CN114515601A - Modified polymerization mesoporous material catalyst and preparation method and application thereof - Google Patents

Modified polymerization mesoporous material catalyst and preparation method and application thereof Download PDF

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CN114515601A
CN114515601A CN202011301889.9A CN202011301889A CN114515601A CN 114515601 A CN114515601 A CN 114515601A CN 202011301889 A CN202011301889 A CN 202011301889A CN 114515601 A CN114515601 A CN 114515601A
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mesoporous material
polymeric
catalyst
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preparation
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CN114515601B (en
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刘红梅
亢宇
张蓝溪
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
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    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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Abstract

The invention relates to the field of fine chemical engineering, and discloses a modified polymeric mesoporous material catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing and contacting a polymeric mesoporous material, p-toluenesulfonic acid and a solvent to obtain a mixture; (2) and cooling, separating, drying and roasting the mixture to obtain the modified polymeric mesoporous material catalyst. The modified polymeric mesoporous material catalyst is used for the esterification reaction of methacrylic acid, and can obtain higher methacrylic acid conversion rate and methyl methacrylate selectivity.

Description

Modified polymerization mesoporous material catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a modified polymeric mesoporous material catalyst and a preparation method and application thereof.
Background
Methyl Methacrylate (MMA) is mainly used in the industries of organic glass (PMMA) coating, textile, adhesive, leather, papermaking, floor polishing, unsaturated resin modification, methacrylic acid high-grade esters, wood impregnating compound, printing and dyeing auxiliary agent, plastic plasticizer and the like. In recent years, the demands of domestic and foreign MMA polymers, profiles, plates, coatings, emulsions and the like are increased, the application fields are continuously widened, and the rapid development of the MMA industry is promoted. At present, the domestic methyl methacrylate production technology is still at the beginning stage, and the development of a methacrylic acid esterification catalyst and a matched process are the development requirements of the MMA production industry in China.
For esterification reaction of methacrylic acid and methanol, the traditional production process using inorganic acids such as sulfuric acid, phosphoric acid, boric acid and the like as catalysts is gradually eliminated, and the organic acids such as p-toluenesulfonic acid and the like as catalysts have the defects of serious environmental pollution, low selectivity and difficult product separation. At present, the production of methyl methacrylate is generally carried out by industrially using acidic cation exchange resin, and the cation exchange resin has the advantages of good stability, high selectivity, lower cost, easy separation and the like in the esterification reaction. However, the cation exchange resin has poor heat resistance (generally, the cation exchange resin is decomposed at a temperature of not higher than 250 ℃), small specific surface area and pore volume, and the cation exchange resin is easy to swell, so that the cation exchange resin is poor in reaction activity as an esterification catalyst and low in ester yield.
Compared with resin catalysts, the inorganic mesoporous material has the structural advantages of large specific surface area and pore volume and the performance advantage of high temperature resistance. However, the surface of the all-silicon mesoporous molecular sieve with the basic framework structure consisting of silicon and oxygen does not contain functional groups, and does not show any activity in the esterification reaction of methacrylic acid. Therefore, it is not practical to directly apply the all-silicon mesoporous molecular sieve material to the esterification reaction of methacrylic acid.
At present, for researchers of methacrylic esterification catalysts, the development of novel esterification catalysts and the improvement of catalytic activity, ester selectivity and stability thereof are urgent research efforts.
Disclosure of Invention
The invention aims to solve the problems of low methacrylic acid conversion rate and low methyl methacrylate yield in the production process of methyl methacrylate in the prior art, and provides a modified polymerization mesoporous material catalyst, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a modified polymeric mesoporous material catalyst, wherein the method comprises:
(1) mixing and contacting a polymeric mesoporous material, p-toluenesulfonic acid and a solvent to obtain a mixture;
(2) and cooling, separating, drying and roasting the mixture to obtain the modified polymeric mesoporous material catalyst.
The second aspect of the invention provides a modified mesoporous polymeric material catalyst prepared by the preparation method.
