阅读说明：本技术 合成环己基苯的方法 (Process for synthesizing cyclohexylbenzene ) 是由 王高伟 高焕新 魏一伦 尤陈佳 于 2018-06-06 设计创作，主要内容包括：本发明涉及一种合成环己基苯的方法。所述方法包括在有效反应条件下,使苯和氢气与催化剂接触合成环己基苯的步骤；所述催化剂包含第一分子筛、不同于所述第一分子筛的第二分子筛和至少一种加氢金属的复合材料；所述第一分子筛的孔口直径小于0.5纳米。该方法可用于环己基苯的工业生产中。(The invention relates to a method for synthesizing cyclohexylbenzene. The process comprises the steps of contacting benzene and hydrogen with a catalyst under effective reaction conditions to synthesize cyclohexylbenzene; the catalyst comprises a composite of a first molecular sieve, a second molecular sieve different from the first molecular sieve, and at least one hydrogenation metal; the diameter of the orifice of the first molecular sieve is less than 0.5 nanometer. The method can be used for the industrial production of the cyclohexylbenzene.)

1. A process for synthesizing cyclohexylbenzene, comprising the step of contacting benzene and hydrogen with a catalyst under effective reaction conditions to synthesize cyclohexylbenzene; the catalyst comprises a composite of a first molecular sieve, a second molecular sieve different from the first molecular sieve, and at least one hydrogenation metal; the diameter of the orifice of the first molecular sieve is less than 0.5 nanometer.

2. The method for synthesizing cyclohexylbenzene according to claim 1, wherein the weight ratio of the first molecular sieve to the second molecular sieve is 0.05 to 10, preferably 0.1 to 5, and more preferably 0.4 to 2.

3. The method for synthesizing cyclohexylbenzene according to claim 1, wherein the content of the hydrogenation metal is 0.01 to 5% by weight based on the total weight of the catalyst.

4. The process for synthesizing cyclohexylbenzene as set forth in claim 1, wherein the first molecular sieve has an MFI topology, preferably a ZSM-5 molecular sieve.

5. The process for synthesizing cyclohexylbenzene as set forth in claim 1, wherein the packing fraction of the hydrogenation metal in the first molecular sieve channels is at least 80%, preferably at least 90%, more preferably 100%.

6. The process for synthesizing cyclohexylbenzene as set forth in claim 5, wherein the first molecular sieve has SiO at the outer surface and the orifice thereof₂And (4) coating.

7. the process for synthesizing cyclohexylbenzene according to claim 1, characterized in that the second molecular sieve is selected from at least one of molecular sieves having MWW, BEA, MOR and FAU topology, preferably at least one of molecular sieves having MWW and BEA topology.

8. The process for synthesizing cyclohexylbenzene as set forth in claim 1, wherein the second molecular sieve is selected from at least one of an MCM-22 family molecular sieve and a Beta molecular sieve.

9. The process for synthesizing cyclohexylbenzene according to claim 1, characterized in that the hydrogenation metal is selected from at least one of palladium, ruthenium, platinum, rhodium and iridium, preferably at least one of palladium and ruthenium.

10. The process for synthesizing cyclohexylbenzene as set forth in claim 1, wherein the effective reaction conditions include: the reaction temperature is 100-300 ℃, the reaction pressure is 0.5-5.0 MPa, the hydrogen/benzene molar ratio is 0.1-5, and the benzene weight space velocity is 0.1-10 h < -1 >; the preferable reaction temperature is 150-250 ℃, the reaction pressure is 1.0-4.0 MPa, the hydrogen/benzene molar ratio is 0.2-2, and the benzene weight space velocity is 0.2-5 hours^-1。

Technical Field

The invention relates to a method for synthesizing cyclohexylbenzene.

Background

The cyclohexylbenzene is an important fine chemical intermediate, has a high boiling point and a condensation point close to room temperature, and has special physical and chemical properties. Cyclohexylbenzene has been widely used in the battery industry as an additive in lithium ion battery electrolytes, has overcharge prevention properties, and can improve the safety of batteries. In addition, cyclohexylbenzene can also be used for synthesizing liquid crystal materials.

