CN111054426A - Catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation and application thereof - Google Patents

Catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation and application thereof Download PDF

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CN111054426A
CN111054426A CN201811201402.2A CN201811201402A CN111054426A CN 111054426 A CN111054426 A CN 111054426A CN 201811201402 A CN201811201402 A CN 201811201402A CN 111054426 A CN111054426 A CN 111054426A
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catalyst
molecular sieve
toluene
alkali metal
methanol
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蒋见
缪长喜
卢媛娇
孙清
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/082—X-type faujasite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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Abstract

The invention mainly relates to a catalyst for synthesizing ethylbenzene and styrene by side chain alkylation of toluene and methanol, and mainly solves the problems of low methanol utilization rate and low ethylbenzene and styrene selectivity when the catalyst used in the prior art is used for side chain alkylation of toluene and methanol. The invention adopts the catalyst comprising: FAU molecular sieve materials, alkali metal oxides and alkaline earth metal oxides; the composition of which can be expressed as MnSi192‑nAlnO384Exces nxM' O, wherein M is an alkali metal; m' is additionally loaded alkali goldThe metal x and the alkaline earth metal x represent the content of extra loaded alkali metal and alkaline earth metal, the range is 0.2-6%, the technical scheme of the catalytic material containing a composite pore structure with macropores, mesopores and micropores better solves the problem, and the catalytic material can be used for industrial production of ethylbenzene and styrene synthesized by the side alkylation reaction of methylbenzene and methanol.

Description

Catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation and application thereof
Technical Field
The invention relates to a molecular sieve catalyst for preparing ethylbenzene and styrene and application thereof, in particular to a molecular sieve catalyst for preparing ethylbenzene styrene by toluene and methanol side chain alkylation and application thereof.
Background
Styrene monomer is an important organic chemical raw material, and is mainly used for producing products such as polystyrene, (ABS) resin, styrene-butadiene rubber, unsaturated resin and the like. In addition, the method can also be used for pharmacy, dyes or preparation of pesticide emulsifiers, mineral dressing agents and the like, and has wide application. The yield of the styrene series resin is second to PE and PVC in the synthetic resin and is named as the third. At present, most industrial styrene is obtained by carrying out Friedel-Craft reaction on benzene and ethylene to generate ethylbenzene and then carrying out catalytic dehydrogenation. The method has the advantages of longer process, more side reactions, high energy consumption, raw material cost accounting for 85% of the variable production cost, and higher production cost. The alkylation of toluene and methanol is a potential application prospect route for producing styrene, and Sidorenko and the like successfully synthesize ethylbenzene and styrene by using toluene and methanol as catalysts by using X-type and Y-type zeolites exchanged by alkali metal ions for the first time in 1967. Compared with the traditional process, the method has the advantages of wide raw material source, low cost, low energy consumption, less pollution and the like. Therefore, the response has been reported to be regarded as important, and research on the response is increasing.
The catalyst for preparing styrene by toluene and methanol side chain alkylation belongs to a solid base catalyst, but the catalytic process is a one-acid-base concerted catalytic reaction and takes base active site catalysis as the leading factor. The acidic site of the catalyst can play a role in stabilizing toluene benzene ring, and the basic site can activate methyl groups of toluene and methanol. Firstly, methanol is decomposed into formaldehyde on an alkali center, toluene is adsorbed on an acid center, a side chain methyl group of the toluene is activated by the alkali center, then the formaldehyde and the activated methyl group react to produce styrene, and part of the styrene reacts with generated hydrogen to produce ethylbenzene. If the catalyst is too strong in alkalinity, the formaldehyde can be further decomposed, and more hydrogen and ethylbenzene are generated; if the catalyst is too strong in acidity, alkylation of benzene rings and toluene disproportionation can occur to generate benzene and xylene, so that the catalyst is required to have proper acid-base matching, and meanwhile, the existence of the benzene rings requires that the catalyst has a certain spatial pore structure.
