CN108722474B - Shape-selective alkylation catalyst and preparation method and application thereof - Google Patents
Shape-selective alkylation catalyst and preparation method and application thereof Download PDFInfo
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C—CHEMISTRY; METALLURGY
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- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
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- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
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- C07C2529/80—Mixtures of different zeolites
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Abstract
The invention provides a shape-selective alkylation catalyst, a preparation method and application thereof, belonging to the field of heterogeneous catalysis. The catalyst comprises the following components in percentage by mass: 60-88% of ZSM-5/ZSM-11 cocrystallized molecular sieve, 9-34% of binder and 2-7% of oxide of IIA, IIIA or VA group elements. The preparation method of the catalyst mainly comprises the following steps: firstly, mixing and kneading a ZSM-5/ZSM-11 co-crystallization molecular sieve and a binder, extruding, molding, drying and roasting, then converting into a hydrogen form through ion exchange, then adopting hydrothermal treatment, and then carrying out modification treatment by using a solution of IIA, IIIA or VA group element compounds. The catalyst is applied to alkylation of toluene and ethylene, can effectively improve selectivity of p-methyl ethylbenzene, inhibit generation of o-methyl ethylbenzene, shows excellent reaction stability, and has important application value.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysis, and particularly relates to a shape-selective alkylation catalyst, and a preparation method and application thereof.
Background
Methyl ethyl benzene is a key raw material for producing methyl styrene and further preparing chemicals such as resin, plastics, rubber, paint and the like. Methyl ethylbenzene exists in three isomers: the p-methyl styrene (PMS) obtained by dehydrogenation of PET can be used for producing high-end special chemicals such as high-end resin, high-performance rubber, novel plastic and special paint, and downstream products of the p-methyl styrene (PMS) have wide application in various industries such as automobiles, energy sources, chemical engineering and materials; the meta-methylstyrene (MMS) produced by the dehydrogenation of MET can also be widely applied to resin coatings, composite materials, vinyl resins and VPI insulating impregnating varnish; in the process of OET dehydrogenation, indene, indane and other substances which affect the properties of the final polymer are generated and are difficult to remove from methyl styrene, in other words, OET has little use value. Therefore, it is important to improve the selectivity of PET and avoid the formation of OET as much as possible when synthesizing methyl ethyl benzene.
The alkylation reaction of toluene and ethylene can be used for preparing methyl ethylbenzene, but the methyl ethylbenzene obtained by the conventional Friedel-Crafts catalyst is three isomers with thermodynamic equilibrium, wherein MET is 50 percent, PET is 30 percent, and OET is 20 percent. Therefore, in order to improve the selectivity of PET (selectivity of PET in methyl ethyl benzene, the same applies hereinafter) and suppress the formation of OET, the development of a catalyst having a shape-selective effect is important. PET-based end-products have a significant advantage over MET end-products, and much research has been devoted to developing catalysts with high PET selectivity (typically > 95%). USP5698756 discloses that a catalyst obtained by modifying a ZSM-5 molecular sieve by silicon deposition for multiple times by using a silicone polymer and then carrying out alkali metal ion exchange has high PET selectivity under the hydrogen condition. CN201110217577.4 discloses that the selectivity of PET of the catalyst obtained by modifying mordenite with alkaline earth metal compounds and copper-containing compounds respectively, adding IVA group element compounds and binders, extruding into strips, drying and roasting under the hydrogen condition can reach more than 95%. However, high PET selectivity is often accompanied by rapid deactivation of the catalyst, frequent regeneration of the catalyst and recycle of ethylene, both of which adversely affect the operability and economics of the process. And with the development of the technology for separating MET from PET, the extraction of high-concentration PET (and further the obtaining of p-methylstyrene) from the mixture of MET and PET has made a breakthrough. Therefore, the development of the shape-selective alkylation catalyst which has high activity and good stability and is used for generating p-methyl ethylbenzene and m-methyl ethylbenzene (wherein the selectivity of PET is obviously higher than a thermodynamic equilibrium value) has application value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops a shape-selective alkylation catalyst and a preparation method thereof by taking a ZSM-5/ZSM-11 cocrystallized molecular sieve as a main body and utilizing various means such as high-temperature roasting, ion exchange, hydrothermal treatment, element modification and the like to modulate the acidity and the pore structure of the molecular sieve and carrying out a great deal of research work, and the catalyst is used for the alkylation process of toluene and ethylene, can inhibit the generation of o-methyl ethylbenzene (OET selectivity is less than 0.5 percent) and has the selectivity of p-methyl ethylbenzene which is obviously higher than the thermodynamic equilibrium value (PET selectivity is more than or equal to 37 percent).