The peroxidation of cyclohexylbenzene can produce phenol and cyclohexanone. Phenol plays an important role as an important product in the chemical industry. At present, the industrial production mainly adopts the peroxidation reaction of cumene to prepare phenol, but a large amount of acetone is generated as a byproduct in the reaction process. Compared with the process for preparing phenol by a cumene oxidation method, the oxidation products of the cyclohexylbenzene are phenol and cyclohexanone. The latter is an important raw material for producing caprolactam and nylon, so that the problem of utilization of byproducts does not exist.

Document US5053571 discloses a process for preparing cyclohexylbenzene by hydroalkylation of benzene over a Ru and Ni loaded Beta molecular sieve. Document US5146024 discloses a process for the hydroalkylation of benzene to produce cyclohexylbenzene by loading metallic Pd on an X or Y molecular sieve, the catalyst being modified with an alkali metal or a rare earth metal. The exxonmobil company, in documents US6037513, US7579511, US7847128, US7910778, US8084648, US8106243, US8178728, US8329956, US8519194, US20100191017, US20110015457, US20110288341, US20120178969 and in documents CN101687728, CN101754940, CN101796000, CN101925561, CN101998942, CN102015589, CN102177109 and CN103261126, carries out the hydroalkylation reaction under a hydrogen atmosphere using a catalytic system of molecular sieves of the MCM-22 family and at least one hydrogenation metal (palladium, platinum, nickel and ruthenium). The reaction conditions are as follows: the temperature is 140-175 deg.C, the pressure is 931-1207 KPa, the molar ratio of hydrogen to benzene is 0.3-0.65 and 0.26-1.05 hr^-1The weight hourly space velocity of benzene. The highest yield of cyclohexylbenzene was about 40%. The document US20120157718 discloses a method for preparing cyclohexyl by benzene and cyclohexene alkylation using a Y molecular sieve and benzene hydroalkylation reaction of the Y molecular sieve loaded with a hydrogenation metal (palladium, platinum, nickel and ruthenium).

because the aromatic hydrocarbon raw material contains a certain amount of sulfur-containing impurities, such as thiophene, benzothiophene, dibenzothiophene and the like, the sulfur impurities can generate a toxic effect on the supported metal catalyst, so that the activity of the catalyst is reduced. Generally in industrial processes, guard beds are used to clean the aromatic feedstock. The use, regeneration, and final disposal of the adsorbent in the guard bed increases operating costs.

Disclosure of Invention

The present inventors have assiduously studied on the basis of the prior art and found that at least one of the aforementioned problems can be solved by using two different molecular sieves, the first molecular sieve serving a shape-selective action and the second molecular sieve serving an alkylation action, and thus have completed the present invention.

Specifically, the invention relates to a method for synthesizing cyclohexylbenzene, which comprises the steps of contacting benzene and hydrogen with a catalyst under effective reaction conditions to synthesize cyclohexylbenzene; the catalyst comprises a composite of a first molecular sieve, a second molecular sieve different from the first molecular sieve, and at least one hydrogenation metal; the diameter of the orifice of the first molecular sieve is less than 0.5 nanometer.

According to one aspect of the invention, the weight ratio of the first molecular sieve to the second molecular sieve is 0.05 to 10, preferably 0.1 to 5, more preferably 0.4 to 2.

According to one aspect of the invention, the content of the hydrogenation metal is 0.01-5% based on the total weight of the catalyst.

According to one aspect of the invention, the first molecular sieve has an MFI topology, preferably a ZSM-5 molecular sieve.

According to one aspect of the invention, the packing fraction of the hydrogenation metal in the first molecular sieve channels is at least 80%, preferably at least 90%, more preferably 100%.

according to one aspect of the invention, the first molecular sieve has SiO at its outer surface and at its openings₂And (4) coating.

According to one aspect of the invention, the second molecular sieve is selected from at least one of molecular sieves having MWW, BEA, MOR and FAU topology, preferably at least one of molecular sieves having MWW and BEA topology.

According to one aspect of the invention, the second molecular sieve is selected from at least one of molecular sieves of the MCM-22 family and molecular sieves Beta.

According to one aspect of the invention, the hydrogenation metal is selected from at least one of palladium, ruthenium, platinum, rhodium and iridium, preferably at least one of palladium and ruthenium.

