CN109701592B - Side chain alkylation catalyst and method of use - Google Patents
Side chain alkylation catalyst and method of use Download PDFInfo
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Abstract
The invention mainly relates to a catalyst for preparing ethylbenzene and styrene by alkylating a toluene and C1 source side chain, and mainly solves the problems of low utilization rate of a C1 source and low selectivity of styrene when the catalyst used in the prior art is used for toluene side chain alkylation reaction. Under the condition of toluene side chain alkylation, raw materials are contacted with a catalyst to generate ethylbenzene and styrene; the catalyst is SiO with the molar ratio of silicon to aluminum2/Al2O3The catalyst is an X or Y molecular sieve of 2-4, the X or Y molecular sieve is subjected to ion exchange by at least one of potassium ions, rubidium ions or cesium ions before use, and then at least one metal element of silver and palladium is loaded on the molecular sieve catalyst by adopting an impregnation method.
Description
Technical Field
The invention relates to a molecular sieve catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation, in particular to a molecular sieve catalyst for preparing ethylbenzene and styrene by toluene methanol side chain alkylation.
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 C1 source is a potential application route for producing styrene, and Sidorenko, etc. successfully synthesizes ethylbenzene and styrene by using toluene and methanol as catalysts and 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 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 main 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 C1 sources such as toluene, methanol and the like. First, the C1 source is decomposed into formaldehyde in the alkali center, toluene is adsorbed on the acid center, the side chain methyl group 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 the generated hydrogen to produce ethylbenzene. If the catalyst is too basic, the formaldehyde will decompose further, producing more hydrogen and ethylbenzene.
The toluene side alkylation reaction has been extensively studied over a variety of catalysts. Many molecular sieves such as X, Y, L, beta, ZSM-5, and some basic oxides such as MgO, MgO-TiO2And CaO-TiO2Are reported to be studied in the reactions catalyzing the alkylation OF the side chains OF toluene with methanol, such as JOURNAL OF CATALYSIS 173, 490-500 (1998) and CN101623649A, CN 101623650A. 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 center activationConversion of the C1 source to the methylating agent formaldehyde; a weak Lewis acid center is required to stabilize toluene and polarize its methyl group; toluene and C1 sources should have a good stoichiometric adsorption balance on the catalyst; the catalyst must have a microporous pore structure. Thus, the results of studies on the catalytic activity of some zeolites indicate that alkali metal cation exchanged X-type zeolites and Y-type zeolites are relatively effective catalysts. While other zeolites such as L, beta, ZSM-5 type do not have ideal reactivity, and some alkaline oxides without microporous structure such as MgO, MgO-TiO2And CaO-TiO2Etc. have only low activity. However, the prior art has the defects that the toluene side chain alkylation catalyst has lower activity and lower selectivity of styrene in reaction products. Therefore, how to improve the activity and selectivity of such catalysts becomes a key point for preparing styrene from toluene.
Disclosure of Invention
The invention aims to solve the problems of low activity of a toluene side chain alkylation catalyst and low styrene selectivity in the prior art, and provides a novel catalyst for synthesizing ethylbenzene and styrene by alkylation of C1 source side chain alkyl such as toluene and methanol. The catalyst has the characteristics of high methanol utilization rate and high styrene selectivity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a side chain alkylation catalyst comprises the following components in parts by weight:
a) 50-89.9 parts of an X molecular sieve and/or a Y molecular sieve;
b) 2-5 parts of alkali metal sodium;
c) 8-40 parts of at least one selected from potassium, rubidium and cesium;
d) 0.1-5 parts of at least one element selected from palladium, silver and ruthenium or oxide thereof.
In the above technical solution, preferably, the component a) is SiO with molar ratio of silicon to aluminum (si — al)2/Al2O3Is an X molecular sieve of 2-3.
In the above technical solution, preferably, the component c) in the catalyst is added by means of ion exchange.
In the above technical solution, it is more preferable that the component c) in the catalyst includes at least two of potassium, rubidium, and cesium.
In the above technical solution, more preferably, the X molecular sieve sequentially and respectively exchanges with the potassium ion source, the rubidium ion source, and the cesium ion source at least once.
In the above technical solution, preferably, the content of the component c) is 20 to 40 parts by weight.
In the above technical solution, preferably, the content of the component d) is 0.5 to 2 parts by weight.
In the above technical solution, preferably, the component d) is selected from one element of palladium and silver or an oxide thereof.
In the above technical solution, preferably, the catalyst further comprises 0.1 to 4 parts by weight of a component e), and the component e) is at least one selected from cobalt and nickel.
In the above technical solution, preferably, the palladium, silver, ruthenium, cobalt and nickel elements in the catalyst are added by direct impregnation. The impregnation sequence may be a stepwise impregnation or a one-step impregnation.