The third aspect of the invention provides an application of the modified polymeric mesoporous material catalyst in esterification reaction of methacrylic acid and methanol.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) the modified polymeric mesoporous material catalyst provided by the invention has the advantages of stable structure, good high temperature resistance, no deformation and no swelling in the reaction process.
(2) The modified polymerization mesoporous material catalyst provided by the invention has the advantages of easily available raw materials, simple preparation method and process, easily controlled conditions and good product repeatability.
(3) The modified polymeric mesoporous material catalyst provided by the invention is used for the esterification reaction of methacrylic acid, and has mild technological conditions and low requirements on reaction devices; and the conversion rate of the methacrylic acid is high, and the selectivity of the methyl methacrylate is high.
Drawings
FIG. 1(a) is an XRD spectrum of a polymeric mesoporous material A prepared in example 1 of the present invention; FIG. 1(b) is an XRD spectrum of the modified mesoporous polymeric material catalyst A prepared in example 1 of the present invention;
FIG. 2(a) is a diagram illustrating the distribution of the pore diameter of the polymeric mesoporous material A prepared in example 1 of the present invention; FIG. 2(b) is a diagram showing a distribution of pore diameters of the modified polymeric mesoporous material catalyst A prepared in example 1 of the present invention;
FIG. 3 is a perspective electron microscope image of the polymeric mesoporous material A prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a preparation method of a modified polymeric mesoporous material catalyst, wherein the preparation method comprises the following steps:
(1) mixing and contacting a polymeric mesoporous material, p-toluenesulfonic acid and a solvent to obtain a mixture;
(2) and cooling, separating, drying and roasting the mixture to obtain the modified polymeric mesoporous material catalyst.
According to the present invention, esterification catalysts for producing methyl methacrylate are classified into homogeneous catalysts and heterogeneous catalysts in the prior art. The homogeneous catalyst mainly comprises inorganic acid solution and organic acid, has the advantages of low price and good catalytic activity, but is gradually eliminated due to the defects that the product and the catalyst are difficult to separate, the side reactions are more, the equipment is easy to corrode, and the like. The heterogeneous catalyst mainly comprises a solid acid esterification catalyst and cation exchange resin, and although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the heterogeneous catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like; in contrast to the above catalysts, the production of methyl methacrylate with (acidic) cation exchange resins as esterification catalysts is currently the main process for industrial use. The resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but the resin catalyst is an organic high polymer material, is easy to swell in an organic solvent and is easy to deform or even decompose in a high-temperature environment, and the main reason of poor temperature resistance of the resin catalyst is that the resin catalyst is a high-molecular material.
The inventors of the present invention found that: if the structural defects of the resin catalyst are to be solved and the catalytic performance of the methacrylation catalyst is to be improved, a novel material having excellent structural characteristics is selected first. Furthermore, the inventors of the present invention have found that the polymeric mesoporous material has a large pore size, and is very suitable for catalytic reactions involving macromolecules, and further, the inventors of the present invention properly modify the polymeric mesoporous material to graft acidic groups on the pore walls and pore channels, so that the polymeric mesoporous material can be used as a methacrylation reaction catalyst, and can exhibit good catalytic activity and ester selectivity.
According to the invention, the weight ratio of the polymeric mesoporous material to the p-toluenesulfonic acid to the solvent is 1: (0.2-20): (1-50), preferably 1: (0.5-10): (2-20), more preferably 1: (0.8-2): (5-17). In the invention, the weight ratio of the polymeric mesoporous material, the p-toluenesulfonic acid and the solvent is limited to be within the range, and the prepared modified polymeric mesoporous material catalyst can show good catalytic activity and ester selectivity.
According to the present invention, the solvent is an organic solvent, preferably one or more of methanol, ethanol, isopropanol or acetone, more preferably ethanol.
