CN109746036B - Side chain alkylation catalyst and use thereof - Google Patents
Side chain alkylation catalyst and use thereof Download PDFInfo
- Publication number
- CN109746036B CN109746036B CN201711057098.4A CN201711057098A CN109746036B CN 109746036 B CN109746036 B CN 109746036B CN 201711057098 A CN201711057098 A CN 201711057098A CN 109746036 B CN109746036 B CN 109746036B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular sieve
- chain alkylation
- side chain
- mesoporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Side chain alkylation catalysts and uses thereof. The invention mainly relates to a catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation, which 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 toluene and methanol side chain alkylation reaction. In the invention, a mesoporous guiding agent is introduced in the process of a hydrothermal synthesis method to synthesize a microporous-mesoporous composite pore X molecular sieve as a catalyst material; the technical scheme that the catalyst carries out ion exchange on at least two of potassium ions, rubidium ions or cesium ions for the composite pore X molecular sieve before use better solves the problem, and can be used in the industrial production of preparing ethylbenzene and styrene by the side chain alkylation reaction of methylbenzene and methanol.
Description
Technical Field
The invention relates to a composite molecular sieve catalyst for preparing ethylbenzene and styrene, in particular to a composite molecular sieve catalyst for preparing ethylbenzene styrene by toluene and 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 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, 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 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. Thus, the results of some studies of the catalytic activity of zeolites indicate that alkali metal cation exchanged type X zeolites are relatively effective catalysts. The reactivity of the type Y zeolite is inferior to that of the type X zeolite. 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. At present, most Fau-type molecular sieve catalysts for toluene methanol side chain alkylation reported in literature are conventional X-type and Y-type molecular sieve catalysts, and the molecular sieves only contain micropores and do not have mesoporous channels. This patent adopts compound hole X type molecular sieve catalyst material, has reduced the decomposition of methyl alcohol in the toluene methanol side chain alkylation reaction, effectively solves the problem that methyl alcohol utilization ratio is low in the toluene methanol side chain alkylation reaction.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low raw material utilization rate when the catalyst used in the prior art is used in the side chain alkylation reaction, and the invention provides a novel side chain alkylation catalyst which has the characteristics of high methanol utilization rate and high ethylbenzene and styrene selectivity. The invention also provides a novel preparation method of the side chain alkylation catalyst, and the method has the advantages of simple preparation process and the like when being used for preparing the side chain alkylation catalyst.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a catalyst for side chain alkylation, characterized in that the catalyst comprises a composite molecular sieve.
In the above technical scheme, preferably, the composite molecular sieve contains two pore channel structures of a micropore and a mesopore.
In the technical scheme, the volume ratio of micropores to mesopores of the composite molecular sieve is preferably 0.5-15, and more preferably 3-8.
In the technical scheme, preferably, the size range of mesoporous pores of the composite molecular sieve is 2-20 nm; more preferably 2 to 15 nm.
In the above technical scheme, preferably, the composite molecular sieve is modified by alkali metal ions.
In the above technical scheme, preferably, the composite molecular sieve is modified by aluminum; more preferably, the aluminum modification is performed by using sodium metaaluminate; preferably, the content of the sodium metaaluminate used for modification is 2-5% in percentage by weight of the catalyst.
In the above technical solution, preferably, the catalyst further contains 0.1-2 wt% of Bi2O3(ii) a More preferably, the content of Bi is 0.5 to 1.5%2O3。
In order to solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a side chain alkylation catalyst comprises the following preparation steps: sodium aluminate, sodium silicate, sodium hydroxide, potassium hydroxide, a mesoporous directing agent hexadecyltrimethylammonium chloride (or a mesoporous directing agent such as hexadecyltrimethylammonium bromide, poly-dimethyldiallylammonium chloride) and water are used as raw materials and mixed according to a certain proportion, the mixture is crystallized for a certain time at the temperature of 60-150 ℃, and then the crystallized mixture is roasted to synthesize the composite porous X or Y molecular sieve material containing micropores and mesopores.
