based on MCM-22 series molecular sieves (US 2011/0015457a1, cn104105679 a) have the problems of slow catalytic rate and higher selectivity to by-product cyclohexane. Other catalysts such as Ni-rare earth treated HY molecular sieves as support (US 4219689) have the problems of low benzene conversion and low yield of product cyclohexylbenzene. Subsequently, it is reported (Molecular Catalysis 2017,442,27-38) that cyclohexylbenzene is prepared by one-step catalytic benzene hydroalkylation by using Pd/HY supported molecular sieve as a catalyst, the initial conversion rate of benzene is 42.2%, the selectivity of cyclohexylbenzene is maintained to be about 75%, and the selectivity of the hyperalkylated byproduct dicyclohexylbenzene is as high as about 20%. In summary, the prior art mainly has the problems of low benzene conversion rate and poor product selectivity, which brings about a great problem for industrial practical application.

Patent WO01/66464A2 provides a molecular sieve SSZ-55 material with a larger pore structure, and the special 12-membered ring pore structure provides considerable prospect for acid-catalyzed aromatic compound reaction. However, the method still has the problems that only specific silicon-aluminum ratio structure can be synthesized and the total acid amount of the material is limited, so that the method has poor application effect in acid catalysis. In addition, the templates used are limited to synthesis applications in laboratories, and have limited practical industrial and economic values.

Disclosure of Invention

The invention aims to solve the technical problems of low benzene conversion rate, poor product selectivity and the like in the prior art for producing cyclohexylbenzene by benzene hydroalkylation, and provides a catalyst for producing cyclohexylbenzene, a preparation method thereof and application thereof in producing cyclohexylbenzene by benzene hydroalkylation. The catalyst of the invention is used for producing cyclohexylbenzene by benzene hydroalkylation, and has the characteristics of high benzene conversion rate, good product selectivity and the like.

In a first aspect, the present invention provides a catalyst for producing cyclohexylbenzene, the catalyst having the formula "xM·ySiO ₂ ·zAl ₂ O ₃ "schematic chemical composition shown;

wherein M is a metal element selected from one or more of ruthenium, platinum, palladium, copper and nickel metals; preferably ruthenium metal;

wherein, in the chemical composition, x/y is more than or equal to 0.001 and less than or equal to 0.02,8 and y/z is more than or equal to 80.

Further, in the catalyst, the mass content of the metal M is 0.2% to 2%, preferably 0.2% to 1.5%, more preferably 0.3% to 1%, such as, but not limited to, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc., based on the mass of the catalyst.

Further, the catalyst has an X-ray diffraction pattern as shown in the following Table A-1,

table A-1

(a) And = ±0.3° (b) varies with 2θ.

Further, the catalyst also comprises an X-ray diffraction pattern shown in the following table A-2,

table A-2

(a) And = ±0.3° (b) varies with 2θ.

Further, the total acid amount of the catalyst is 500-1500 mu mol g ^-1 Preferably 800 to 1500. Mu. Mol.g ^-1 The ratio of the amount of B acid to the amount of L acid is 3 to 10, preferably 5 to 7.

Further, in the catalyst, the M exists in at least one form of simple substance, oxide, chloride and nitrate. Wherein the particle diameter of the M metal particles is 0.5-10 nm, preferably 1-5 nm.

Further, in the catalyst, the crystals have a long-strip or rod-like morphology, the average length of the crystals is 0.3-3 μm, and the aspect ratio is 2-20.

Further, the specific surface area of the catalyst is 200-600 m ² Per gram, preferably 250 to 500 meters ² /g; the micropore volume of the catalyst is 0.05-0.30 cm ³ Per gram, preferably 0.10 to 0.25 cm ³ /g.

The second aspect of the present invention provides a method for preparing the catalyst for producing cyclohexylbenzene, comprising the steps of:

(1) Mixing a silicon source, an aluminum source, a fluorine source, an organic structure directing agent and water, heating for pretreatment, crystallizing, and roasting to obtain a sample B;

(2) The catalyst was prepared by adding the M metal-containing solution to sample B of step (1), drying and reducing.

Further, in the step (1), the silicon source is added as SiO ₂ For counting, aluminum source is Al ₂ O ₃ For metering F as fluorine source ^- The molar ratio of the organic structure guiding agent a to water is 1 (0.02-0.2) (0.5-2) (0.25-1.5) (3-15), preferably 1 (0.05-0.15) (0.5-1) (5-10).

