CN114515601B - Modified polymeric mesoporous material catalyst and preparation method and application thereof - Google Patents
Modified polymeric mesoporous material catalyst and preparation method and application thereof Download PDFInfo
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
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- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- 239000012752 auxiliary agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/64—Pore diameter
- 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)
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
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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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- C—CHEMISTRY; METALLURGY
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
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- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of fine chemical engineering, and discloses a modified polymeric mesoporous material catalyst, 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 polymer mesoporous material catalyst. The modified polymeric mesoporous material catalyst is used for the methacrylate reaction, and can obtain higher methacrylic acid conversion rate and methyl methacrylate selectivity.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a modified polymeric mesoporous material catalyst, a preparation method and application thereof.
Background
Methyl Methacrylate (MMA) is mainly used in industries such as organic glass (PMMA) coating, textile, adhesive, leather, papermaking, floor polishing, unsaturated resin modification, methacrylic acid higher esters, wood impregnating compound, printing and dyeing auxiliary agent, plasticizer of plastics and the like. In recent years, the demands of MMA polymers, profiles, plates, coatings, emulsions and the like at home and abroad are increased, the application fields are continuously widened, and the rapid development of MMA industry is promoted. At present, the domestic methyl methacrylate production technology is still in the starting stage, and the development of a methacrylate catalyst and a matched process is the development requirement facing the MMA production industry in China.
For the esterification reaction of methacrylic acid and methanol, the traditional production process using inorganic acid such as sulfuric acid, phosphoric acid, boric acid and the like as a catalyst is gradually eliminated, and the organic acid such as p-toluenesulfonic acid and the like as a catalyst has the defects of serious environmental pollution, low selectivity and difficult separation of products. At present, acid cation exchange resin is widely used in industry for producing methyl methacrylate, and the cation exchange resin has the advantages of good stability, high selectivity, lower cost, easy separation and the like in esterification reaction. However, the cation exchange resin itself has poor heat resistance (generally, decomposition is carried out at a temperature of not higher than 250 ℃), a small specific surface area and a small pore volume, and the cation exchange resin is easily swelled, has poor reactivity as an esterification catalyst, and has low ester yield.
Compared with the resin catalyst, the inorganic mesoporous material has the structural advantages of large specific surface area and large pore volume and the performance advantages of high temperature resistance. However, the surface of the all-silicon mesoporous molecular sieve having a basic framework structure composed of silicon and oxygen does not contain a functional group, and does not exhibit 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, the development of novel esterification catalysts and the improvement of the catalytic activity, the ester selectivity and the stability of the novel esterification catalysts are urgent for researchers of the methacrylate catalysts.
Disclosure of Invention
The invention aims to solve the problems of low methacrylic acid conversion rate and low methyl methacrylate yield in the methyl methacrylate production process in the prior art, and provides a modified polymeric mesoporous material catalyst, a preparation method and application thereof.
In order to achieve the above object, the 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 polymer mesoporous material catalyst.
The second aspect of the invention provides a modified polymeric mesoporous 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 of 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 polymeric 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 methacrylate reaction, and has mild process conditions and low requirements on reaction devices; and the conversion rate of methacrylic acid is high, and the selectivity of 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 a modified polymeric mesoporous material catalyst A prepared in example 1 of the present invention;
FIG. 2 (a) is a pore size distribution diagram of a polymeric mesoporous material A prepared in example 1 of the present invention; FIG. 2 (b) is a pore size distribution diagram of the modified polymeric mesoporous material catalyst A prepared in example 1 of the present invention;
fig. 3 is a perspective electron microscope picture of the polymeric mesoporous material a prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of 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 polymer mesoporous material catalyst.
According to the present invention, in the prior art, esterification catalysts for producing methyl methacrylate are classified into homogeneous catalysts and heterogeneous catalysts. The homogeneous catalyst mainly comprises an inorganic acid solution and an organic acid, and has the advantages of low price and good catalytic activity, but the defects of difficult separation of products and the catalyst, more side reactions, easy corrosion to equipment and the like are eliminated. The heterogeneous catalyst mainly comprises a solid acid esterification catalyst and cation exchange resin, and the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, but has the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like, and is rarely applied to industrial production; in contrast to the catalysts described above, the production of methyl methacrylate using (acidic) cation exchange resins as esterification catalysts is currently the main process for industrial application. The resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but is an organic polymer material, is easy to swell in an organic solvent, is easy to deform and even decompose in a high-temperature environment, and is a main reason for poor temperature resistance of the resin catalyst.