The invention relates to a shape-selective alkylation catalyst, which comprises the following components in percentage by mass: 60-88% of ZSM-5/ZSM-11 cocrystallized molecular sieve, 9-34% of binder and 2-7% of IIA, IIIA or VA group element oxide.
The ZSM-5/ZSM-11 cocrystallization molecular sieve contains 10-40% of ZSM-5 molecular sieve by mass percentage; the binder is aluminum oxide or silicon oxide; the IIA group element oxide is magnesium oxide or calcium oxide, the IIIA group element oxide is boron oxide, and the VA group element oxide is phosphorus oxide.
A method of preparing a shape selective alkylation catalyst comprising the steps of:
(1) mixing a ZSM-5/ZSM-11 cocrystallized molecular sieve with a binder according to the mass percentage of a dry basis of 65-90%: 10-35 percent of the total mass of the cocrystallized molecular sieve and the binder, then adding sesbania powder accounting for 2-4 percent of the total mass of the cocrystallized molecular sieve and the binder, and uniformly mixing, wherein the dry basis total mass ratio of the cocrystallized molecular sieve to the binder is 0.3-0.6: 1, kneading and extruding the mixture by using a dilute nitric acid solution with the mass concentration of 7-12%, drying the mixture for 4-15 hours at the temperature of 100-120 ℃, and roasting the dried mixture for 3-6 hours at the temperature of 530-560 ℃ at the heating rate of 1-3 ℃/min to obtain a formed object a;
(2) and (3) carrying out ion exchange on the formed product a for 1-3 times by adopting an ammonium chloride solution with the molar concentration of 0.6-1.0M or a dilute hydrochloric acid solution with the molar concentration of 0.1-0.2M, wherein the solid-to-liquid ratio is 1: 2.5-4.5 g/ml, and the ion exchange conditions of each time are as follows: the temperature is 60-90 ℃, and the time is 1-3 h; washing with water for three times, wherein the solid-liquid ratio is 1: 4-8 g/ml, and the washing conditions of each time are as follows: the temperature is 60-90 ℃, the time is 2 hours, then the mixture is dried for 8-20 hours at the temperature of 100-120 ℃, and roasted for 3 hours at the temperature of 500-520 ℃, so as to obtain a forming object b;
(3) and (3) performing water vapor treatment on the molded object b to obtain a molded object c, wherein the water vapor treatment conditions are as follows: the temperature is 500-570 ℃, the time is 2-6 h, and the solid-water ratio is 1: 2-4 g/ml;
(4) and (3) modifying the formed object c by using a solution containing a compound of the IIA, IIIA or VA group elements by adopting an immersion method, and drying at 100-120 ℃ for 6-12 h and roasting at 500-530 ℃ for 3-6 h to obtain the final catalyst.
In the step (4), the solution of the IIA group element magnesium compound is a magnesium nitrate solution or a magnesium acetate solution, and the solution of the calcium compound is a calcium nitrate solution; the solution of the IIIA group element boron compound is boric acid solution; the solution of the VA group element phosphorus compound is any one of dilute phosphoric acid, ammonium hydrogen phosphate solution or ammonium dihydrogen phosphate solution.
The application of a shape-selective alkylation catalyst in the process of preparing p-methyl ethylbenzene and m-methyl ethylbenzene by alkylating toluene and ethylene.