Further, in the step (1), the silicon source is at least one selected from silicic acid, silica gel, silica sol, tetraethyl silicate, and water glass; the aluminum source is selected from at least one of pseudo-boehmite and aluminum isopropoxide.

Further, in step (1), the fluorine source is selected from hydrofluoric acid; the organic structure directing agent is selected from 4-pyrrolidinylpyridine.

Further, in the step (1), the heating pretreatment method is rotary evaporation of water or open heating of water, and the open heating treatment condition is that the mixture is heated and stirred at 50-100 ℃, preferably at 70-90 ℃.

Further, in the step (1), after the raw material mixture is subjected to a heating pretreatment, a silicon source (in SiO during crystallization ₂ Based on the molar ratio of 1 (1-10), preferably 1 (1.5-6.5) and water.

Further, in step (1), the crystallization conditions are: the temperature is 120-200 ℃, the time is 7-21 days, preferably, the temperature is 150-200 ℃ and the time is 7-15 days.

Further, in the step (1), the crystallization may be performed in any manner conventionally known in the art, and for example, there may be mentioned a method of mixing the silicon source, the aluminum source, the fluorine source, the organic structure directing agent and water in a predetermined ratio and subjecting the obtained mixture to heat crystallization under crystallization conditions.

Further, in step (1), after the crystallization step is ended, a product may be obtained from the obtained mixture by any conventionally known separation means and calcination treatment. Examples of the separation method include a method of filtering, washing and drying the obtained mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply suction-filtered. The washing may be performed using deionized water and/or ethanol, for example. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be performed under normal pressure or under reduced pressure.

Further, in step (1), the firing may be performed in any manner conventionally known in the art, such as a firing temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a firing time of generally 1 to 12 hours, preferably 2 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

Further, in the step (2), the M metal-containing solution may be formulated with a soluble metal compound, the metal being selected from one or more of ruthenium, platinum, palladium, copper and nickel metals; the metal solution is prepared by using ruthenium as an example, such as ruthenium nitrate or ruthenium chloride.

Further, in the step (2), the concentration of the M metal-containing solution is 2 to 50g/L.

Further, in the step (2), the M metal-containing solution is added dropwise to the sample B of the step (1). The dropping conditions are not particularly limited in the present invention, and for example, the mixture may be mixed for 1 to 10 hours after dropping at room temperature.

Further, in step (2), the drying may be performed in a conventional manner, preferably: the drying temperature is 40-90 ℃ and the drying time is 4-12 hours. The calcination may be carried out in a conventional manner, preferably: the roasting temperature is 300-550 ℃ and the roasting time is 3-8 hours. The reduction may be carried out using hydrogen, the reduction conditions preferably being as follows: the reduction temperature is 300-450 ℃ and the reduction time is 3-6 hours.

In a third aspect, the invention provides a method for preparing cyclohexylbenzene by using the catalyst in a benzene hydrogenation one-step method.

Further, the method comprises the steps of carrying out contact reaction on raw material benzene and the catalyst, and preparing cyclohexylbenzene by taking hydrogen gas as a hydrogen source.

Further, the mass ratio of the raw material benzene to the catalyst is 8 to 40, preferably 10 to 40.

Further, the reaction temperature is 100 to 220 ℃, preferably 120 to 200 ℃. The reaction time is 2 to 8 hours, preferably 2.5 to 6 hours.

Further, the reaction hydrogen pressure is 0.8-2.5 MPa, preferably 1.0-2.5 MPa.

Compared with the prior art, the invention has the beneficial effects that:

1. the catalyst provided by the invention, wherein the molecular sieve belongs to an ATS type silicon-aluminum molecular sieve, the silicon-aluminum ratio of the molecular sieve is low, and the chemical composition of the molecular sieve is never obtained before in the field. The catalyst also contains metal with hydrogenation activity, and has stronger hydrogenation performance. In addition, the catalyst has special acid property, large acid quantity and high acid strength.

2. According to the preparation method, 4-pyrrolidinyl pyridine is used as an organic structure guiding agent, alkali is not required to be added in the reaction process, and the catalyst can be used without ammonium ion exchange.

3. The catalyst provided by the invention has the double functions of hydrogenation and solid acid, the benzene is subjected to hydrogenation alkylation reaction to generate cyclohexylbenzene under mild reaction conditions, the benzene conversion rate and the main product cyclohexylbenzene selectivity are very high, and the reaction system has good stability.