In order to solve the second technical problem, the invention also adopts the following technical scheme: a side chain alkylation catalyst is prepared by the following steps: the method comprises the steps of mixing aluminum hydroxide, silica sol, sodium hydroxide, potassium hydroxide, a mesoporous guiding agent cetyl trimethyl ammonium chloride (or a mesoporous guiding agent such as cetyl trimethyl ammonium bromide and poly dimethyl diallyl ammonium chloride) and water serving as raw materials according to a certain proportion, crystallizing for a certain time at the temperature of 60-150 ℃, and then roasting to synthesize the composite pore X or Y molecular sieve material containing micropores and mesopores.
The size of the micropore of the synthesized composite molecular sieve is 0.6-0.8 nm, the size of the mesopore is 2-20 nm, the volume ratio of the micropore to the mesopore is 0.5-15, and the ratio of silicon to aluminum is SiO2/Al2O3The range is 1-7. In the above technical scheme, preferably, the composite molecular sieve material has a silica-alumina ratio of SiO2/Al2O3The range is 2-3, and the more preferable silicon-aluminum ratio of the composite molecular sieve material SiO2/Al2O3An X molecular sieve material in the range of 2-2.5;
in the above technical scheme, preferably, the mesoporous size of the composite molecular sieve material is between 5nm and 15 nm;
in the above technical scheme, preferably, the volume ratio of micropores to mesopores of the composite molecular sieve material is 3-8.
As can be seen from the figure, the adsorption and desorption isotherm of the molecular sieve of the composite pore has a hysteresis loop, which indicates that the molecular sieve contains mesopores, and the pore size distribution is obvious.
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:
the method of the invention selects the synthesized composite pore X-type molecular sieve as the catalyst material, which is beneficial to the diffusion of reaction molecules in the pore canal of the molecular sieve catalyst and reduces the decomposition of methanol, thereby effectively improving the utilization rate of methanol. Particularly when Al is adopted for modification, the catalytic activity of the alkylation catalyst is further improved; the catalytic effect is greatly improved. By adopting the method, the molar ratio of the toluene to the methanol is 5: 1, the reaction temperature is 415 ℃, the reaction pressure is 0MPa, and the weight space velocity of the raw material is 2.5 hours-1Under the condition, the utilization rate of the methanol can reach 54 percent, the total selectivity of the ethylbenzene and the styrene can reach 98 percent, and a better technical effect is achieved.
Drawings
FIG. 1 is an adsorption-desorption isotherm and pore size distribution diagram of a conventional X molecular sieve catalyst described in comparative example 1.
Fig. 2 is an adsorption-desorption isotherm and pore size distribution diagram of the composite pore X molecular sieve catalyst described in example 1.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, potassium hydroxide, a mesoporous guiding agent hexadecyltrimethylammonium chloride and water according to a certain proportion, crystallizing for 16 hours at 100 ℃, filtering, washing and roasting a synthesized product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.0, and the mesoporous size is about 7 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then 50 ml of 1 mol/l RbNO3Carrying out ion exchange in the solution for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 82.3%.
Tabletting the obtained catalyst into 40-60 mesh granulesAnd (3) adding a catalyst into a reactor, wherein the molar ratio of methylbenzene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 2 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, potassium hydroxide, a mesoporous guiding agent cetyl trimethyl ammonium bromide and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthetic product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.0, and the mesoporous size is about 8 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 86.7%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 3 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, potassium hydroxide, a mesoporous directing agent poly dimethyl diallyl ammonium chloride and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthetic product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.0, and the mesoporous size is about 5 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 83.7%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and filling the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol under normal pressure is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 4 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, a mesoporous guiding agent hexadecyltrimethylammonium chloride and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthetic product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.3, and the mesoporous size is about 12 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was dried at 100 ℃ for 10 hours. After the exchange, the ion exchange degree of sodium ions in the alkali metal ion exchange molecular sieve in the catalyst is 83.1 percent
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 5 ]
Sodium aluminate, sodium silicate, sodium hydroxide, a mesoporous guiding agent cetyl trimethyl ammonium bromide and water are taken as raw materials to be mixed according to a certain proportion, crystallized for a certain period of 16 hours at the temperature of 100 ℃,and filtering and washing the synthesized product, and then roasting to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.3, and the mesoporous size is about 14 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 85.7%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 6 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, a mesoporous directing agent poly dimethyl diallyl ammonium chloride and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthetic product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.3, and the mesoporous size is about 10 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 86.7%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of 415 ℃,N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 7 ]
The method comprises the steps of mixing sodium aluminate, sodium silicate, sodium hydroxide, potassium hydroxide, a mesoporous guiding agent cetyl trimethyl ammonium bromide and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthetic product to obtain the composite porous Y molecular sieve material. SiO for synthesizing composite hole Y molecular sieve2/Al2O3The ratio is 5.0, and the mesoporous size is about 8 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was dried at 100 ℃ for 10 hours. After the exchange, the ion exchange degree of sodium ions in the alkali metal ion exchange molecular sieve in the catalyst was 85.8%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 8 ]
The method comprises the steps of mixing aluminum hydroxide, silica sol, sodium hydroxide, potassium hydroxide, a mesoporous guiding agent hexadecyltrimethylammonium chloride and water serving as raw materials according to a certain proportion, crystallizing for 16 hours at the temperature of 100 ℃, filtering, washing and roasting a synthesized product to obtain the composite porous X molecular sieve material. SiO for synthesizing composite hole X molecular sieve2/Al2O3The ratio is 2.0, and the mesoporous size is about 7 nm.