According to the invention, the specific surface area of the polymeric mesoporous material is 200-500m2Per g, pore volume of 0.3-1.0cm3(ii)/g, average pore diameter is 2-5 nm; preferably, the specific surface area of the composite mesoporous material is 294-317m2Per g, pore volume of 0.5-0.6cm3(ii)/g, the average pore diameter is 3.4-3.8 nm. In the present invention, the specific surface area, pore volume and average pore diameter of the polymeric mesoporous material are defined within the aforementioned ranges, which is more favorable for grafting acid groups on the pore walls and pore channels of the polymeric mesoporous material when modifying the polymeric mesoporous material.
According to the invention, in step (1), the conditions of the contacting comprise: the temperature is 60-180 ℃, preferably 90-150 ℃; the time is 1-30h, preferably 5-20 h.
According to the invention, in step (2), the cooling is carried out at room temperature and the cooling time may be from 3 to 40 hours, preferably from 5 to 24 hours, more preferably from 10 to 24 hours. Preferably, in order to achieve better contact reaction effect, the components in the mixed reaction system can be dispersed more uniformly by means of electronic stirring, electromagnetic stirring or ultrasonic dispersion and the like during the contact reaction and the cooling reaction.
According to the present invention, the separation method is not particularly required, and may be a method known in the art, for example: and removing the liquid in the mixed system by a filtration or vacuum filtration method.
According to the invention, the drying conditions are preferably: the drying temperature is 60-150 ℃, and the drying time is 3-20 h.
According to the invention, in the step (2), the conditions of the calcination treatment include: the temperature is 200-400 ℃, preferably 220-300 ℃; the time is 2-10h, preferably 3-8 h.
According to the present invention, the preparation method of the polymeric mesoporous material comprises:
(S1) mixing phenol, an aqueous formaldehyde solution and an aqueous sodium hydroxide solution to perform a first contact to obtain a product;
(S2) carrying out second contact on the product and a template agent aqueous solution, and then carrying out drying and roasting treatment to obtain the polymeric mesoporous material.
According to the present invention, in the step (S1), the concentration of the aqueous formaldehyde solution is 20 to 50%; the concentration of the sodium hydroxide aqueous solution is 0.05-0.2 mol/L.
According to the invention, the weight ratio of the phenol, the aqueous formaldehyde solution and the aqueous sodium hydroxide solution is 1: (0.5-10): (5-50).
According to the invention, the conditions of the first contact comprise: the temperature is 50-100 ℃ and the time is 1-3 h.
According to the present invention, in the step (S2), the template may be various nonionic surfactants conventionally used in the art; preferably, the templating agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer; more preferably P123 (formula EO)20PO70EO20) (ii) a The concentration of the template agent aqueous solution is 5-20%;
according to the invention, the weight ratio of the phenol to the aqueous templating agent solution is 1: (10-50).
According to the invention, the conditions of the second contact comprise: firstly, contacting for 50-250h at the temperature of 50-90 ℃; then contacting for 24-100h under the temperature condition of 60-100 ℃.
In the present invention, preferably, during the first mixing contact, the second mixing contact and the third mixing contact, the components in the mixed system can be dispersed more uniformly by means of electronic stirring, electromagnetic stirring or ultrasonic dispersion.
According to the invention, the method further comprises: in the step (S2), after the product and the template aqueous solution are subjected to the second contact, the solid sample obtained after the centrifugal separation is dried and calcined to obtain the polymeric mesoporous material.
According to the present invention, the centrifugation is a well known way of separating small particles of liquid from solid to a person skilled in the art.
According to the invention, the drying conditions comprise: the drying temperature is 60-100 deg.C, and the drying time is 5-30 h.
According to the invention, the conditions of the calcination include: the roasting temperature is 200 ℃ and 400 ℃, the roasting temperature rise rate is 0.5-3 ℃/min, and the time is 3-20 h.
The second aspect of the invention provides a modified mesoporous polymeric material catalyst prepared by the preparation method.
According to the invention, the specific surface area of the modified polymeric mesoporous material catalyst is 100-300m2Per g, pore volume of 0.2-0.8cm3(ii)/g, average pore diameter is 1-4 nm; preferably, the specific surface area of the modified polymeric mesoporous material catalyst is 171-250m2Per g, pore volume of 0.3-0.5cm3G, average pore diameter of 1.9-2.8 nm.