Drawings

FIG. 1 is an XRD spectrum of the catalyst prepared in example 1;

FIG. 2 is a TEM image of the catalyst prepared in example 1;

FIG. 3 is an SEM image of the catalyst prepared in example 1.

Detailed Description

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.

The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

In the context of the present specification, the structure of a sample is determined by X-ray diffraction patterns (XRD) determined by an X-ray powder diffractometer using a Cu-ka radiation source, a nickel filter.

In the context of the present specification, including in the examples and comparative examples below, the model of the X-ray powder diffractometer for the sample is a model Panalytical X PERPRO X-ray powder diffractometer, the phase of the sample is analyzed, cuK alpha radiation source

The scanning range of 2-50 DEG for the nickel filter, the operating voltage of 40kV, the current of 40mA and the scanning speed of 10 DEG/min.

In the context of the present specification, including in the examples and comparative examples below, the model of a Scanning Electron Microscope (SEM) for samples is a type S-4800II field emission scanning electron microscope. The method for measuring the crystal grain size of the sample comprises the following steps: the molecular sieve is observed under the magnification of 1 ten thousand times by using the scanning electron microscope, one observation view field is randomly selected, the average value of the sum of the particle sizes of all crystals in the observation view field is calculated, and the operation is repeated 10 times. The average value of the sum of the average values of 10 times was taken as the crystal grain size.

In the context of the present specification, included in the examples and comparative examples below, the methods of measuring sample dimensions are: molecular sieves were observed using a transmission electron microscope (FEI company G2F30 transmission electron microscope, netherlands, working voltage 300 kV) at a magnification of 10 ten thousand times, randomly selecting an observation field, calculating the average value of the sum of the sizes of all particles in the observation field, repeating the operation 10 times in total, and taking the average value of the sum of the average values of 10 times as the size of nanoparticles.

In the context of this specification, including in the examples and comparative examples below, the molecular sieve acid amount, acid species were determined using the pyridine adsorption infrared method (Nicolet Model 710 spectrometer). The specific operation steps are as follows: a. sample pretreatment. The sample (about 30 mg) was pressed into a thin disk 13mm in diameter and loaded into an infrared sample cell. Thereafter, the samples were pretreated under vacuum cell conditions at 400℃for 1h. After the sample cell cooled to room temperature, the sample extra-fuchsin data was scanned as background. b. Pyridine adsorption. Pyridine vapor was introduced in situ at room temperature and under vacuum until adsorption reached equilibrium for 1h. c. And (3) pyridine desorption. After the adsorption is finished, vacuumizing is carried out at 100 ℃ until the internal pressure is not changed, the desorption time is 40min, and the infrared absorption spectra are respectively scanned and recorded. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption-infrared absorption spectrum. Semi-quantitative calculation of acid amount of the sample was performed according to the spectrum:

where r and w are the diameter (cm) and mass (g) of the catalyst thin disk, and A is the integrated value of absorbance at a specified wavenumber peak according to the scanning pyridine adsorption-infrared absorption spectrum. IMEC is the integrated molar extinction coefficient, IMEC _L 2.22 IMEC _B 1.67. 1545cm ^-1 The nearby peak is B acid, 1455cm ^-1 The nearby peak is L acid.

The reaction product caprolactone was characterized by gas chromatography-mass spectrometry (GC-MS) analysis, and the product caprolactone yield and the conversion of the reaction substrate cyclohexanone were analyzed by Gas Chromatography (GC). The gas chromatograph is Agilent 7890A of Agilent corporation, U.S., the chromatographic column is HP-5 nonpolar capillary column (30 m,0.53 mm), the gas chromatograph is Agilent 7890B, the detector is hydrogen Flame Ionization Detector (FID), the chromatographic column is SE-54 capillary column (30 m,0.53 mm).

The yield and selectivity of the cyclohexylbenzene product are calculated as follows:

yield% of product cyclohexylbenzene = (molar amount of cyclohexylbenzene formed by reaction × 2)/(molar amount of substrate benzene reacted) ×100%.

The selectivity% of cyclohexylbenzene product = (molar amount of cyclohexylbenzene produced by reaction × 2)/(molar amount of benzene reacted) ×100%.