Taking 10g of the molecular sieve, and carrying out ion exchange in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃ for 2 times; then 50 ml of 1 mol/l RbNO3Carrying out ion exchange in the solution for 2 times; finally dissolved in 50 ml of 1 mol/l CsNO3Carrying out ion exchange in the solution for 2 times; after filtration, the mixture was 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 82.3%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 9 ]
10g of the catalyst of example 1 was used to impregnate NaAlO2Loaded on a catalyst to obtain the catalyst containing 2 percent NaAlO2X molecular sieve catalyst.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 10 ]
The other is the same as [ example 9 ], except that NaAlO2The loading of (b) was 4%.
[ example 11 ]
The other is the same as [ example 9 ], except that NaAlO2The loading of (b) was 5%.
[ example 12 ]
The composite porous mordenite molecular sieve material is prepared by mixing sodium aluminate, sodium silicate, sodium hydroxide, a mesoporous directing agent cetyl trimethyl ammonium bromide and water according to a certain proportion, crystallizing for 24 hours at 160 ℃, filtering, washing and roasting a synthetic product. The mesoporous size of the synthesized composite pore mordenite molecular sieve is about 8 nm.
3 g of the above molecular sieve was mechanically mixed with 7 g of the molecular sieve [ example 4 ] at 80 ℃ in 100 ml of 1 mol/l KNO3Ion exchange is carried out in the solution for 2 hours and 2 times; then 50 ml of 1 mol/l RbNO3Ion exchange in solutionExchange 2 times; finally 50 ml of 1 mol/l CsNO3Carrying out ion exchange in the solution for 2 times; after filtration, the mixture was 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 80.8%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 13 ]
Taking [ example 4 ] 7 g of X molecular sieve and 3 g of Y molecular sieve, mechanically mixing uniformly, and heating at 80 ℃ under the condition of 100 ml of KNO with the concentration of 1 mol/L3Ion exchange is carried out in the solution for 2 hours and 2 times; then 50 ml of 1 mol/l RbNO3Carrying out ion exchange in the solution for 2 times; finally 50 ml of 1 mol/l CsNO3Carrying out ion exchange in the solution for 2 times; after filtration, the mixture was 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 80.8%.
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 14 ]
The procedure was repeated in the same manner as in example 4 except that the starting material methanol was changed to formaldehyde in the evaluation of the catalyst.
[ example 15 ]
The rest was the same as [ example 4 ] except that the starting material toluene was changed to p-xylene at the time of catalyst evaluation.
[ example 16 ]
The other is the same as [ example 4 ] except that the catalyst is ion-exchanged with cesium nitrate only three times.
[ example 17 ]
10g of the catalyst of example 1 was used to impregnate Bi2O3Loaded on a catalyst to obtain a catalyst containing 0.5 percent of Bi2O3The molecular sieve catalyst of (1).
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
[ example 18 ]
10g of the catalyst of example 1 was used to impregnate Bi2O3Loaded on a catalyst to obtain a catalyst containing 1.5 percent of Bi2O3The molecular sieve catalyst of (1).