According to one aspect of the invention, the effective reaction conditions include: the reaction temperature is 100-300 ℃, the reaction pressure is 0.5-5.0 MPa, and the hydrogen/benzene molar ratio is 0.1 ∞5, the benzene weight space velocity is 0.1-10 h < -1 >; the preferable reaction temperature is 150-250 ℃, the reaction pressure is 1.0-4.0 MPa, the hydrogen/benzene molar ratio is 0.2-2, and the benzene weight space velocity is 0.2-5 hours^-1。

The invention has the beneficial effects that: the invention obtains the bifunctional catalyst which can be used for synthesizing the cyclohexylbenzene by benzene hydrogenation alkylation reaction by mixing the two molecular sieves. The first molecular sieve acts as a shape-selective agent and the second molecular sieve acts as an alkylation agent. Particularly, the hydrogenation metal is positioned in the first molecular sieve pore canal with the pore canal size less than 0.5nm, and the toxic action of sulfur species on the hydrogenation metal can be avoided through the shape selectivity of the molecular sieve; meanwhile, metal is placed in the pore channel of the first molecular sieve, and the sintering of metal particles is inhibited due to the confinement effect, so that the activity of the catalyst can be effectively maintained, the stability of the catalyst is ensured, and the catalyst has the characteristic of long service life.

Detailed Description

The following describes in detail specific embodiments of the present invention. It is to be noted, however, that the scope of the present invention is not limited thereto, but is defined by the appended claims.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

Unless otherwise expressly indicated, all percentages, ratios, etc. mentioned within this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.

In this specification, the metal encapsulation efficiency is defined as: the amount of metal active sites located in the openings of the first molecular sieve is a percentage of the total amount of metal active sites on the first molecular sieve. The metal encapsulation rate is quantitatively calculated by taking benzene hydroalkylation reaction as probe reaction. In the case of the reaction using pure benzene, the conversion of benzene is counted as C; when benzene containing 10ppm of thiophene was used as a raw material for the reaction, the conversion was counted as Cs; the metal encapsulation rate is Cs/Cx 100%.

The invention provides a method for synthesizing cyclohexylbenzene by hydroalkylation. The process includes the step of contacting benzene and hydrogen with a catalyst under effective reaction conditions to synthesize cyclohexylbenzene.

Any commercially available benzene feedstock can be used in the present invention. In particular, the present invention can treat benzene feedstocks that contain certain sulfur impurities, such as thiophene, benzothiophene, and dibenzothiophene. The total sulfur impurity content in the benzene feed was less than 10 ppm.

The source of the hydrogen is not critical, as long as the hydrogen is at least 99% pure.

According to the invention, the catalyst comprises a composite of a first molecular sieve, a second molecular sieve different from the first molecular sieve, and at least one hydrogenation metal.

According to the invention, the first molecular sieve has an MFI topology, preferably a ZSM-5 molecular sieve, and acts as a shape-selective function, controlling the diameter of its pores to be less than 0.5 nm.

According to the present invention, the second molecular sieve effects alkylation. The second molecular sieve is selected from at least one of molecular sieves having MWW, BEA, MOR and FAU topologies, preferably at least one of molecular sieves having MWW and BEA topologies, more preferably at least one of a molecular sieve of the MCM-22 family and a Beta molecular sieve. The MCM-22 family molecular sieves include MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-2, MCM-36, MCM-49, MCM-56, UZM-8 and mixtures thereof.

According to the invention, the weight ratio of the first molecular sieve to the second molecular sieve is 0.05 to 10, preferably 0.1 to 5, more preferably 0.4 to 2. E.g. 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0.

any known hydrogenation metal can be used in accordance with the present invention, with palladium and ruthenium being particularly advantageous, although suitable metals include palladium, ruthenium, platinum, rhodium and iridium. The content of hydrogenation metal is 0.01 to 5%, for example 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, based on the total weight of the catalyst.

According to the present invention, it is desirable that the hydrogenation metal be located as much as possible within the channels of the first molecular sieve. The encapsulation rate of the hydrogenation metal in the first molecular sieve pore channels is at least 80%, preferably at least 90%, and more preferably 100%. As previously mentioned, the first molecular sieve pore diameters are less than 0.5 nanometers in diameter, while the kinetic diameters of common sulfur species, such as thiophene, benzothiophene, and dibenzothiophene, are all greater than 0.5 nanometers. Thus, the sulfur species cannot poison the hydrogenation metal in the channels due to the shape-selective effect of the channels.

The preparation method of the catalyst comprises the following steps: synthesizing a first molecular sieve with hydrogenation metal in the pore channel; silanizing the first molecular sieve; mixing the first molecular sieve and the second molecular sieve, and molding.

In order to obtain the first molecular sieve with hydrogenation metal in the pore canal, an in-situ hydrothermal synthesis mode can be adopted. The "in situ hydrothermal synthesis" is well known in the art and is typically: the precursor for synthesizing the molecular sieve is dispersed in water solution in advance, and then the molecular sieve is formed through the processes of nucleation, growth, crystallization and the like at the crystallization temperature and the self pressure. The precursor of the first molecular sieve for synthesizing the packaging metal comprises a silicon source, an aluminum source, alkali, an ammonia complex of hydrogenation metal and water.

In order to obtain the first molecular sieve with the hydrogenation metal in the pore canal, alkali treatment, dipping and loading the hydrogenation metal and secondary crystallization can be adopted. According to the method, firstly, alkali treatment is carried out to form 'defects' on the surface of the molecular sieve, then the 'defects' provide more 'loading sites' for hydrogenation metal during impregnation, and finally, the metal can be coated in the pore channels and the cages of the molecular sieve through a secondary crystallization process, so that the first molecular sieve with the hydrogenation metal packaged in the pore channels of the molecular sieve is formed. Among them, alkali treatment, impregnation of a hydrogenation metal, and secondary crystallization are well known in the art. For example, the alkali treatment is to contact the molecular sieve with an alkali solution at least once, at a contact temperature of 10-100 ℃ and for a contact time of 1-48 hours. The alkali solution can be selected from sodium hydroxide solution, and the molar concentration is 0.01-5 mol/L. The impregnation loading of the hydrogenation metal is to contact the molecular sieve with the hydrogenation metal salt solution at least once, wherein the contact temperature is 10-100 ℃, and the contact time is 0.1-24 hours. The hydrogenation metal salt may be selected from the group consisting of chlorides and nitrates containing the hydrogenation metal. The secondary crystallization is that the mixture of the molecular sieve loaded with metal and the precursor is subjected to the secondary crystallization processes of nucleation, growth and crystallization again at the crystallization temperature and the self pressure.

The silanization of the first molecular sieve means that after the hydrogenated metal is encapsulated in the pore channel of the first molecular sieve, the first molecular sieve is contacted with a silanization reagent, so that the diameter of the pore opening of the first molecular sieve is controlled to be less than 0.5 nanometer. The contact conditions include: the temperature is 100-200 ℃, and the liquid-solid ratio is 0.05-1. The silanization reagent is selected from at least one of organosilane or organic silazane. The organosilane is selected from at least one of trimethylchlorosilane, dichlorodimethylsilane, monochlorobibromodimethylsilane, nitrotrimethylsilane, triethylchlorosilane, dimethylbutyliodosilane, dimethylphenylchlorosilane, dimethylchlorobromosilane, N-trimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole or N-trimethylsilylpiperidine, N, O-bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N- (trimethylsilyl) trifluoroacetamide or N-methyl-N-trimethylsilylheptafluorobutanamide And (4) seed preparation. The organic silazane is at least one selected from hexamethyldisilazane, heptamethyldisilazane, 1,3, 3-tetramethyldisilazane, 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 1, 3-diphenyl tetramethyldisilazane.

ZSM-5 has a special pore structure and physicochemical properties, and is widely used in various chemical fields. The ZSM-5 skeleton contains two intercrossed pore channel systems. The 10 circular ring pore channels parallel to the a axis direction are S-shaped and bent, the corners of the 10 circular ring pore channels are about 150 degrees, the pore diameter is 0.55nm multiplied by 0.51nm, the 10 circular ring pore channels parallel to the b axis direction are linear, and the pore diameter of the oval pore channels is 0.53nm multiplied by 0.56 nm. The size of the channels can be modified by using silanization reagents. The silanization reagent can react with the hydroxyl on the outer surface and pore opening of the zeolite to form SiO after being calcined in the air₂The coating is deposited on the outer surface and the pore openings of the zeolite, so that the pore openings of the zeolite are reduced in size, and the purpose of controlling the effective pore diameter of the zeolite is achieved.

According to the bookIn accordance with the present invention, the hydroalkylation reaction can be carried out in a wide range of reactor configurations including fixed bed, slurry bed, catalytic distillation columns. The effective reaction conditions include: the reaction temperature is 100-300 ℃, the reaction pressure is 0.5-5.0 MPa, the hydrogen/benzene molar ratio is 0.1-5, and the benzene weight space velocity is 0.1-10 hours^-1(ii) a The preferable reaction temperature is 150-250 ℃, the reaction pressure is 1.0-4.0 MPa, the hydrogen/benzene molar ratio is 0.2-2, and the benzene weight space velocity is 0.2-5 hours^-1。

The invention is further illustrated by the following examples.

[ example 1-1 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, and 0.619 g of ruthenium hexaammine trichloride is added, and the material ratio (mol ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Ru/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. Placing the calcined sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-Trimethylsilylimidazole (TSIM) into the reactor by nitrogen through a bubbler, reacting for 1.5hr, and then purging for 2hr under nitrogen atmosphere to obtain a silanization modified sample.

10 g of the sample is mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes. The catalyst is numbered Ru @ ZSM-5-TSIM/MCM-22.

[ examples 1-2 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g, 3.2 g of sodium hydroxide, 144.0 g of water was added thereto and the mixture was stirred to dissolve,Then 60 g of 40% silica sol is added, 0.619 g of ruthenium hexammine trichloride is added, and the material ratio (mol ratio) of reactants is as follows:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Ru/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. Placing the roasted sample in a quartz tube reactor, heating to 200 ℃, introducing nitrogen, introducing Hexamethyldisilazane (HMDS) into the reactor by the aid of the nitrogen through a bubbler, reacting for 1.5 hours, and then purging for 2 hours in a nitrogen atmosphere to obtain a silanization modified sample.

10 g of the sample is mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes. The catalyst number is Ru @ ZSM-5-HDMS/MCM-22.

[ examples 1 to 3 ]

sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, and 0.619 g of ruthenium hexaammine trichloride is added, and the material ratio (mol ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Ru/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. Placing the calcined sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-Trimethylsilylimidazole (TSIM) into the reactor by nitrogen through a bubbler, reacting for 1.5hr, and then purging for 2hr under nitrogen atmosphere to obtain a silanization modified sample.

10 g of the sample is taken, 12 g of Beta molecular sieve with BEA topological structure is mixed, tabletting and granulation are carried out, and 40-60 mesh granules are taken for performance evaluation. The catalyst number is Ru @ ZSM-5-TSIM/Beta.

[ examples 1 to 4 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, and 0.619 g of ruthenium hexaammine trichloride is added, and the material ratio (mol ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Ru/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. Placing the roasted sample in a quartz tube reactor, heating to 200 ℃, introducing nitrogen, introducing Hexamethyldisilazane (HMDS) into the reactor by the aid of the nitrogen through a bubbler, reacting for 1.5 hours, and then purging for 2 hours in a nitrogen atmosphere to obtain a silanization modified sample.

10 g of the sample is taken, 12 g of Beta molecular sieve with BEA topological structure is mixed, tabletting and granulation are carried out, and 40-60 mesh granules are taken for performance evaluation. The catalyst number is Ru @ ZSM-5-HMDS/Beta.

[ examples 1 to 5 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, 0.598 g of tetraamminepalladium nitrate is added, and the material ratio (molar ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Pd/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. Placing the calcined sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-Trimethylsilylimidazole (TSIM) into the reactor by nitrogen through a bubbler, reacting for 1.5hr, and then purging for 2hr under nitrogen atmosphere to obtain a silanization modified sample.

10 g of the sample is mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes. The catalyst is numbered as Pd @ ZSM-5-TSIM/MCM-22.

[ examples 1 to 6 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, 0.598 g of tetraamminepalladium nitrate is added, and the material ratio (molar ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Pd/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. And placing the roasted sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-Trimethylsilylimidazole (TSIM) into the reactor by the aid of the nitrogen through a bubbler, reacting for 1.5 hours, and then purging for 2 hours in a nitrogen atmosphere to obtain a silanization modified Pd-ZSM-5-TSIM sample.

10 g of the sample is taken, 12 g of Beta molecular sieve with BEA topological structure is mixed, tabletting and granulation are carried out, and 40-60 mesh granules are taken for performance evaluation. The catalyst number is Pd @ ZSM-5-TSIM/Beta.

[ examples 1 to 7 ]

Sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, then 60 g of 40% silica sol is added, and 0.670 g of tetraammineplatinum chloride is added, and the material ratio (mol ratio) of the reactants is:

SiO₂/Al₂O₃＝50

NaOH/SiO₂＝0.2

H₂O/SiO₂＝25

Pt/SiO₂＝0.005

After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain the Ru-ZSM-5 sample. And (3) placing the roasted sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-trimethylsilyl imidazole into the reactor by the aid of the nitrogen through a bubbler, reacting for 1.5 hours, and then purging for 2 hours in a nitrogen atmosphere to obtain a silanization modified Pt-ZSM-5-TSIM sample.

10 g of the sample is taken, 12 g of MCM-22 molecular sieve with MWW topological structure is mixed and then tabletting granulation is carried out, and 40-60 mesh particles are taken for performance evaluation. The catalyst number is Pt @ ZSM-5-TSIM/MCM-22.

[ COMPARATIVE EXAMPLES 1 to 1 ]

Consistent with [ example 1 ], except that no silylation agent was used for treatment, a Ru @ ZSM-5 sample was obtained. 10 g of the sample is mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes. The catalyst is numbered Ru @ ZSM-5/MCM-22.

[ COMPARATIVE EXAMPLES 1 to 2 ]

Taking Al₂O₃10 g of ruthenium hexaammine trichloride 0.258 g, impregnated with equal volumeMethod for obtaining Ru-Al₂O₃A catalyst. The samples are mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, then tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes. Catalyst number Ru-Al₂O₃/MCM-22。

[ COMPARATIVE EXAMPLES 1 to 3 ]

0.258 g of ruthenium hexammine trichloride was taken, and Ru was isovolumetrically impregnated into 12 g of MCM-22 molecular sieve having MWW topology using isovolumic impregnation method. And tabletting and granulating after roasting, and evaluating the granules of 40-60 meshes. The catalyst was numbered Ru/MCM-22.

[ examples 1 to 8 ]

The catalyst synthesized in [ example 1-1 to 1-7 ] was packed in a fixed bed tubular reactor in H₂/N₂At 200 ℃ for 2 hours, wherein H₂The flow rate is 40ml/min, N₂The flow rate was 60 ml/min. After reduction with N₂Purging and cooling. Pure benzene and hydrogen are introduced to carry out a hydrogenation alkylation reaction, and the liquid phase composition is analyzed by using an online chromatograph after gas-liquid separation after the reaction. The reaction condition is that the weight space velocity of the benzene is 1.0h^-1The molar ratio of hydrogen to benzene is 0.5, the reaction temperature is 150 ℃, and the reaction pressure is 1.0 MPa.

The reaction was continued for 50 hours, and the reaction results are shown in Table 1.

TABLE 1

The catalyst synthesized in [ example 1-1 to 1-7 ] was packed in a fixed bed tubular reactor in H₂/N₂At 200 ℃ for 2 hours, wherein H₂The flow rate is 40ml/min, N₂The flow rate was 60 ml/min. After reduction with N₂Purging and cooling. Then benzene containing thiophene and hydrogen are introduced to carry out hydrogenation alkylation reaction, and the liquid phase composition is analyzed by using an online chromatograph after gas-liquid separation after the reaction. The reaction conditions are as follows: the weight space velocity of the benzene is 1.0h^-1The molar ratio of hydrogen to benzene is 0.5, the reaction temperature is 150 ℃, and the reaction is carried outThe pressure is 1.0MPa, wherein the benzene contains 10mg/Kg of thiophene.

The reaction was continued for 50 hours, and the reaction results are shown in Table 2.

TABLE 2

[ COMPARATIVE EXAMPLES 1 to 4 ]

In the same manner as in [ examples 1-8 ], the catalyst synthesized in [ comparative examples 1-1 to 1-3 ] was packed in a fixed bed tubular reactor and continuously reacted for 50 hours, and the reaction results are shown in tables 1 and 2.

[ example 2-1 ]

Synthesizing a ZSM-5 molecular sieve: sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, 60 g of 40% silica sol is added, and the material ratio (mol ratio) of the reactants is as follows: SiO 2₂/Al₂O₃＝50，NaOH/SiO₂＝0.2，H₂O/SiO₂25. After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain a ZSM-5 sample.

And (3) soaking in equal volume: 10 g of the sample was treated at room temperature in an aqueous NaOH solution having a molar concentration of 0.2. After 2h, it was filtered, washed and dried. Taking 5g of the sample, taking a sample containing 0.051g of RuCl₃The aqueous solution of (a) was subjected to an equal volume impregnation and then dried.