Example 1

1. And (3) preparing a catalyst:

mixing 4g deionized water, 0.75g 4-pyrrolidinylpyridine, 0.42g aluminum isopropoxide, 1.5g silica sol and 0.5g hydrofluoric acid to obtain 1SiO composition ₂ :0.1Al ₂ O ₃ :1F ^- :29H ₂ O:0.5OSDA, followed by an open heat pretreatment at 80℃to give a bulk mixture, which is heat pretreated to crystallize the silicon source (in SiO ₂ Calculated as a molar ratio of 1:5) and water, and then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

4mL of 3.2g/L ruthenium chloride solution was taken and added dropwise to 1g of sample B. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

XRD spectrum data of the catalyst are shown in table I-1, XRD spectrum data are shown in figure 1, and TEM and SEM pictures are shown in figure 2. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) Ru mass fraction is 0.3%, i.e. x/y=0.0021, y/z=10.

According to SEM FIG. 3, in the catalyst, the crystals have a long-strip morphology, the average length of the crystals is 0.4-1.5 μm, and the aspect ratio is 2-10.

TABLE I-1

Example 2

1. And (3) preparing a catalyst:

8mL of 3.2g/L ruthenium chloride solution was taken and added dropwise to 1g of sample B. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

XRD spectrum data of the catalyst are shown in Table I-2, and XRD spectrum data is similar to that of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) =10, ru mass fraction is 0.6%, i.e. x/y=0.0041, y/z=10.

The SEM of the catalyst is similar to that of fig. 3 in which the crystals have an elongated morphology, the average length of the crystals is 0.4 to 1.5 μm, and the aspect ratio is 2 to 10.

TABLE I-2

Example 3

1. And (3) preparing a catalyst:

20mL of 3.2g/L ruthenium chloride solution was taken and added dropwise to 1g of sample B. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

XRD spectrum data of the catalyst are shown in tables I-4, and XRD spectrum data is similar to that of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) =10, ru mass fraction 1.5%, i.e. x/y=0.0104, y/z=10.

TABLE I-3

Example 4

1. And (3) preparing a catalyst:

deionizing 4gWater, 1.1g of 4-pyrrolidinylpyridine, 0.42g of aluminum isopropoxide, 1.5g of silica sol and 0.75g of hydrofluoric acid, and uniformly mixing to obtain a composition of 1SiO ₂ :0.1Al ₂ O ₃ :1.5F ^- :29H ₂ O: components of 0.75OSDA, followed by open heat pretreatment at 80 ℃ to give a bulk mixture, which after heat pretreatment, is crystallized as a silicon source (in SiO ₂ Calculated as a mole ratio) and water is 1:4.5. Then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

XRD spectrum data of the catalyst are shown in Table I-3, and XRD spectrum data is similar to that of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) Ru mass fraction is 0.3%, i.e. x/y=0.0021, y/z=10.

The SEM of the catalyst is similar to that of fig. 3 in which the crystals have an elongated morphology, the average length of the crystals is 0.4 to 2.0 μm, and the aspect ratio is 2 to 15.

TABLE I-4

Example 5

1. And (3) preparing a catalyst:

mixing 4g deionized water, 1.5g 4-pyrrolidinylpyridine, 0.42g aluminum isopropoxide, 1.5g silica sol and 1g hydrofluoric acid uniformly to obtain a composition of 1SiO ₂ :0.1Al ₂ O ₃ :2F ^- :30H ₂ O:1OSDA, followed by an open heat pretreatment at 80℃to give a cake mixture, the raw material mixture being subjected to an addition ofAfter the heat pretreatment, the silicon source (SiO in the form of ₂ Calculated as a mole ratio) and water is 1:4.5. Then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

The SEM of the catalyst is similar to that of fig. 3 in which the crystals have an elongated morphology, the average length of the crystals is 0.5 to 2.5 μm, and the aspect ratio is 3 to 20.

TABLE I-5

Example 6

1. And (3) preparing a catalyst:

mixing 4g deionized water, 0.75g 4-pyrrolidinylpyridine, 0.42g aluminum isopropoxide, 1.5g silica sol and 0.5g hydrofluoric acid to obtain 1SiO composition ₂ :0.1Al ₂ O ₃ :1F ^- :29H ₂ O:0.5OSDA, followed by an open heat pretreatment at 80℃to give a bulk mixture, which is heat pretreated to crystallize the silicon source (in SiO ₂ Calculated as a molar ratio of 1:5) to water and then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

4mL of a 2.7g/L palladium chloride solution was used and added dropwise to 1g of sample B. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

XRD spectra of catalystsThe data are shown in tables I-5, and the XRD patterns are similar to those of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) =10, pd mass fraction is 0.3%, i.e. x/y=0.0021, y/z=10.