The toluene methanol side alkylation reaction has been extensively studied over a variety of catalysts, many molecular sieves such as X, Y, L, β, ZSM-5, and some basic oxides such as MgO, MgO-TiO2And CaO-TiO2Are reported to be applied to the reaction for catalyzing the alkylation OF the side chain OF toluene and methanol, such as JOURNAL OF CATALYSIS173, 490-500 (1998) and CN101623649A 'basic molecular sieve catalyst for preparing styrene', CN101623650A 'preparation method OF catalyst for preparing styrene by the alkylation OF the side chain OF toluene and methanol'. As a result of the studies, it was found that in order to achieve a better catalytic effect of side chain alkylation, the catalyst must satisfy the following four requirements: the catalyst must have sufficient basic sites to activate the conversion of methanol to the methylating agent formaldehyde; a weak Lewis acid center is required to stabilize toluene and polarize its methyl group; toluene and methanol have a good stoichiometric adsorption balance on the catalyst; the catalyst must have a microporous pore structure. Therefore, how to further improve the activity becomes a key point for preparing the ethylbenzene styrene by the toluene methanol.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low methanol utilization rate when the catalyst used in the prior art is used in the toluene and methanol side chain alkylation reaction, and provides a novel catalyst for synthesizing ethylbenzene and styrene by the toluene and methanol side chain alkylation. The catalyst has the characteristics of high methanol utilization rate and good activity. The second technical problem to be solved by the present invention is a method for preparing a catalyst corresponding to the first technical problem. The third technical problem solved by the invention is the application of the catalyst corresponding to the first technical problem in the alkylation of the side chain of the toluene and the methanol.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a catalyst for the side-chain alkylation of toluene with methanol to prepare ethylbenzene and styrene, which comprises: FAU molecular sieve materials, alkali metal oxides and alkaline earth metal oxides; the composition of which can be expressed as MnSi192-nAlnO384·excess nxM ' O (where M ' O represents an oxide of metal M ' and does not represent the true composition of the oxide), wherein M is an alkali metal; m 'is additionally loaded alkali metal and alkaline earth metal, n is a positive integer less than 192, exos nxM' O is additionally loaded alkali metal or alkaline earth metal oxide, x represents the content of the additionally loaded alkali metal and alkaline earth metal, the range is 0.1-7%, and the catalytic material contains a composite pore structure of macropores, mesopores and micropores.
In the technical scheme, the FAU molecular sieve material is selected from an X molecular sieve or a Y molecular sieve; the molar content x of the additionally loaded alkali metal and alkaline earth metal is in the range of 0.2-6%.
In the above technical solution, the range of the molar content x of the additional supported alkali metal and alkaline earth metal is more preferably 0.5 to 5%.
In the above technical solution, the molecular sieve material is more preferably an X molecular sieve.
The molar ratio of the additional alkali metal to the alkaline earth metal is (0.015-70): 1.
in the above technical solution, the additional alkali metal is selected from at least one of K, Rb, Cs elements; the additional alkaline earth metal is selected from Mg, Ca, Sr, Ba.
Among the above solutions, the most preferred solution is that the additional alkali metal is selected from Rb and Cs; the additional alkaline earth metal is selected from Ba; wherein the additional alkali metal and alkaline earth metal elements are mixed and used synergistically, has unexpected effect in the toluene methanol side alkylation reaction.
In the above technical scheme, the molecular sieve material is selected from X molecular sieve and SiO2/Al2O32 to 2.5.
In the technical scheme, the diameter of the macropore contained in the catalytic material is 500-5000 nm, the diameter of the mesopore contained in the catalytic material is 5-50 nm, and the diameter of the micropore contained in the catalytic material is 0.6-0.8 nm.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation is characterized by comprising the following steps: a) before use, the X molecular sieve or the Y molecular sieve catalyst is subjected to ion exchange by using at least one of a potassium ion solution, a rubidium ion solution or a cesium ion solution with the concentration of 0.5-2.5 mol/L, the exchange temperature is 50-90 ℃, the exchange time is 1-3 hours each time, the solid-liquid weight ratio is 1: 5-10, and then extra alkali metal and alkaline earth elements are loaded on the molecular sieve by adopting an impregnation method and dried at the temperature of 80-150 ℃ to obtain the modified molecular sieve.
b) Kneading the modified molecular sieve, silica sol, sesbania powder, carboxymethyl cellulose and a graphite pore-forming agent, extruding into strips, molding, and roasting at 450-550 ℃ to obtain the catalyst, wherein the catalytic material contains a macroporous, mesoporous and microporous composite pore structure.