The main body of the catalyst in the technical scheme of the invention adopts a ZSM-5/ZSM-11 cocrystallization molecular sieve, so that the advantages of the ZSM-5 and ZSM-11 molecular sieves can be utilized, and a synergistic effect is generated; the acidity and the pore texture properties of the molecular sieve catalyst can be effectively adjusted by reasonably applying high-temperature roasting, ion exchange and hydrothermal treatment and introducing modified elements. The prepared catalyst can improve the selectivity of p-methyl ethylbenzene in the alkylation process of toluene and ethylene, effectively inhibit the generation of o-methyl ethylbenzene, simultaneously has good reaction stability, overcomes the defects of the prior art, and has important application value.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to the examples set forth herein.
Example 1
Taking 120g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 10 mass percent of ZSM-5 and 77.8g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 65: 35%, adding 3.2g of sesbania powder (accounting for 2% of the total dry basis mass of the cocrystallized molecular sieve and the alumina), uniformly mixing, adding 96g of dilute nitric acid solution with the mass concentration of 7% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.6:1), carrying out mixing kneading and extrusion molding, then drying at 100 ℃ for 15h, raising the temperature to 530 ℃ at the heating rate of 3 ℃/min, and roasting for 6h to obtain a formed matter a 1; and (3) carrying out ion exchange on the formed product a1 by adopting an ammonium chloride solution with the molar concentration of 0.6M, wherein the solid-to-liquid ratio is 1: 4.5g/ml, each ion exchange condition: the temperature is 90 ℃, and the time is 1 h; washing with water for three times, wherein the solid-liquid ratio is 1: 4g/ml, and the washing conditions are as follows: the temperature is 60 ℃, the time is 2 hours, then the mixture is dried for 8 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 500 ℃ to obtain a forming object b 1; and (3) carrying out water vapor treatment on the molded object b1 to obtain a molded object c1, wherein the water vapor treatment conditions are as follows: the temperature is 500 ℃, the time is 6h, and the solid-water ratio is 1: 2 g/ml; the c1 was impregnated with boric acid solution, dried at 110 ℃ for 8h and calcined at 500 ℃ for 6h to give the finished catalyst Cat-1, the composition of which is shown in Table 1.
Example 2
Taking 150g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 20 mass percent of ZSM-5 and 84.2g of silica sol, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the silica sol is 80: 20%, adding 4.8g of sesbania powder (accounting for 3% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 48g of dilute nitric acid solution with the mass concentration of 8.5% (the total dry basis mass ratio of the cocrystallized molecular sieve and the silica is 0.3:1), kneading, extruding into strips, forming, drying at 110 ℃ for 10 hours, raising the temperature to 550 ℃ at the heating rate of 1.5 ℃/min, and roasting for 4 hours to obtain a formed object a 2; and (3) carrying out 1-time ion exchange on the formed product a2 by adopting an ammonium chloride solution with the molar concentration of 1.0M, wherein the solid-to-liquid ratio is 1: 4g/ml, ion exchange conditions: the temperature is 80 ℃, and the time is 2 h; washing with water for three times, wherein the solid-liquid ratio is 1: 5g/ml, and the washing conditions are as follows: drying at the temperature of 80 ℃ for 2h, drying at the temperature of 100 ℃ for 20h, and roasting at the temperature of 520 ℃ for 3h to obtain a formed product b 2; and (3) carrying out water vapor treatment on the molded object b2 to obtain a molded object c2, wherein the water vapor treatment conditions are as follows: the temperature is 530 ℃, the time is 4.5h, and the solid-water ratio is 1: 2.5 g/ml; the catalyst Cat-2 was obtained by impregnating c2 with a magnesium acetate solution, drying at 100 ℃ for 12 hours and calcining at 530 ℃ for 3 hours, and its composition is shown in table 1.