TABLE I-6

Example 7

1. And (3) preparing a catalyst:

mixing 4g deionized water, 0.75g 4-pyrrolidinyl pyridine, 0.21g aluminum isopropoxide, 1.5g silica sol and 0.5g hydrofluoric acid to obtain 1SiO composition ₂ :0.05Al ₂ O ₃ :1F ^- :29H ₂ O:0.5OSDA, followed by an open heat pretreatment at 80℃to give a bulk mixture, which is heat pretreated to crystallize the silicon source (in SiO ₂ Calculated as a mole ratio) and water is 1:5. Then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

XRD spectrum data of the catalyst are shown in tables I-6, and XRD spectrum data is similar to that of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) Ru mass fraction is 0.3%, i.e. x/y=0.0021, y/z=20.

The SEM of the catalyst is similar to that of fig. 3 in which the crystals have an elongated morphology, the average length of the crystals is 0.4 to 1.5 μm, and the aspect ratio is 2 to 12.

TABLE I-7

Example 8

1. And (3) preparing a catalyst:

mixing 4g deionized water, 0.75g 4-pyrrolidinylpyridine, 0.08g aluminum isopropoxide, 1.5g silica sol and 0.5g hydrofluoric acid to obtain 1SiO composition ₂ :0.02Al ₂ O ₃ :1F ^- :29H ₂ O:0.5OSDA, followed by an open heat pretreatment at 80℃to give a bulk mixture, which is heat pretreated to crystallize the silicon source (in SiO ₂ Calculated as a mole ratio) and water is 1:5. Then crystallizing for 15 days at 170 ℃ in a crystallization kettle. And taking out the product, washing with deionized water for 3 times, drying, and roasting at 550 ℃ for 6 hours to obtain a required sample B.

XRD spectrum data of the catalyst are shown in tables I-7, and XRD spectrum data is similar to that of FIG. 1. Wherein the composition is n (SiO ₂ ):n(Al ₂ O ₃ ) =50, ru mass fraction is 0.3%, i.e. x/y=0.0021, y/z=50.

TABLE I-8

Example 9

0.25g of the catalyst synthesized in example 1 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 10

0.25g of the catalyst synthesized in example 1 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.6MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 11

0.25g of the catalyst synthesized in example 1 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 2.0MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 12

0.25g of the catalyst synthesized in example 1 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 180 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 13

0.25g of the catalyst synthesized in example 1 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 200 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 14

0.25g of the catalyst synthesized in example 2 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 15

0.25g of the catalyst synthesized in example 3 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 16

0.25g of the catalyst synthesized in example 4 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 17

0.25g of the catalyst synthesized in example 5 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 18

0.25g of the catalyst synthesized in example 6 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Example 19

0.25g of the catalyst synthesized in example 7 was charged into a high-pressure reaction vessel, followed by adding 8g of benzene to the vessel and charging hydrogen gas to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

For comparison, the evaluation data are summarized in table 2.

Table 1 catalyst properties for each example

Table 2 catalytic performance of the examples

Example 21

The catalyst prepared in example 1 is washed, dried and put into the next reaction, and the reaction is carried out for 6 times in a total cycle. Wherein the catalyst was evaluated to preserve the reaction conditions in example 8, i.e., 8g of benzene was added to the autoclave and hydrogen was introduced to bring the system pressure to 1.2MPa. The system was then warmed to 150 ℃ until the reaction was completed after 4 h.

TABLE 2

Cycle times	Yield of cyclohexylbenzene (%)	Cyclohexylbenzene Selectivity (%)
			1	61	97.6
2	60	96.8
			3	61	96.6
4	61	97.4
			5	60	96.9
6	61	97.4

Comparative example 1

1. And (3) preparing a catalyst:

preparation method referring to example 1, sample B was changed to n (Si) only: n (Al) =10.

20mL of 3.2g/L ruthenium chloride solution was taken and added dropwise to 10g of the Y zeolite molecular sieve. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

2. Catalyst evaluation:

the catalyst evaluation method is shown in example 9.

The composition of the catalyst and the evaluation results are shown in Table 3 for comparison.

Comparative example 2

1. And (3) preparing a catalyst:

preparation method referring to example 1, sample B was changed to n (Si) only: n (Al) =20.

2. Catalyst evaluation:

the catalyst evaluation method is shown in example 9.

Comparative example 3

1. And (3) preparing a catalyst:

preparation method referring to example 8, sample B was changed to n (Si) only: n (Al) =20.