In the above technical solution, the alkali metal ion solution is selected from hydroxides, inorganic acid salts (such as halide salts and nitrate salts), organic acid salts (such as acetate salts), and the like.
In the technical scheme, the method is characterized in that the X molecular sieve or Y molecular sieve catalyst is subjected to ion exchange by sequentially using a potassium ion solution, a rubidium ion solution and a cesium ion solution with the concentration of 0.5-2.5 mol/L.
In the technical scheme, after ion exchange, the ion exchange degree of sodium ions in the alkali metal ion exchange molecular sieve of at least one of potassium ions, rubidium ions or cesium ions in the catalyst is 10-90%.
In the technical scheme, when the extra alkali metal and alkaline earth metal elements adopt an impregnation method, the salt or hydroxide solution of the alkali metal and the alkaline earth metal is used as a precursor to be impregnated on the catalyst, the impregnation temperature is 40-80 ℃, and the impregnation time is 3-8 hours.
In the technical scheme, before the catalyst is used, the catalyst is kneaded, extruded and formed with a silica sol adhesive and one or more pore-forming agents of sesbania powder, carboxymethyl cellulose and graphite, and then the catalyst material is obtained by roasting, wherein the catalyst material contains composite pore structures such as macropores, mesopores, micropores and the like.
In the technical scheme, the mass ratio of the modified molecular sieve to the silica sol (silicon dioxide) is (6-10): 1.
In the technical scheme, the mass ratio of the total mass of the modified molecular sieve and the silica sol to the mass of the sesbania powder, the carboxymethyl cellulose, the graphite and other pore-forming agents is1 (0.009-0.1).
In the technical scheme, the mass ratio of the pore-forming agent sesbania powder to the carboxymethyl cellulose to the graphite is 3 (2.5-1.5) to 0.5-1.5.
In the technical scheme, the temperature of the roasting catalyst is 450-550 ℃.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a toluene and methanol side chain alkylation method takes toluene and methanol as raw materials, the molar ratio of the toluene to the methanol in the raw materials is 0.1-10, the reaction temperature is 200-600 ℃, the reaction pressure is 0-0.5 MPa, and the weight space velocity of the raw materials is 0.1-10 hours-1Under the condition (1), the raw material contacts with the catalyst of any one of claims 1 to 15 to react to generate ethylbenzene and styrene.
In the technical scheme, the molar ratio of the toluene to the methanol is preferably 2-7.
In the technical scheme, the reaction temperature is preferably 350-500 ℃.
In the technical scheme, the reaction pressure is preferably 0-0.2 MPa.
In the above technical scheme, preferably, the weight space velocity of the raw material is 0.5-8 hours-1。
The process of the invention can be carried out in a fixed-bed continuous flow reactor, the process of which is briefly described below: the required amount of catalyst was taken and placed in the constant temperature zone of the reactor, and the lower part of the catalyst was filled with quartz sand. Under the set temperature and pressure, toluene and methanol are mixed, the mixture is pumped to a preheater by a micro pump to be mixed and gasified with nitrogen, the mixture enters the upper end of a reactor and flows through a catalyst bed layer to carry out catalytic reaction, and reaction products are directly injected by a valve to enter a gas chromatography for analysis.
The activity and selectivity of the catalyst were calculated according to the following formulas:
Figure RE-GDA0001945476800000041
Figure RE-GDA0001945476800000042
the method of the invention selects the X molecular sieve or the Y molecular sieve which is used for alkali metal ion exchange to load extra alkali metal and alkaline earth metal element auxiliary agents, and simultaneously, the pore-forming agent is added during the catalyst forming, thereby effectively improving the catalytic activity of the toluene methanol. By adopting the method of the invention, the molar ratio of the toluene to the methanol is 5: 1, the reaction temperature is 425 ℃, the reaction pressure is normal pressure, and the weight space velocity of the raw material is 3.2 hours-1Under the condition, the utilization rate of the methanol can reach 40.2 percent, the total selectivity of the ethylbenzene and the styrene can reach 97.5 percent, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Drawings
FIG. 1 shows the nitrogen adsorption/desorption isotherm and the pore size distribution (mesoporous measurement) of the catalyst of example 31.
FIG. 2 shows the adsorption-desorption isotherms and pore size distributions (macropores measured) of the mercury intrusion experiments for the catalyst described in example 31.