Tabletting the obtained catalyst to form a 40-60-mesh granular catalyst, and loading the granular catalyst into a reactor, wherein the molar ratio of toluene to methanol is 5: 1. at 2.5 hours-1Liquid space velocity of (D), 415 ℃, N2The activity evaluation was performed at a flow rate of 10 ml/min, and the results are shown in Table 1.
Comparative example 1
Taking a purchased common X molecular Sieve (SiO)2/Al2O3The ratio is 2.0, no mesopores are contained), 10g, ion exchange is carried out in 100 ml of 1 mol/L KNO3 solution for 2 hours at 80 ℃, and the exchange is carried out for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 82.9%.
The activity of the catalyst was evaluated in accordance with the method of [ example 1 ], and the results are shown in Table 1.
Comparative example 2
Taking purchased common Y molecular Sieve (SiO)2/Al2O35.0 without mesopores) 10g, and performing ion exchange in 100 ml of 1 mol/l KNO3 solution for 2 hours at 80 ℃ for 2 times;then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 82.9%.
The activity of the catalyst was evaluated in accordance with the method of [ example 1 ], and the results are shown in Table 1.
Comparative example 3
Taking the purchased common mordenite molecular Sieve (SiO)2/Al2O3Ratio of 10, no mesopores) 10g, ion exchange is carried out in 100 ml of 1 mol/l KNO3 solution for 2 hours at 80 ℃, and the exchange is carried out for 2 times; then ion exchange is carried out in 50 ml of RbNO3 solution with 1 mol/L for 2 times; finally, ion exchange is carried out in 50 ml of 1 mol/L CsNO3 solution for 2 times; after filtration, the mixture was 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 82.9%.
The activity of the catalyst was evaluated in accordance with the method of [ example 1 ], and the results are shown in Table 1.
TABLE 1
a. Utilization rate of formaldehyde
b. Overall selectivity to methyl ethyl benzene and methyl styrene
c.X the molecular sieve was exchanged with cesium ions only.
Claims (7)
1. A catalyst for side chain alkylation, characterized in that the catalyst comprises a composite molecular sieve; wherein the catalyst further contains 0.1-2 wt% of Bi2O3(ii) a Wherein the composite pores contain micropores andthe mesoporous material has two pore channel structures, the volume ratio of micropores to mesopores is 0.5-15, and the size range of the mesopores is 2-20 nm; the molecular sieve is at least one of an X molecular sieve, a Y molecular sieve, an L molecular sieve and a mercerized molecular sieve; the side chain alkylation catalyst is synthesized by introducing a mesoporous guiding agent in a hydrothermal synthesis method: the composite molecular sieve catalyst is synthesized by taking sodium aluminate, sodium silicate, sodium hydroxide, a mesoporous guiding agent and water as raw materials and mixing the raw materials according to a certain proportion, and crystallizing and roasting the mixture at the temperature of 60-150 ℃.
2. The side chain alkylation catalyst according to claim 1, wherein the volume ratio of micropores to mesopores is 3 to 8.
3. The side-chain alkylation catalyst according to claim 1, wherein the mesoporous size is in the range of 2 to 15 nm.
4. The side-chain alkylation catalyst according to claim 1, wherein Bi2O3The content of (B) is 0.5-1.5%.
5. The side-chain alkylation catalyst according to claim 1, wherein the mesoporous directing agent is selected from at least one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polydimethyldiallylammonium chloride.
6. A side chain alkylation method, which adopts aromatic hydrocarbon and side chain alkylation reagent to react under the action of the catalyst of any claim 1 to 5 to obtain a side chain alkylation product.