Example 3
Taking 170g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 30 mass percent of ZSM-5 and 22.2g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 90: 10%, adding 6.4g of sesbania powder (accounting for 4% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 80g of dilute nitric acid solution with the mass concentration of 12% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.5:1), kneading, extruding into strips, forming, drying at 120 ℃ for 4h, raising the temperature to 560 ℃ at the heating rate of 1 ℃/min, and roasting for 3h to obtain a formed object a 3; and (3) carrying out ion exchange on the formed product a3 for 2 times by using a dilute hydrochloric acid solution with the molar concentration of 0.1M, wherein the solid-to-liquid ratio is 1: 4.5g/ml, each ion exchange condition: the temperature is 80 ℃, and the time is 2 h; washing with water for three times, wherein the solid-liquid ratio is 1: 6g/ml, and the washing conditions are as follows: the temperature is 80 ℃, the time is 2 hours, then the mixture is dried for 15 hours at the temperature of 110 ℃ and roasted for 3 hours at the temperature of 520 ℃, and a forming object b3 is obtained; and (3) carrying out water vapor treatment on the molded object b3 to obtain a molded object c3, wherein the water vapor treatment conditions are as follows: temperature 540 ℃, time 4h, solid-to-water ratio 1: 3 g/ml; the catalyst Cat-3 was obtained by impregnating c3 with calcium nitrate solution, drying at 120 ℃ for 6 hours and calcining at 520 ℃ for 4 hours, and its composition is shown in table 1.
Example 4
Taking 119g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 40 mass percent of ZSM-5 and 77.8g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 65: 35%, adding 4.8g of sesbania powder (accounting for 3% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 80g of dilute nitric acid solution with the mass concentration of 9% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.5:1), kneading, extruding into strips, forming, drying at 114 ℃ for 8h, raising the temperature to 540 ℃ at the heating rate of 2 ℃/min, and roasting for 5h to obtain a formed object a 4; and (3) carrying out 1-time ion exchange on the formed product a4 by using a dilute hydrochloric acid solution with the molar concentration of 0.2M, wherein the solid-to-liquid ratio is 1: 2.5g/ml, ion exchange conditions: the temperature is 60 ℃, and the time is 3 h; washing with water for three times, wherein the solid-liquid ratio is 1: 8g/ml, and the washing conditions are as follows: the temperature is 90 ℃, the time is 2 hours, then the mixture is dried for 8 hours at the temperature of 120 ℃, and roasted for 3 hours at the temperature of 520 ℃, thus obtaining a forming object b 4; and (3) carrying out water vapor treatment on the molded object b4 to obtain a molded object c4, wherein the water vapor treatment conditions are as follows: the temperature is 560 ℃, the time is 2.5h, the solid-water ratio is 1: 2 g/ml; the c4 was impregnated with magnesium nitrate solution, dried at 110 ℃ for 8h and calcined at 520 ℃ for 4h to give the finished catalyst Cat-4, the composition of which is shown in Table 1.
Example 5
Taking 160.6g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 30 mass percent of ZSM-5 and 33.3g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 85: 15%, adding 4.8g of sesbania powder (accounting for 3% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 72g of dilute nitric acid solution with the mass concentration of 9.3% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.45:1), carrying out mixed kneading and extrusion molding, then drying at 110 ℃ for 10h, increasing the temperature rise rate to 550 ℃ at the speed of 2 ℃/min, and roasting for 4h to obtain a formed object a 5; and (3) carrying out 2 times of ion exchange on the formed product a5 by adopting an ammonium chloride solution with the molar concentration of 0.8M, wherein the solid-to-liquid ratio is 1: 3g/ml, each ion exchange condition was: the temperature is 80 ℃, and the time is 2 h; washing with water for three times, wherein the solid-liquid ratio is 1: 5g/ml, and the washing conditions are as follows: the temperature is 80 ℃, the time is 2 hours, then the mixture is dried for 8 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 520 ℃, and a forming object b5 is obtained; and (3) carrying out water vapor treatment on the molded object b5 to obtain a molded object c5, wherein the water vapor treatment conditions are as follows: the temperature is 520 ℃, the time is 5h, and the solid-water ratio is 1: 4 g/ml; the c5 was impregnated with magnesium nitrate solution, dried at 110 ℃ for 8h and calcined at 500 ℃ for 6h to give the finished catalyst Cat-5, the composition of which is shown in Table 1.
Example 6
Taking 168.8g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 20 mass percent of ZSM-5 and 22.2g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 90: 10%, adding 6.4g of sesbania powder (accounting for 4% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 80g of dilute nitric acid solution with the mass concentration of 11% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.5:1), carrying out mixing kneading and extrusion molding, then drying at 110 ℃ for 10h, raising the temperature to 540 ℃ at the heating rate of 2 ℃/min, and roasting for 5h to obtain a formed object a 6; and (3) carrying out 2 times of ion exchange on the formed product a6 by adopting an ammonium chloride solution with the molar concentration of 0.8M, wherein the solid-to-liquid ratio is 1: 3g/ml, each ion exchange condition was: the temperature is 80 ℃, and the time is 2 h; washing with water for three times, wherein the solid-liquid ratio is 1: 6g/ml, and the washing conditions are as follows: the temperature is 80 ℃, the time is 2 hours, then the mixture is dried for 12 hours at the temperature of 110 ℃ and roasted for 3 hours at the temperature of 520 ℃, and a forming object b6 is obtained; and (3) carrying out water vapor treatment on the molded object b6 to obtain a molded object c6, wherein the water vapor treatment conditions are as follows: the temperature is 570 ℃, the time is 2h, and the solid-water ratio is 1: 3 g/ml; the catalyst Cat-6 was obtained by impregnating c6 with a solution of ammonium hydrogen phosphate, drying at 110 ℃ for 8 hours and calcining at 530 ℃ for 3 hours, and its composition is shown in table 1.
Example 7
Taking 155.6g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 40 mass percent of ZSM-5 and 33.3g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 85: 15%, adding 4.8g of sesbania powder (accounting for 3 percent of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 88g of dilute nitric acid solution with the mass concentration of 8 percent (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.55:1), carrying out mixing kneading and extrusion molding, then drying at 120 ℃ for 4h, raising the temperature to 540 ℃ at the heating rate of 2 ℃/min, and roasting for 5h to obtain a formed object a 7; and (3) carrying out 2 times of ion exchange on the formed product a7 by adopting an ammonium chloride solution with the molar concentration of 0.8M, wherein the solid-to-liquid ratio is 1: 3g/ml, each ion exchange condition was: the temperature is 80 ℃, and the time is 2 h; washing with water for three times, wherein the solid-liquid ratio is 1: 5g/ml, and the washing conditions are as follows: the temperature is 80 ℃, the time is 2 hours, then the mixture is dried for 12 hours at the temperature of 110 ℃ and roasted for 3 hours at the temperature of 520 ℃, and a forming object b7 is obtained; and (3) carrying out water vapor treatment on the molded object b7 to obtain a molded object c7, wherein the water vapor treatment conditions are as follows: the temperature is 550 ℃, the time is 3h, and the solid-water ratio is 1: 3.5 g/ml; the c7 was impregnated with ammonium dihydrogen phosphate solution, dried at 110 ℃ for 8h and calcined at 530 ℃ for 3h to give the finished catalyst Cat-7, the composition of which is shown in Table 1.