In the above technical solution, it is more preferable that the catalyst contains palladium and cobalt.
In the above technical solution, more preferably, the catalyst contains silver and nickel.
In the above technical solution, the catalyst preferably contains palladium and cobalt at a weight ratio of (1:9) to (9: 1).
In the above technical solution, the catalyst preferably contains silver and nickel at a weight ratio of (1:9) to (9: 1).
In the above-mentioned aspect, preferably, the catalyst further contains Mo or an oxide thereof.
In the above technical solution, more preferably, the content of Mo or its oxide is 0.5 to 1 part by weight.
In the technical scheme, the catalyst is suitable for a method for preparing the catalyst for preparing the styrene and the ethylbenzene by the side-chain alkylation reaction of the toluene: toluene and a C1 source are used as raw materials, the molar ratio of the toluene to the C1 source is (0.1-10): 1,the reaction temperature is 300-500 ℃, the reaction pressure is 0-0.2 MPa, and the mass space velocity of the raw material is 0.1-5.0 h-1Under the condition of generating ethylbenzene and styrene after the contact reaction of the raw materials and the catalyst of any one of claims 1 to 10.
In the method of the present invention, examples of the ion source include hydroxides, inorganic acid salts (for example, halide salts, nitrate salts, etc.) and organic acid salts (for example, acetate salts, etc.) of these alkali metals, and are not particularly limited. The manner in which the molecular sieve is contacted with the alkali metal ion source for ion exchange is not particularly limited and may be performed in a manner conventional in the art. For example, the temperature is 50-90 ℃, the contact time is 1-3 hours each time, and the liquid-solid weight ratio is 5-10.
In the method of the present invention, the manner of supporting the palladium, silver, ruthenium, cobalt and nickel elements on the X or Y molecular sieve is an impregnation method well known in the art, and a salt solution of palladium, silver, ruthenium, cobalt and nickel (such as halide salt and silver nitrate) is used to support them on the X or Y molecular sieve. The dipping temperature is 40-80 ℃, and the dipping time is 3-8 hours.
In the process of the present invention, methanol, formaldehyde, paraformaldehyde or methylal can be used as the C1 raw material for the toluene side-alkylation. In the examples of the present invention methanol was used as the source of C1 for the side-alkylation with toluene.
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 into the constant temperature zone of the reactor and the lower part of the catalyst was filled with quartz wool. 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:
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution and RbNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then adding sodium sulfateAnd preparing palladium acid into a solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, solution,RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into a solution, dipping the solution on the modified molecular sieve material, drying the solution at 100 ℃ for 10 hours, preparing cobalt nitrate into a solution, and dipping the solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 7 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing a mixed solution from palladium nitrate and cobalt nitrate, and soaking the mixed solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid space velocity of (2), 425 ℃, N2Flow rate of 10 mlThe activity was evaluated at a time of one minute. The results are shown in Table 1.
[ example 8 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing silver nitrate into solution, and dipping the silver on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing silver nitrate and nickel nitrate into a mixed solution, and dipping the mixed solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing nickel nitrate into a solution, dipping the nickel nitrate into the modified molecular sieve material, drying the nickel nitrate for 10 hours at 100 ℃, preparing silver nitrate into a solution, and dipping the silver nitrate into the modified molecular sieve material. CatalysisThe components of the agent are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing ruthenium chloride into solution, and dipping ruthenium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing a mixed solution from palladium nitrate and silver nitrate, and soaking the mixed solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing a mixed solution from cobalt nitrate and nickel nitrate, soaking the mixed solution on the modified molecular sieve material, drying the mixed solution at 100 ℃ for 10 hours, preparing a mixed solution from palladium nitrate and silver nitrate, and soaking the mixed solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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/Al2O3NaY molecular sieve 3.2 with certain amount of KNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with certain amount of CsNO3The solution was ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with certain amount of CsNO3The solution was ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate and ammonium molybdate into a solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with certain amount of CsNO3The solution was ion exchanged, filtered and dried at 100 ℃ for 10 hours. And then preparing palladium nitrate into a solution, dipping the solution on the modified molecular sieve material, drying the solution at 100 ℃ for 10 hours, preparing ammonium molybdate into a solution, and dipping the solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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 2.19 with a certain amount of KNO3The solution was ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then