7. A method for preparing ethylbenzene and styrene adopts methanol and toluene as raw materials, and ethylbenzene and styrene are obtained by reaction under the action of the catalyst of any one of claims 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711057098.4A CN109746036B (en) | 2017-11-01 | 2017-11-01 | Side chain alkylation catalyst and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711057098.4A CN109746036B (en) | 2017-11-01 | 2017-11-01 | Side chain alkylation catalyst and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109746036A CN109746036A (en) | 2019-05-14 |
| CN109746036B true CN109746036B (en) | 2021-12-28 |
Family
ID=66397670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711057098.4A Active CN109746036B (en) | 2017-11-01 | 2017-11-01 | Side chain alkylation catalyst and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109746036B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114588918B (en) * | 2022-03-04 | 2024-02-06 | 太原理工大学 | Preparation method and application of catalyst for preparing ethylbenzene and styrene by toluene and methanol side chain alkylation reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006015798A1 (en) * | 2004-08-05 | 2006-02-16 | Basf Aktiengesellschaft | Method for producing alkyl-aromatic compounds by direct alkylation of aromatic hydrocarbons with alkanes |
| CN102774855A (en) * | 2011-05-12 | 2012-11-14 | 北京化工大学 | Preparation method of microporous-mesoporous composite zeolite |
| CN102909064A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene with methanol, and preparation method and applications thereof |
| CN106032280A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院大连化学物理研究所 | Synthesis method, product and applications of mordenite having mesopores and micropores |
-
2017
- 2017-11-01 CN CN201711057098.4A patent/CN109746036B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006015798A1 (en) * | 2004-08-05 | 2006-02-16 | Basf Aktiengesellschaft | Method for producing alkyl-aromatic compounds by direct alkylation of aromatic hydrocarbons with alkanes |
| CN102774855A (en) * | 2011-05-12 | 2012-11-14 | 北京化工大学 | Preparation method of microporous-mesoporous composite zeolite |
| CN102909064A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene with methanol, and preparation method and applications thereof |
| CN106032280A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院大连化学物理研究所 | Synthesis method, product and applications of mordenite having mesopores and micropores |
Non-Patent Citations (2)
| Title |
|---|
| 付晓琴.基于咪唑型离子液体微介孔Y分子筛的制备与性能研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2017, * |
| 基于咪唑型离子液体微介孔Y分子筛的制备与性能研究;付晓琴;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170215;摘要、第1.4.2节、第2.6.1节、第3.2.2节、第3.4节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109746036A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11305265B2 (en) | Aromatization catalyst and preparation process and use thereof | |
| US3775501A (en) | Preparation of aromatics over zeolite catalysts | |
| CN104926580B (en) | Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation | |
| Wang et al. | Dimethyl ether carbonylation over nanosheet-assembled hierarchical mordenite | |
| Kallo et al. | Adsorption and catalytic properties of sedimentary clinoptilolite and mordenite from the Tokaj Hills, Hungary | |
| CN101885662A (en) | Toluene methanol alkylation method | |
| CN106607070B (en) | For methylbenzene methanol side chain alkylation synthesizing ethyl benzene phenylethylene catalyst and application thereof | |
| CN106607073B (en) | Methylbenzene methanol side chain alkylation prepares ethylbenzene phenylethylene catalyst and application thereof | |
| CN108114739A (en) | Support type multi-stage porous HZSM-5 catalyst | |
| CN104557422B (en) | Side chain alkylation method of toluene with methanol | |
| US8907151B2 (en) | Conversion of methane to aromatic compounds using UZM-39 aluminosilicate zeolite | |
| CN109746036B (en) | Side chain alkylation catalyst and use thereof | |
| CN101348260B (en) | Preparation of binderless MFI/FAU composite zeolite molecular sieve | |
| CN109746037B (en) | Side chain alkylation composite pore molecular sieve catalyst and application thereof | |
| CN101602639A (en) | Produce the method for ethylene, propylene | |
| CN103539601B (en) | For toluene and methanol side chain alkylation ethylbenzene and cinnamic method | |
| CN107537546B (en) | The catalyst and application thereof of ethylbenzene styrene is prepared for methylbenzene methanol side chain alkylation | |
| CN107955639A (en) | The method of six alkane cracking of carbon | |
| CN109746035B (en) | Method for preparing methyl ethyl benzene and methyl styrene by side chain alkylation of xylene and methanol | |
| CN103664477B (en) | Toluene shape-selective disproportionation method | |
| CN111054429A (en) | Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof | |
| CN106607072B (en) | The catalyst and application thereof of ethylbenzene and styrene is prepared for methylbenzene methanol side chain alkylation | |
| CN103831128B (en) | Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof | |
| CN109701592B (en) | Side chain alkylation catalyst and method of use | |
| CN109701593B (en) | Side chain alkylation catalyst and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |