Method for synthesizing cyclohexylbenzene by hydroalkylation
阅读说明：本技术 加氢烷基化合成环己基苯的方法 (Method for synthesizing cyclohexylbenzene by hydroalkylation ) 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：本发明涉及一种加氢烷基化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。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 by hydroalkylation. 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 method can be used for the industrial production of the cyclohexylbenzene.)
1. A process for the hydroalkylation of 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.
2. The hydroalkylation process of 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 hydroalkylation process of claim 1, wherein the hydrogenation metal is present in an amount of 0.01 to 5 wt% based on the total weight of the catalyst.
4. The hydroalkylation process of claim 1, wherein the hydrogenation metal is encapsulated in the first molecular sieve channels at a level of at least 80%, preferably at least 90%, and more preferably 100%.
5. The hydroalkylation synthesis of cyclohexylbenzene according to claim 1, wherein the first molecular sieve has an orifice diameter of less than 0.5 nm.
6. The hydroalkylation synthesis of cyclohexylbenzene according to claim 1, wherein the first molecular sieve is selected from at least one molecular sieve having CHA, SOD, GIS, ANA, LTA, and NAT topology.
7. The hydroalkylation process of claim 1, wherein the first molecular sieve is selected from at least one of synthetic chabazite, sodalite, synthetic ferrierite, analcime, NaA-type zeolite, and synthetic natrolite.
8. The hydroalkylation process of claim 1, wherein the second molecular sieve is selected from at least one molecular sieve having MFI, MWW, BEA, MOR and FAU topology, preferably at least one molecular sieve having MWW and BEA topology.
9. The hydroalkylation synthesis of cyclohexylbenzene according to claim 1, wherein the second molecular sieve is selected from at least one of molecular sieves of the MCM-22 family and molecular sieves Beta.
10. The hydroalkylation synthesis of 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.
11. The hydroalkylation synthesis of cyclohexylbenzene according to claim 1, wherein the effective reaction conditions comprise: 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 by hydroalkylation.
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.
In particular, the invention relates to a method for synthesizing cyclohexylbenzene by hydroalkylation. 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.
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 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 an orifice diameter of less than 0.5 nanometers.
According to one aspect of the invention, the first molecular sieve is selected from at least one of molecular sieves having CHA, SOD, GIS, ANA, LTA, and NAT topologies.
According to one aspect of the invention, the first molecular sieve is selected from at least one of synthetic chabazite, sodalite, synthetic ferrierite, analcime, NaA-type zeolite and synthetic natrolite.
According to one aspect of the invention, the second molecular sieve is selected from at least one of molecular sieves having MFI, 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, 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 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.
Drawings
FIG. 1 is [ example 1 ] an electron micrograph of a Ru @ NaA sample, with a 20nm scale.
FIG. 2 is an electron micrograph of a Ru-NaA sample (comparative example 1) at 100 nm.
The electron microscope model is Tecnai G220S-Twin, produced by FEI of the Netherlands.
as can be seen from FIG. 1, the hydrogenated metal particles are uniform, have a diameter of about 1nm, and are located in the pore channels of the NaA molecular sieve.
As can be seen from FIG. 2, the hydrogenation metal has a particle size of about 20nm and is located on the outer surface of the NaA molecular sieve.
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 content of total sulfur impurities in the benzene raw material is not more than 10 mg/kg.
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 acts as a shape selective sieve having pore openings with a diameter of less than 0.5 nm. The first molecular sieve is selected from at least one of molecular sieves having CHA, SOD, GIS, ANA, LTA, and NAT topologies. Preferably, the first molecular sieve is selected from at least one of synthetic chabazite, sodalite, synthetic ferrierite, analcime, NaA-type zeolite and synthetic natrolite.
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 MFI, MWW, BEA, MOR and FAU topologies, preferably at least one of molecular sieves having MWW and BEA topologies, more preferably at least one of molecular sieves of the MCM-22 family and Beta molecular sieves. 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; 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 channel, a hydrothermal synthesis mode can be adopted. The "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.
According to the present invention, the hydroalkylation reaction can be carried out in a wide range of reactor configurations including fixed beds, slurry beds, 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 ]
Sodium aluminate (Al)2O345 wt.%) 39.2 g and 29.8 g of sodium hydroxide were mixed, 367.9 g of water was added and the mixture was stirred to dissolve, 50 g of 40% silica sol was added, 0.516 g of ruthenium hexaammine trichloride was added, and the mixture ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝1.9
NaOH/SiO2＝2.2
H2O/SiO2＝66.3
Ru/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. And after being taken out, the Ru @ NaA sample is obtained after filtering, washing, drying and roasting for 5 hours at 500 ℃.
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 @ NaA/MCM-22.
[ example 2 ]
Sodium aluminate (Al)2O345 wt.%) 39.2 g and 29.8 g of sodium hydroxide were mixed, 367.9 g of water was added and the mixture was stirred to dissolve, 50 g of 40% silica sol was added, 0.516 g of ruthenium hexaammine trichloride was added, and the mixture ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝1.9
NaOH/SiO2＝2.2
H2O/SiO2＝66.3
Ru/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. And after being taken out, the Ru @ NaA sample is obtained after filtering, washing, drying and roasting for 5 hours at 500 ℃.