The third aspect of the invention provides an application of the modified polymeric mesoporous material catalyst in esterification reaction of methacrylic acid and methanol.
According to the invention, the esterification reaction conditions comprise: the temperature is 40-150 ℃, preferably 60-120 ℃; the pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the methacrylic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The mass space velocity of the methanol is 0.01-50h-1Preferably 0.1 to 30h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the XRD spectrum of the sample was obtained on an X' Pert MPD type X-ray powder diffractometer manufactured by Philips, with Cu K α ray, λ 0.154178nm, and a scan range of 2 θ 0.5 ° to 10 °. The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The sample was degassed at 350 ℃ for 4 hours under vacuum before measurement, and the specific surface area of the sample was calculated by the BET method and the pore volume was calculated by the BJH model. High resolution transmission electron microscopy images of the samples were obtained on a high resolution transmission electron microscope model TecnaiF20, produced by FEIPhilips, Netherlands.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) used in the examples and comparative examples was purchased from Sigma-Aldrich Chemistry.
Other reagents used in examples and comparative examples were purchased from national pharmaceutical group chemical agents, ltd, and the purity of the reagents was analytical grade.
Example 1
This example illustrates a modified mesoporous polymeric material catalyst prepared according to the present invention.
(1) Preparation of polymeric mesoporous material
Sequentially adding 10g of phenol, 25 g of 38% formaldehyde aqueous solution and 250 g of 0.1mol/L sodium hydroxide solution into a 1000ml three-necked bottle, heating and stirring at 72 ℃ for 1.5 hours, cooling to room temperature, adding 280 g of 10% P123 aqueous solution into the three-necked bottle, heating to 64 ℃, stirring for reaction for 120 hours, heating to 72 ℃, stirring for reaction for 48 hours, cooling to room temperature, performing centrifugal separation to obtain a solid sample, and drying the solid sample in an oven at 80 ℃ for 15 hours to obtain the raw powder of the polymerized mesoporous material. Heating the raw powder of the polymerized mesoporous material to 350 ℃ in a flowing air atmosphere at the heating rate of 1 ℃/min, and roasting at 350 ℃ for 8 hours to remove the template agent, thereby obtaining the polymerized mesoporous material A.
The specific surface area of the polymeric mesoporous material A is 317m2Per g, pore volume 0.6cm3In terms of/g, the mean pore diameter is 3.4 nm.
FIG. 1(a) is an XRD spectrum of the polymeric mesoporous material A. The XRD spectrogram shows that the polymeric mesoporous material A generates diffraction signals in a small-angle area, which indicates that the material has a good ordered mesoporous structure.
FIG. 2(a) is a diagram showing the distribution of the pore diameter of the polymeric mesoporous material A. As can be seen from the pore size distribution diagram, the material has the advantages of narrow pore size distribution, good symmetry, very uniform pore channels and most probable pore size of 3-4 nm.
FIG. 3 is a TEM image of the polymerized mesoporous material A. As can be seen from the figure, the material has an ordered cubic and hexagonal blended mesoporous channel structure.
(2) Preparation of esterification catalyst
10g of the polymeric mesoporous material, 13g of p-toluenesulfonic acid and 110g of ethanol are mixed, and the mixture is heated to 120 ℃ under the condition of stirring to react for 10 hours. After the reaction, the mixture was cooled to room temperature, and the reaction was continued for 20 hours with stirring. After the reaction is finished, a solid product is obtained through suction filtration and separation. Drying at 100 ℃ for 8h, and roasting at 250 ℃ for 4h to obtain the modified polymeric mesoporous material catalyst A.
The specific surface area of the modified mesoporous polymeric material catalyst A is 234m2Per g, pore volume 0.5cm3In terms of/g, the mean pore diameter is 2.5 nm.
FIG. 1(b) is an XRD spectrum of the modified mesoporous polymeric material catalyst A. It is obvious from the XRD spectrogram that the polymeric mesoporous material catalyst a still maintains a typical mesoporous structure after being modified.