Example 8
Taking 151.1g of ZSM-5/ZSM-11 cocrystallized molecular sieve containing 30 mass percent of ZSM-5 and 44.4g of alumina, wherein the dry basis mass percent of the ZSM-5/ZSM-11 cocrystallized molecular sieve and the alumina is 80: 20%, adding 4.8g of sesbania powder (accounting for 3% of the total dry basis mass of the cocrystallized molecular sieve and the silica), uniformly mixing, adding 80g of dilute nitric acid solution with the mass concentration of 7.6% (the total dry basis mass ratio of the cocrystallized molecular sieve and the alumina is 0.5:1), carrying out mixing kneading and extrusion molding, then drying at 110 ℃ for 10h, increasing the temperature rise rate to 560 ℃ at the speed of 1 ℃/min, and roasting for 3h to obtain a formed object a 8; and (3) carrying out ion exchange on the formed product a8 for 2 times by using a dilute hydrochloric acid solution with the molar concentration of 0.1M, wherein the solid-to-liquid ratio is 1: 4g/ml, each ion exchange condition was: the temperature is 70 ℃, and the time is 2.5 h; washing with water for three times, wherein the solid-liquid ratio is 1: 6g/ml, and the washing conditions are as follows: drying at the temperature of 70 ℃ for 2h, drying at the temperature of 110 ℃ for 12h, and roasting at the temperature of 520 ℃ for 3h to obtain a formed product b 8; and (3) carrying out water vapor treatment on the molded object b8 to obtain a molded object c8, wherein the water vapor treatment conditions are as follows: the temperature is 530 ℃, the time is 4.5h, and the solid-water ratio is 1: 3 g/ml; the c8 was impregnated with dilute phosphoric acid, dried at 110 ℃ for 8h and calcined at 520 ℃ for 4h to give the finished catalyst Cat-8, the composition of which is shown in Table 1.
Example 9
The catalysts obtained in examples 1 to 8 were used in the alkylation of toluene with ethylene. The evaluation of the reactivity of the catalyst was carried out on a conventional fixed bed reactor, using 3g of catalyst. Pretreating the catalyst for 1h at 450 ℃ in the nitrogen atmosphere, and then cooling to the reaction temperature; and (3) feeding the materials in and out, quickly injecting methylbenzene into the reaction system by using a plunger pump, and introducing ethylene (the required amount is controlled by a mass flow meter) to carry out alkylation reaction after the methylbenzene flows out from the outlet of the reaction device. 2 wt.% methane was added to the ethylene feed as an internal standard, and both gas and liquid phase components were analyzed by Agilent Technologies 7890B gas chromatography using FID detector, PONA chromatography column. The reaction conditions are as follows: the pressure is 0.5MPa, the temperature is 370 ℃, the toluene/ethylene (mol ratio) is 7, and the weight space velocity of the ethylene is 0.3h-1. The results of the reaction for 24h are shown in Table 1. As can be seen from Table 1, the catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, Cat-6, Cat-7 and Cat-8 in the embodiment of the invention have high reaction activity and good selectivity to methyl ethylbenzene, and can remarkably inhibit the generation of o-methyl ethylbenzene. In addition, the evaluation of the stability of the catalyst Cat-5 of example 5 for 500 hours under the above reaction conditions showed that the catalyst had an average ethylene conversion of 99.24%, an average PET selectivity of 49.10% and an average OET selectivity of 0.05%, indicating its excellent reaction stability and good product selectivity, further illustrating the superiority of the present invention.
The performance of the catalyst prepared by the invention is judged by the following method:
ethylene conversion of 100% × (ethylene/methane fed-ethylene/methane discharged)/(ethylene/methane fed)
PET (or MET or OET) selectivity is 100% × (PET formation (or MET or OET)/methyl ethylbenzene formation).
TABLE 1 compositions of catalysts obtained in examples 1-7 and the results of toluene and ethylene alkylation
Claims (5)
1. Use of a shape selective alkylation catalyst, characterized by: the shape-selective alkylation catalyst is used for the process of preparing p-methyl ethylbenzene and m-methyl ethylbenzene by alkylating toluene and ethylene;
the catalyst comprises the following components in percentage by mass: 60-88% of ZSM-5/ZSM-11 co-crystallization molecular sieve, 9-34% of binder and 2-7% of IIA, IIIA or VA group element oxide;
the ZSM-5/ZSM-11 cocrystallization molecular sieve contains 10-40% of ZSM-5 molecular sieve by mass percent.
2. Use according to claim 1, characterized in that: the binder is alumina or silica.
3. Use according to claim 1, characterized in that: the IIA group element oxide is magnesium oxide or calcium oxide, the IIIA group element oxide is boron oxide, and the VA group element oxide is phosphorus oxide.
4. A method for preparing a shape selective alkylation catalyst, comprising: the method comprises the following steps:
(1) mixing a ZSM-5/ZSM-11 cocrystallized molecular sieve with a binder according to the mass percentage of a dry basis of 65-90%: 10-35 percent of the total mass of the cocrystallized molecular sieve and the binder, then adding sesbania powder accounting for 2-4 percent of the total mass of the cocrystallized molecular sieve and the binder, and uniformly mixing, wherein the dry basis total mass ratio of the cocrystallized molecular sieve to the binder is 0.3-0.6: 1, kneading and extruding the mixture by using a dilute nitric acid solution with the mass concentration of 7-12%, drying the mixture for 4-15 hours at the temperature of 100-120 ℃, and roasting the dried mixture for 3-6 hours at the temperature of 530-560 ℃ at the heating rate of 1-3 ℃/min to obtain a formed object a;
(2) and (3) carrying out ion exchange on the formed product a for 1-3 times by adopting an ammonium chloride solution with the molar concentration of 0.6-1.0M or a dilute hydrochloric acid solution with the molar concentration of 0.1-0.2M, wherein the solid-to-liquid ratio is 1: 2.5-4.5 g/ml, and the ion exchange conditions of each time are as follows: the temperature is 60-90 ℃, and the time is 1-3 h; washing with water for three times, wherein the solid-liquid ratio is 1: 4-8 g/ml, and the washing conditions of each time are as follows: the temperature is 60-90 ℃, the time is 2 hours, then the mixture is dried for 8-20 hours at the temperature of 100-120 ℃, and roasted for 3 hours at the temperature of 500-520 ℃, so as to obtain a forming object b;
(3) and (3) performing water vapor treatment on the molded object b to obtain a molded object c, wherein the water vapor treatment conditions are as follows: the temperature is 500-570 ℃, the time is 2-6 h, and the solid-water ratio is 1: 2-4 g/ml;
(4) modifying the formed object c by using a solution containing a compound of IIA, IIIA or VA group elements by adopting an immersion method, and drying at 100-120 ℃ for 6-12 h and roasting at 500-530 ℃ for 3-6 h to obtain a final catalyst;
the catalyst comprises the following components in percentage by mass: 60-88% of ZSM-5/ZSM-11 co-crystallization molecular sieve, 9-34% of binder and 2-7% of IIA, IIIA or VA group element oxide;
the ZSM-5/ZSM-11 cocrystallization molecular sieve contains 10-40% of ZSM-5 molecular sieve by mass percent.
5. A process for preparing a shape selective alkylation catalyst according to claim 4, wherein:
in the step (4), the solution of the IIA group element magnesium compound is a magnesium nitrate solution or a magnesium acetate solution, and the solution of the calcium compound is a calcium nitrate solution; the solution of the IIIA group element boron compound is boric acid solution; the solution of the VA group element phosphorus compound is any one of dilute phosphoric acid, ammonium hydrogen phosphate solution or ammonium dihydrogen phosphate solution.
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| CN111604057A (en) * | 2020-04-01 | 2020-09-01 | 深圳泰利能源有限公司 | Preparation method of animal and vegetable oil hydrogenation direct deoxidation catalyst |
| CN114073976B (en) * | 2020-08-10 | 2023-04-07 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
| CN114130421B (en) * | 2020-09-04 | 2024-01-09 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and preparation method and application thereof |
| CN114425412A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Non-hydroisomerization catalyst for alkyl aromatic hydrocarbon and preparation method and application thereof |
| CN115707510B (en) * | 2021-08-18 | 2024-04-16 | 中国科学院大连化学物理研究所 | Preparation method and application of modified MOR molecular sieve |
| CN114849769B (en) * | 2022-04-25 | 2023-06-13 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
| CN115608413A (en) * | 2022-10-12 | 2023-01-17 | 陕西延长石油（集团）有限责任公司 | Gas phase aluminum supplement regeneration method for molecular sieve-containing catalyst |
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