Detailed Description
[ example 1 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 2 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.5 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 3 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 3 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 4 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 6 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Then preparing cesium nitrate into a solution, and impregnating additional cesium withTo the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 5 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 0.1%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 6 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 0.2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2Flow rate of 1The activity was evaluated at 0 ml/min. The results are shown in Table 1.
[ example 7 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 0.5%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 8 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 4%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 9 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution is sequentially subjected to ion exchangeAnd then dried at 100 ℃ for 10 hours after filtration and washing. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 5%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 10 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 6%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 11 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate into a solution, and soaking additional cesium on the modified molecular sieve material. The additional supported molar amount x of the cesium catalyst after supporting was 7%.
Subjecting the obtainedTabletting and forming the catalyst into 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out reaction for 3.2 hours at the normal pressure and the toluene-methanol molar ratio of 5-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 12 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Potassium nitrate was then formulated into a solution and additional potassium was impregnated onto the modified molecular sieve material. The additional molar loading x of the potassium catalyst after loading was 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 13 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Then preparing rubidium nitrate into a solution, and dipping additional rubidium into the modified molecular sieve material. The additional loading molar quantity x of the loaded catalyst rubidium is 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 14 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Magnesium nitrate is then made into a solution and additional magnesium is impregnated onto the modified molecular sieve material. The additional supported molar amount x of the catalyst magnesium after supporting is 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 15 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Calcium nitrate is then formulated into a solution and additional calcium is impregnated onto the modified molecular sieve material. The additional loading molar quantity x of the catalyst calcium after loading is 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 16 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Then adding sodium sulfatePreparing strontium acid into solution, and soaking additional strontium on the modified molecular sieve material. The additional loading molar quantity x of the supported catalyst strontium is 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 17 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Then preparing barium nitrate into a solution, and soaking additional barium on the modified molecular sieve material. The additional loading molar quantity x of the catalyst barium after loading is 2%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 18 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Magnesium nitrate and potassium nitrate were then made into a solution and additional potassium and magnesium were impregnated onto the modified molecular sieve material. The additional loading molar weight x of the potassium and magnesium of the loaded catalyst is 2 percent, and the molar ratio of the metal potassium to the metal magnesium is 1: 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out reaction under normal pressure,Toluene methanol molar ratio of 5, at 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 19 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And then preparing a solution from rubidium nitrate and calcium nitrate, and soaking additional rubidium and calcium on the modified molecular sieve material. The additional loading molar weight x of the calcium of the loaded catalyst is 2%, and the molar ratio of the metal rubidium to the metal calcium is 1: 1.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 20 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate and barium nitrate into a solution, and soaking additional cesium and barium on the modified molecular sieve material. The additional loading molar quantity x of the cesium and barium of the loaded catalyst is 2%, and the molar ratio of the metal cesium to the metal barium is 1: 1.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 21 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate and barium nitrate into a solution, and soaking additional cesium and barium on the modified molecular sieve material. The additional loading molar quantity x of the cesium and barium of the loaded catalyst is 2%, and the molar ratio of the metal cesium to the metal barium is 3: 0.1.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 22 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate and barium nitrate into a solution, and soaking additional cesium and barium on the modified molecular sieve material. The additional loading molar quantity x of the cesium and barium of the loaded catalyst is 2%, and the molar ratio of the metal cesium to the metal barium is 2: 1.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 23 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate and barium nitrate into a solution, and soaking additional cesium and barium on the modified molecular sieve material. The additional loading molar quantity x of the cesium and barium of the loaded catalyst is 2%, and the molar ratio of the metal cesium to the metal barium is 1: 2.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 24 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. And preparing cesium nitrate and barium nitrate into a solution, and soaking additional cesium and barium on the modified molecular sieve material. The additional loading molar quantity x of the cesium and barium of the loaded catalyst is 2%, and the molar ratio of the metal cesium to the metal barium is 0.1: 3.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 25 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%. Then adding cesium nitrate and nitric acidIf prepared in solution with barium nitrate, additional cesium, rubidium and barium are impregnated onto the modified molecular sieve material. The additional loading molar weight x of the loaded catalysts cesium, rubidium and barium is 2%, and the molar ratio of metal cesium, rubidium and metal barium is 1:1: 1.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 1.
[ example 26 ]
80 g of the catalyst which is not tabletted and formed in the example 25, 25 g of 40% silica sol and 2.5 g of carboxymethyl cellulose are mixed, then proper amount of water is added for kneading, extruding and forming, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 27 ]
80 g of the catalyst which is not tabletted in the embodiment 25, 25 g of 40% silica sol and 1.7 g of sesbania powder are mixed, and then proper amount of water is added for kneading, extruding and molding, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 28 ]
80 g of the catalyst which is not tabletted and formed in the example 25, 25 g of 40% silica sol and 0.9 g of graphite are mixed, then proper amount of water is added for kneading, extruding and forming, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of 425 ℃,N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 29 ]
80 g of the catalyst which is not tabletted in example 25, 25 g of 40% silica sol, 2.5 g of carboxymethyl cellulose and 1.7 g of sesbania powder are mixed, and then a proper amount of water is added for kneading, extruding and molding, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 30 ]
80 g of the catalyst which is not tabletted and formed in the example 25, 25 g of 40% silica sol, 1.7 g of sesbania powder and 0.9 g of graphite are mixed, then proper amount of water is added for kneading, extruding and forming, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 31 ]
80 g of the catalyst which is not tabletted and formed in example 25, 25 g of 40% silica sol, 2.5 g of carboxymethyl cellulose and 0.9 g of graphite are mixed, then a proper amount of water is added for kneading, extruding and forming, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 32 ]
80 g of the catalyst which is not tabletted in the example 25, 25 g of 40% silica sol, 3.6 g of carboxymethyl cellulose, 2.7 g of sesbania powder and 1.7 g of graphite are mixed, and then a proper amount of water is added to be kneaded, extruded into strips, molded, dried and roasted at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 33 ]
80 g of the catalyst which is not tabletted in the example 25, 28 g of 40% silica sol, 2.6 g of carboxymethyl cellulose, 1.9 g of sesbania powder and 1.0 g of graphite are mixed, and then a proper amount of water is added to knead, extrude, form, dry and bake at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 34 ]
80 g of the catalyst which is not tabletted in the example 25, 25 g of 40% silica sol, 2.5 g of carboxymethyl cellulose, 1.7 g of sesbania powder and 0.9 g of graphite are mixed, and then a proper amount of water is added to be kneaded, extruded into strips, molded, dried and roasted at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 35 ]
80 g of the catalyst which is not tabletted in the example 25, 21 g of 40% silica sol, 2.3 g of carboxymethyl cellulose, 1.2 g of sesbania powder and 0.9 g of graphite are mixed, and then a proper amount of water is added to be kneaded, extruded into strips, molded, dried and roasted at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ example 36 ]
80 g of the catalyst which is not tabletted in the example 25, 31.5 g of 40% silica sol, 1.5 g of carboxymethyl cellulose, 1.1 g of sesbania powder and 0.3 g of graphite are mixed, and then a proper amount of water is added for kneading, extruding, molding, drying and roasting at 470 ℃ to obtain the catalyst.
The catalyst obtained above was charged into a reactor at normal pressure with a toluene-methanol molar ratio of 5 for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min. The results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.2 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and washed, and then dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min.
As a result: the utilization rate of methanol is 30.5 percent, and the total selectivity of ethylbenzene and styrene is 96.8 percent.
[ COMPARATIVE EXAMPLE 2 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaY molecular sieve 6 with KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. After the exchange, the alkali metal ion in the catalyst exchanged the sodium ion in the molecular sieve with an ion exchange degree of 85%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, loading the granular catalyst into a reactor, and carrying out a toluene-methanol molar ratio of 5 under normal pressure for 3.2 hours-1Liquid space velocity of (2), 425 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min.
As a result: the utilization rate of methanol is 12.2 percent, and the total selectivity of ethylbenzene and styrene is 97.2 percent.
TABLE 1
Figure RE-GDA0001945476800000151
TABLE 2
Figure RE-GDA0001945476800000161

Claims (11)

1. A catalyst for the side-chain alkylation of toluene with methanol to prepare ethylbenzene and styrene, which comprises: FAU molecular sieve materials, alkali metal oxides and alkaline earth metal oxides; the composition of which can be expressed as MnSi192-nAlnO384excessnxM ' O (where M ' O represents an oxide of the metal M ' and does not represent the true composition of the oxide), where M is an alkali metal; m 'is additionally loaded alkali metal and alkaline earth metal, n is a positive integer less than 192, exos nxM' O is additionally loaded alkali metal or alkaline earth metal oxide, x represents the content of the additionally loaded alkali metal and alkaline earth metal, the range is 0.1-7%, and the catalytic material contains a composite pore structure of macropores, mesopores and micropores.