FIG. 2(b) is a diagram showing the distribution of the pore diameter of the modified mesoporous polymeric material catalyst A. As can be seen from the pore size distribution, the channels of the catalyst are still very uniform, and the most probable pore size is between 2 and 3 nm.
(3) Evaluation of the Properties of the methacrylation reaction
The performance of the catalyst in the methacrylation reaction was evaluated on a fixed bed reactor. 5.0 g of modified polymeric mesoporous material catalyst A is filled into a stainless steel fixed bed reactor with the inner diameter of 8mm, the reaction temperature is 95 ℃, the reaction pressure is 0.3MPa, and the weight space velocity of methacrylic acid is 1.0h-1The weight space velocity of the methanol is 1.6h-1The reaction time was 50 hours. The product was cooled and analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatographic column and hydrogen flame detector (FID), using programmed temperature and quantitative analysis with calibration factors. The reaction results are shown in Table 3.
Examples 2 to 3
This example illustrates a modified mesoporous polymeric material catalyst prepared according to the present invention.
The preparation conditions of the polymeric mesoporous material of the step (1) in example 1 were changed to obtain polymeric mesoporous materials B and C. The specific surface area, pore volume and average pore diameter of the polymeric mesoporous materials B and C are shown in table 1.
Modified mesoporous polymeric material catalysts B and C were obtained by changing the preparation conditions of the modified mesoporous polymeric material catalyst of step (2) in example 1. The specific surface area, pore volume and average pore diameter of the modified polymeric mesoporous material catalysts B and C are shown in table 2.
The catalysts B and C were tested for their catalytic performance according to the method for evaluating the performance of the methacrylation reaction of step (3) in example 1. The results of the catalyst reaction performance evaluation are shown in Table 3.
Comparative example 1
A modified polymeric mesoporous material catalyst was prepared in the same manner as in example 1, except that: the catalytic performance of the ceramic balls (non-catalyst) was tested according to the methacrylation reaction performance evaluation method of the step (3) of example 1, with the elimination of the step (1) and the step (2) of example 1.
The results of the reaction property evaluations are shown in Table 3.
Comparative example 2
A modified polymeric mesoporous material catalyst was prepared in the same manner as in example 1, except that: the catalytic performance of the resin catalyst was tested according to the methacrylation reaction performance evaluation method of the step (3) in example 1, with the elimination of the step (1) and the step (2) in example 1.
The results of the reaction property evaluations are shown in Table 3.
Comparative example 3
This example illustrates a modified mesoporous polymeric material catalyst prepared according to the present invention.
A modified polymeric mesoporous material catalyst was prepared in the same manner as in example 1, except that: the modified mesoporous polymeric material catalyst D was obtained by changing the preparation conditions of the modified mesoporous polymeric material catalyst of step (2) in example 1.
The specific surface area, pore volume and average pore diameter of the modified polymeric mesoporous material catalyst D are shown in table 2.
The catalyst performance of catalyst D was tested according to the method for evaluating the performance of the methacrylation reaction of step (3) in example 1. The results of the catalyst reaction performance evaluation are shown in Table 3.
TABLE 1
Figure BDA0002787140850000101
Figure BDA0002787140850000111
TABLE 2
Figure BDA0002787140850000112
TABLE 3
Figure BDA0002787140850000113
As can be seen from Table 3, the modified mesoporous polymeric material catalyst provided by the present invention can directly convert methacrylic acid and methanol to generate methyl methacrylate. The modified polymerization mesoporous material catalyst provided by the invention can obtain the methacrylic acid conversion rate of more than 91% and the methyl methacrylate selectivity of more than 99%.
Comparing the data of example 1 and comparative example 1, it can be seen that if the ceramic beads are used instead of the modified polymeric mesoporous material catalyst to be loaded into the reactor, the conversion rate of methacrylic acid is very low and no methyl methacrylate is generated.
Comparing the data of example 1 and comparative example 2, it can be seen that the conversion rate of methacrylic acid of the modified mesoporous polymeric material catalyst is improved by about 10% and the selectivity of methyl methacrylate is improved by more than 2% compared with the resin catalyst.