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 @ NaA/Beta.
[ example 3 ]
Sodium aluminate (Al)2O345 wt.%) 39.2 g and 29.8 g of sodium hydroxide were mixed, 367.9 g of water were added and the mixture was stirred to dissolve, 50 g of 40% silica sol was added, 0.498 g of tetraamminepalladium nitrate was added, and the material ratios (molar ratios) of the reactants were:
SiO2/Al2O3＝1.9
NaOH/SiO2＝2.2
H2O/SiO2＝66.3
Pd/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. After being taken out, the solution is filtered, washed, dried and roasted at 500 ℃ for 5 hours to obtain a Pd @ NaA 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 is numbered Pd @ NaA/MCM-22.
[ example 4 ]
Sodium aluminate (Al)2O345 wt.%) 37.8 g and 86.7 g of sodium hydroxide, 465 g of water are added and stirred to dissolve the mixture, 50 g of 40% silica sol is added, 0.516 g of ruthenium hexaammine trichloride is added, and the material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝2.0
NaOH/SiO2＝6.5
H2O/SiO2＝82.5
Ru/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 12 hours at 90 ℃ under stirring. After being taken out, the Ru @ analcite sample is obtained after filtration, washing, drying and roasting for 5 hours at 500 ℃.
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 @ SOD/MCM-22.
[ example 5 ]
Sodium aluminate (Al)2O345 wt.%) 37.8 g and 29.8 g of sodium hydroxide were mixed, 367.9 g of water was added and the mixture was stirred to dissolve, 50 g of 40% silica sol was added, 0.498 g of tetraamminepalladium nitrate was added, and the material ratios (molar ratios) of the reactants were:
SiO2/Al2O3＝2.0
NaOH/SiO2＝6.5
H2O/SiO2＝82.5
Pd/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. After being taken out, the Pd @ analcime sample is obtained after filtration, washing, drying and roasting for 5 hours at 500 ℃.
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 the catalyst number Pd @ SOD/MCM-22.
[ example 6 ]
sodium aluminate (Al)2O345% by weight) of 18.9 g and 30 g of sodium hydroxide were mixed, 255.0 g of water was added thereto and the mixture was stirred to dissolve the mixture, 50 g of 40% silica sol was added thereto, and the mixture was added0.516 g of hexaammine ruthenium trichloride, and the material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝4
NaOH/SiO2＝2.25
H2O/SiO2＝47.5
Ru/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 24 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain a Ru @ synthetic ferrierite 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 @ GIS/MCM-22.
[ example 7 ]
Sodium aluminate (Al)2O345 wt.%) 39.2 g and 29.8 g of sodium hydroxide were mixed, 367.9 g of water was added and the mixture was stirred to dissolve, 50 g of 40% silica sol was added, 0.558 g of tetraammineplatinum chloride was added, and the mixture ratio (mole ratio) of the reactants was:
SiO2/Al2O3＝1.9
NaOH/SiO2＝2.2
H2O/SiO2＝66.3
Pt/SiO2＝0.005
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. After being taken out, the Pt @ NaA sample is obtained after filtration, washing, drying and roasting for 5 hours at 500 ℃.
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 Pt @ NaA/MCM-22.
[ COMPARATIVE EXAMPLE 1 ]
Sodium aluminate (Al)2O345 wt.%) 39.2 g, 29.8 g of sodium hydroxide, and 367.9 g of sodium hydroxide were addedDissolving the mixture by water and stirring, and then adding 50 g of 40% silica sol, wherein the material ratio (mol ratio) of reactants is as follows:
SiO2/Al2O3＝1.9
NaOH/SiO2＝2.2
H2O/SiO2＝66.3
after the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 16 hours at the temperature of 100 ℃ under stirring. And taking out, filtering, washing, drying and roasting at 500 ℃ for 5 hours to obtain a NaA molecular sieve sample.
0.258 g of ruthenium hexammine trichloride is taken to prepare a solution, the solution is immersed in the 10 g of NaA molecular sieve sample in the same volume, and the solution is dried and roasted to obtain a Ru-NaA sample. And mixing 12 g of MCM-22 molecular sieve with MWW topological structure, tabletting and granulating, and evaluating the granules of 40-60 meshes. The catalyst was numbered Ru-NaA/MCM-22.
[ COMPARATIVE EXAMPLE 2 ]
Taking Al2O310 g of ruthenium hexaammine trichloride, 0.258 g, Ru-Al obtained by the method of isovolumetric impregnation2O3A 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 EXAMPLE 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.
[ example 8 ]
The catalysts synthesized in [ examples 1-7 ] were 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 pure benzene and hydrogen are introduced to carry out hydrogenation alkylation reactionAfter the reaction, the liquid phase composition was analyzed by on-line chromatography after gas-liquid separation. 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 catalysts synthesized in [ examples 1-7 ] were 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 condition is that the weight space velocity of the benzene is 1.0h-1. The molar ratio of hydrogen to benzene is 0.5, the reaction temperature is 150 ℃, and the reaction pressure is 1.0 MPa. 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 EXAMPLE 4 ]
In the same manner as in example 8, the catalysts synthesized in comparative examples 1 to 3 were packed in a fixed bed tubular reactor and continuously reacted for 50 hours, and the reaction results are shown in tables 1 and 2.