20mL of 3.2g/L ruthenium chloride solution was taken and added dropwise to 10g of the MCM-22 zeolite molecular sieve described above. Drying at 80 ℃ for 2 hours, and reducing for 3 hours in a fixed bed reactor under the conditions of 350 ℃ and hydrogen flow rate of 10mL/min to obtain the required catalyst.

2. Catalyst evaluation:

the catalyst evaluation method is shown in example 9.

Comparative example 4

1. And (3) preparing a catalyst:

preparation method referring to example 1, sample B was changed to n (Si) only: MCM-22 zeolite molecular sieve with n (Al) =30.

2. Catalyst evaluation:

the catalyst evaluation method is shown in example 9.

TABLE 3 Table 3

Comparative example	Molecular sieve species	n(Si):n(Al)	Yield of cyclohexylbenzene (%)	Cyclohexylbenzene Selectivity (%)
					1	Y	10	54	87.5
2	Y	20	53	83.8
					3	MCM-22	20	57	87.7
4	MCM-22	30	55	84.8

It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims

1. A catalyst for producing cyclohexylbenzene, the catalyst having the formula "xM-ySiO ₂ ·zAl ₂ O ₃ "schematic chemical composition shown;

wherein M is a metal element selected from one or more of ruthenium, platinum, palladium, copper and nickel metals;

2. The catalyst according to claim 1, wherein the mass content of the metal M in the catalyst is 0.2 to 2% based on the mass of the catalyst.

3. The catalyst of claim 1, wherein the catalyst has an X-ray diffraction pattern as shown in Table A-1,

table A-1

(a) And = ±0.3° (b) varies with 2θ.

4. The catalyst of claim 1 or 3, further comprising an X-ray diffraction pattern as shown in Table A-2,

table A-2

(a) And = ±0.3° (b) varies with 2θ.

5. The catalyst according to claim 1, wherein the total acid amount of the catalyst is 500 to 1500. Mu. Mol g ^-1 Preferably 800 to 1500. Mu. Mol.g ^-1 The ratio of the amount of B acid to the amount of L acid is 3 to 10, preferably 5 to 7.

6. The catalyst according to claim 1, wherein the crystals have a long or rod-like morphology, the average length of the crystals is 0.3 to 3 μm, and the aspect ratio is 2 to 20.

7. The catalyst according to claim 1, characterized in that the specific surface area of the catalyst is 200-600 meters ² Per gram, preferably 250 to 500 meters ² /g; the micropore volume of the catalyst is 0.05-0.30 cm ³ Per gram, preferably 0.10 to 0.25 cm ³ /g.

8. A process for preparing the catalyst for producing cyclohexylbenzene as claimed in any one of claims 1 to 7, comprising the steps of:

9. The method of claim 8, wherein in the step (1), the silicon source is added as SiO ₂ For counting, aluminum source is Al ₂ O ₃ For metering F as fluorine source ^- The molar ratio of the organic structure guiding agent a to water is 1 (0.02-0.2) (0.5-2) (0.25-1.5) (3-15), preferably 1 (0.05-0.15) (0.5-1) (5-10).

10. The method according to claim 8 or 9, wherein in step (1), the silicon source is at least one selected from silicic acid, silica gel, silica sol, tetraethyl silicate, water glass; the aluminum source is at least one selected from pseudo-boehmite and aluminum isopropoxide; in step (1), the fluorine source is selected from hydrofluoric acid; the organic structure directing agent is selected from 4-pyrrolidinylpyridine.

11. The process according to claim 8 or 9, wherein in step (1), the starting materialAfter the mixture is pretreated by heating, the silicon source is SiO during crystallization ₂ The molar ratio of the water to the water is 1 (1-10), preferably 1 (1.5-6.5).

12. The method according to claim 8 or 9, wherein in step (1), the crystallization conditions are: the temperature is 120-200 ℃, the time is 7-21 days, preferably, the temperature is 150-200 ℃ and the time is 7-15 days.

13. The production method according to claim 8 or 9, wherein in step (2), the concentration of the M-containing metal solution is 2 to 50g/L.

14. A process for the one-step preparation of cyclohexylbenzene by hydrogenation of benzene using the catalyst of any one of claims 1 to 7.

15. The method according to claim 14, comprising the contact reaction of raw benzene and the catalyst to produce cyclohexylbenzene with hydrogen as a hydrogen source; wherein the mass ratio of the raw material benzene to the catalyst is 8-40; the reaction temperature is 100-220 ℃, the reaction time is 2-8 hours, and the reaction hydrogen pressure is 0.8-2.5 MPa.