palladium nitrate is prepared into solution and is dipped on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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/Al2O3NaY molecular sieve 3.2 with a certain amount of RbNO3The solution was ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing silver nitrate into solution, and dipping the silver on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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/Al2O32.19 NaX molecular sieve and SiO2/Al2O3NaY molecular sieve (3.2), mixing, and adding KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Palladium nitrate and ruthenium chloride are then compounded into a solution, which is then impregnated onto the modified molecular sieve material, with the catalyst components shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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/Al2O32.19 NaX molecular sieve and SiO2/Al2O3NaY molecular sieve (3.2), mixing, and adding KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then firstly preparing palladium nitrate and silver nitrate into solution, and soaking the solution on the surface of the substrateDrying the modified molecular sieve material for 10 hours at 100 ℃, preparing a solution from nickel nitrate and ammonium molybdate, and soaking the solution on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
[ COMPARATIVE EXAMPLE 1 ]
Silicon to aluminum ratio SiO2/Al2O32.19 NaX molecular sieve, dried at 100 ℃ for 10 hours. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
[ COMPARATIVE EXAMPLE 2 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
[ COMPARATIVE EXAMPLE 3 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution is sequentially subjected to ion exchange, filtered and dried for 10 hours at 100 DEG C. Then preparing palladium nitrate into solution, and dipping palladium on the modified molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
[ COMPARATIVE EXAMPLE 4 ]
Taking the ratio of silicon to aluminum SiO2/Al2O3NaX molecular sieve 2.19 with a certain amount of KNO3Solution, RbNO3Solution and CsNO3The solution was sequentially ion exchanged, filtered and dried at 100 ℃ for 10 hours. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
[ COMPARATIVE EXAMPLE 5 ]
Taking the ratio of silicon to aluminum SiO2/Al2O32.19 NaX molecular sieve, dried at 100 ℃ for 10 hours. And (3) preparing palladium nitrate and silver nitrate into a solution, and soaking the solution on the molecular sieve material. The catalyst components are shown in table 1.
Tabletting the obtained catalyst to form 40-60 mesh granular catalyst, loading into a reactor, and standing for 1.5 hr at normal pressure and toluene-methanol molar ratio of 6-1Liquid 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.
TABLE 1
Note: the methanol utilization and styrene selectivity in table 1 are the average values over 24h prior to the reaction.
Claims (10)
1. A side chain alkylation catalyst comprises the following components in parts by weight:
a) 50-89.9 parts of an X molecular sieve and/or a Y molecular sieve;
b) 2-5 parts of alkali metal sodium;
c) 8-40 parts of at least one element selected from potassium, rubidium and cesium or an oxide thereof;
d) 0.1-5 parts of at least one element selected from palladium, silver and ruthenium or an oxide thereof;
e)0.1 to 5 parts of Mo or an oxide thereof.
2. The side-chain alkylation catalyst according to claim 1, characterized in that component c) is added by means of ion exchange.
3. The side-chain alkylation catalyst according to claim 1, wherein the content of the component d) is 0.5 to 2 parts.
4. The side-chain alkylation catalyst according to claim 1, characterized in that component d) is selected from one element of palladium, silver or an oxide thereof.
5. The side chain alkylation catalyst according to claim 1, wherein the catalyst further comprises 0.1 to 4 parts by weight of component f), and the component f) is at least one selected from cobalt and nickel.
6. The side-chain alkylation catalyst according to claim 1 or 5, wherein the catalyst comprises palladium and cobalt.
7. The side-chain alkylation catalyst according to claim 1 or 5, wherein the catalyst contains silver and nickel.
8. The side-chain alkylation catalyst according to claim 1 or 5, wherein the catalyst contains palladium and cobalt in a weight ratio of (1:9) to (9: 1).
9. The side-chain alkylation catalyst according to claim 1 or 5, wherein the catalyst contains silver and nickel in a weight ratio of (1:9) to (9: 1).
10. A method for preparing a catalyst for styrene and ethylbenzene by a toluene side-chain alkylation reaction uses toluene and a C1 source as raw materials, the molar ratio of the toluene to the C1 source is (0.1-10): 1, the reaction temperature is 300-500 ℃, and the mass space velocity of the raw materials is 0.1-5.0 h-1Under the condition of generating ethylbenzene and styrene after the contact reaction of the raw materials and the catalyst of any one of claims 1 to 9.
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| JPS59206050A (en) * | 1983-04-22 | 1984-11-21 | エクソン・リサ−チ・アンド・エンヂニアリング・コムパニ− | Modified zeolite catalyst composition and alkylation of toluene by methanol for forming styrene |
| CN106622338A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Catalyst for side chain alkylation reaction of toluene and methanol and application thereof |
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| JPS59206050A (en) * | 1983-04-22 | 1984-11-21 | エクソン・リサ−チ・アンド・エンヂニアリング・コムパニ− | Modified zeolite catalyst composition and alkylation of toluene by methanol for forming styrene |
| CN106622338A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Catalyst for side chain alkylation reaction of toluene and methanol and application thereof |
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