Secondary crystallization: the powder is transferred into a mixed solution containing tetraethyl silicate and tetrapropylammonium hydroxide, wherein the molar ratio of the tetraethyl silicate to the tetrapropylammonium hydroxide is 25, and the molar ratio of the tetraethyl silicate to the water is 0.0167. After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 12 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours.

Silanization treatment: and placing the roasted sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-trimethylsilyl imidazole into the reactor by the nitrogen through a bubbler, reacting for 1.5hr, and then purging for 2hr under the nitrogen atmosphere to obtain the silanized and modified Ru-ZSM-5-TSIM sample.

10 g of the sample is mixed with 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating are carried out, and evaluation is carried out on particles of 40-60 meshes.

[ example 2-2 ]

Synthesizing a ZSM-5 molecular sieve: sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, 60 g of 40% silica sol is added, and the material ratio (mol ratio) of the reactants is as follows: SiO 2₂/Al₂O₃＝50，NaOH/SiO₂＝0.2，H₂O/SiO₂25. After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain a ZSM-5 sample.

And (3) soaking in equal volume: 10 g of the sample was treated at room temperature in an aqueous NaOH solution having a molar concentration of 0.2. After 2h, it was filtered, washed and dried. Taking 5g of the sample, taking a sample containing 0.051g of RuCl₃An equal volume of aqueous solution was soaked and then dried.

Secondary crystallization: the powder is transferred into a mixed solution containing tetraethyl silicate and tetrapropylammonium hydroxide, wherein the molar ratio of the tetraethyl silicate to the tetrapropylammonium hydroxide is 25, and the molar ratio of the tetraethyl silicate to the water is 0.0167. After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 12 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours.

Silanization treatment: and placing the roasted sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-trimethylsilyl imidazole into the reactor by the nitrogen through a bubbler, reacting for 1.5hr, and then purging for 2hr under the nitrogen atmosphere to obtain the silanized and modified Ru-ZSM-5-TSIM sample.

10 g of the sample is taken, 12 g of Beta molecular sieve with BTA topological structure is mixed and then tabletted and granulated, and the granules of 40-60 meshes are taken for performance evaluation.

[ examples 2 to 3 ]

Synthesizing a ZSM-5 molecular sieve: sodium aluminate (Al)₂O₃45.8 wt.%) 1.78 g and 3.2 g of sodium hydroxide, then 144.0 g of water is added and stirred to dissolve the mixture, 60 g of 40% silica sol is added, and the material ratio (mol ratio) of the reactants is as follows: SiO 2₂/Al₂O₃＝50，NaOH/SiO₂＝0.2，H₂O/SiO₂25. After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 40 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain a ZSM-5 sample.

And (3) soaking in equal volume: 10 g of the sample was treated at room temperature in an aqueous NaOH solution having a molar concentration of 0.2. After 2h, it was filtered, washed and dried. 5g of the above sample was sampled to contain 0.041g of PdCl₂An equal volume of aqueous solution was soaked and then dried.

Secondary crystallization: the powder is transferred into a mixed solution containing tetraethyl silicate and tetrapropylammonium hydroxide, wherein the molar ratio of the tetraethyl silicate to the tetrapropylammonium hydroxide is 25, and the molar ratio of the tetraethyl silicate to the water is 0.0167. After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 12 hours at 180 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours.

Silanization treatment: and placing the roasted sample in a quartz tube reactor, heating to 150 ℃, introducing nitrogen, introducing N-trimethylsilyl imidazole into the reactor by the aid of nitrogen through a bubbler, reacting for 1.5 hours, and purging for 2 hours in nitrogen atmosphere to obtain a silanization modified Pd-ZSM-5-TSIM sample.

10 g of the sample is taken, 12 g of MCM-22 molecular sieve with MWW topological structure is mixed and then tabletting granulation is carried out, and 40-60 mesh particles are taken for performance evaluation.

[ examples 2 to 4 ]

The catalyst synthesized in (example 2-1 to 2-3) was loaded in a fixed bed tubular reactor, and reacted continuously for 50 hours as in (example 1-8), with 5mg/Kg thiophene in the benzene. The reaction results are shown in tables 3 and 4.

TABLE 3

TABLE 4