It can be seen from the comparison between the data of example 1 and comparative example 3 that if the conditions selected during the modification of the mesoporous polymeric material are not within the scope of the claims, the performance of the prepared catalyst is poor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. The preparation method of the modified polymeric mesoporous material catalyst is characterized by comprising the following steps:
(1) mixing and contacting a polymeric mesoporous material, p-toluenesulfonic acid and a solvent to obtain a mixture;
(2) and cooling, separating, drying and roasting the mixture to obtain the modified polymeric mesoporous material catalyst.
2. The preparation method according to claim 1, wherein the weight ratio of the polymeric mesoporous material to the p-toluenesulfonic acid to the solvent is 1: (0.2-20): (1-50), preferably 1: (0.5-10): (2-20).
3. The preparation method according to claim 1 or 2, wherein the specific surface area of the polymeric mesoporous material is 200-500m2Per g, pore volume of 0.3-1.0cm3(iv) g, average pore diameter of 2-5 nm;
preferably, the specific surface area of the polymeric mesoporous material is 294-317m2Per g, pore volume of 0.5-0.6cm3(ii)/g, the average pore diameter is 3.4-3.8 nm.
4. The production method according to claim 1, wherein, in step (1), the conditions of the contacting include: the temperature is 60-180 ℃, preferably 90-150 ℃; the time is 1-30h, preferably 5-20 h.
5. The production method according to claim 1, wherein, in the step (2), the conditions of the calcination treatment include: the temperature is 200-400 ℃, preferably 220-300 ℃; the time is 2-10h, preferably 3-8 h.
6. The method according to any one of claims 1 to 5, wherein the method for preparing the polymeric mesoporous material comprises:
(S1) mixing phenol, an aqueous formaldehyde solution and an aqueous sodium hydroxide solution for a first contact to obtain a product;
(S2) carrying out second contact on the product and a template agent aqueous solution, and then carrying out drying and roasting treatment to obtain the polymeric mesoporous material.
7. The preparation method of claim 6, wherein, in the step (S1), the concentration of the aqueous formaldehyde solution is 20-50%; the concentration of the sodium hydroxide aqueous solution is 0.05-0.2 mol/L;
preferably, the weight ratio of the phenol, the aqueous formaldehyde solution and the aqueous sodium hydroxide solution is 1: (0.5-10): (5-50);
preferably, the conditions of the first contacting include: the temperature is 50-100 ℃ and the time is 1-3 h.
8. The preparation method of claim 6, wherein, in the step (S2), the concentration of the template aqueous solution is 5-20%;
preferably, the weight ratio of the phenol to the aqueous templating agent solution is 1: (10-50);
preferably, the conditions of the second contacting include: firstly, contacting for 50-250h at the temperature of 50-90 ℃; then contacting for 24-100h under the temperature condition of 60-100 ℃;
preferably, the conditions of the calcination include: the roasting temperature is 200 ℃ and 400 ℃, the roasting temperature rise rate is 0.5-3 ℃/min, and the time is 3-20 h.
9. A modified polymerized mesoporous material catalyst prepared by the preparation method of any one of claims 1 to 8.
10. The modified polymeric mesoporous material catalyst as claimed in claim 9, wherein the specific surface area of the modified polymeric mesoporous material catalyst is 100-300m2Per g, pore volume of 0.2-0.8cm3(ii)/g, average pore diameter is 1-4 nm;
preferably, the specific surface area of the modified polymeric mesoporous material catalyst is 171-250m2Per g, pore volume of 0.3-0.5cm3(ii)/g, the average pore diameter is 1.9-2.8 nm.
11. The use of the modified mesoporous polymeric material catalyst of claim 9 or 10 in the esterification of methacrylic acid with methanol.
12. Use according to claim 11, wherein the esterification reaction conditions comprise: the temperature is 40-150 ℃, preferably 60-120 ℃; the pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the methacrylic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The mass space velocity of the methanol is 0.01-50h-1Preferably 0.1 to 30h-1。
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