2. The catalyst for the side chain alkylation of toluene with methanol to ethylbenzene and styrene as claimed in claim 1, wherein the FAU molecular sieve material is selected from X molecular sieve or Y molecular sieve; the molar content x of the additionally loaded alkali metal and alkaline earth metal is in the range of 0.2-6%.
3. The catalyst for preparing ethylbenzene and styrene by the side chain alkylation of toluene and methanol according to claim 1, wherein the molar content x of the additionally loaded alkali metal and alkaline earth metal is 0.5-5%, and the molar ratio of the alkali metal to the alkaline earth metal is (0.015-70): 1.
4. the catalyst for the side-chain alkylation of toluene with methanol to ethylbenzene and styrene according to claim 1, wherein the additional alkali metal is selected from at least one of the elements K, Rb and Cs; the additional alkaline earth metal is selected from at least one of Mg, Ca, Sr and Ba.
5. The catalyst for the side chain alkylation of toluene with methanol to ethylbenzene and styrene as claimed in claim 1, wherein the molecular sieve material is selected from X molecular sieve, SiO2/Al2O32 to 2.5.
6. The catalyst for preparing ethylbenzene and styrene by alkylation of toluene side chains as claimed in claim 1, wherein the catalyst material comprises macropores with a pore diameter ranging from 500 to 5000nm, mesopores with a pore diameter ranging from 5 to 50nm, and micropores with a pore diameter ranging from 0.6 to 0.8 nm.
7. A preparation method of the catalyst for preparing ethylbenzene and styrene by side chain alkylation of toluene and methanol according to any one of claims 1 to 5 is characterized by comprising the following steps:
a) before use, the X molecular sieve or the Y molecular sieve catalyst is subjected to ion exchange by using at least one of a potassium ion solution, a rubidium ion solution or a cesium ion solution with the concentration of 0.5-2.5 mol/L, the exchange temperature is 50-90 ℃, the exchange time is 1-3 hours each time, the solid-liquid weight ratio is 1: 5-10, and then extra alkali metal and alkaline earth elements are loaded on the molecular sieve by adopting an impregnation method to obtain a modified molecular sieve;
b) kneading the modified molecular sieve, a silica sol adhesive and one or more pore-forming agents of sesbania powder, carboxymethyl cellulose and graphite, extruding into strips, molding, and roasting to obtain the catalyst, wherein the catalyst contains a macroporous, mesoporous and microporous composite pore structure.
8. The method for preparing the catalyst for preparing ethylbenzene and styrene by the side chain alkylation of toluene and methanol according to claim 6, wherein the X molecular sieve or Y molecular sieve catalyst is subjected to ion exchange by sequentially using a potassium ion solution, a rubidium ion solution and a cesium ion solution with the concentration of 0.5-2.5 mol/L.
9. The method for preparing the catalyst for preparing ethylbenzene and styrene by the side chain alkylation of toluene and methanol according to claim 6 or 7, wherein after the ion exchange, the ion exchange degree of sodium ions in the alkali metal ion exchange molecular sieve of at least one of potassium ions, rubidium ions or cesium ions in the catalyst is 10-90%.
10. The method of claim 6, wherein the catalyst is impregnated with a salt or hydroxide solution of an alkali metal and an alkaline earth metal as a precursor at a temperature of 40-80 ℃ for 3-8 hours when the additional alkali metal and alkaline earth metal are used in an impregnation method.
11. A preparation method of the catalyst for preparing ethylbenzene and styrene by alkylating the side chains of toluene and methanol according to any one of claims 6 to 9 is characterized in that the mass ratio of the modified molecular sieve to silica sol (silicon dioxide) is (6-10): 1; the ratio of the total mass of the modified molecular sieve and the silica sol to the total mass of the carboxymethyl cellulose, the sesbania powder and the graphite pore-forming agent is1 (0.009-0.1); the mass ratio of the pore-forming agent carboxymethyl cellulose to the sesbania powder to the graphite is 3 (2.5-1.5) to 0.5-1.5.
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