The inventors of the present invention found that: if the structural defect of the resin catalyst itself is to be solved, the catalytic performance of the methacrylation catalyst is improved, and first, a novel material with excellent structural characteristics is to be selected. Furthermore, the invention thermally discovers that the polymer mesoporous material has larger pore diameter, is very suitable for catalytic reaction involving macromolecules, and further, the inventor of the invention properly modifies the polymer mesoporous material to enable acid groups to be grafted in the pore walls and pore channels, so that the polymer mesoporous material can be used as a catalyst for the methacrylate reaction, and can show good catalytic activity and ester selectivity.
According to the invention, the weight ratio of the polymeric mesoporous material, the p-toluenesulfonic acid and 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 to the p-toluenesulfonic acid to 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 200-500m 2 Per gram, pore volume of 0.3-1.0cm 3 /g, average pore size of 2-5nm; preferably, the specific surface area of the mesoporous material is 294-317m 2 Per gram, pore volume of 0.5-0.6cm 3 And/g, the average pore diameter is 3.4-3.8nm. In the invention, the specific surface area, the pore volume and the average pore diameter of the polymeric mesoporous material are limited to be within the ranges, so that the acidic groups can be grafted on the pore walls and pore channels of the polymeric mesoporous material when the polymeric mesoporous material is modified.
According to the invention, in step (1), the conditions of the contacting include: the temperature is 60-180deg.C, preferably 90-150deg.C; the time is 1-30 hours, preferably 5-20 hours.
According to the invention, in step (2), the cooling is carried out at room temperature for a period of time which 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 during the contact reaction and during the cooling reaction.
The separation method according to the present invention is not particularly limited and may be a method known in the art, for example: the liquid in the mixed system is removed by filtration or vacuum filtration.
According to the invention, the drying conditions are preferably: the drying temperature is 60-150 ℃ and the drying time is 3-20h.
According to the present invention, in step (2), the conditions of the firing treatment include: the temperature is 200-400 ℃, preferably 220-300 ℃; the time is 2-10 hours, preferably 3-8 hours.
According to the invention, the preparation method of the polymeric mesoporous material comprises the following steps:
(S1) mixing phenol, formaldehyde aqueous solution and sodium hydroxide aqueous solution for first contact to obtain a product;
(S2) carrying out second contact on the product and the template agent aqueous solution, and then drying and roasting to obtain the polymeric mesoporous material.
According to the invention, in step (S1), the aqueous formaldehyde solution has a concentration of 20-50%; the concentration of the sodium hydroxide aqueous solution is 0.05-0.2mol/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 present invention, the conditions of the first contact include: the temperature is 50-100deg.C, and the time is 1-3h.
According to the present invention, in step (S2), the template may be various nonionic surfactants conventionally used in the art; preferably, the template agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer; more preferably P123 (EO 20 PO 70 EO 20 )；The concentration of the template agent aqueous solution is 5-20%;
according to the invention, the weight ratio of the phenol to the aqueous template solution is 1: (10-50).
According to the present invention, the conditions of the second contact include: firstly, contacting for 50-250h under the temperature condition of 50-90 ℃; then the mixture is contacted for 24 to 100 hours under the temperature condition of 60 to 100 ℃.
In the present invention, preferably, in the first mixing contact, the second mixing contact and the third mixing contact, the components in the mixed system may 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), the product and the template agent aqueous solution are subjected to second contact, and a solid sample obtained after centrifugal separation is dried and roasted to obtain the polymeric mesoporous material.
According to the invention, the centrifugation is a means of separating small particles of liquid from small particles of solid, which is well known to a person skilled in the art.
According to the present invention, the drying conditions include: the drying temperature is 60-100deg.C, and the drying time is 5-30h.
According to the invention, the conditions of the calcination include: the roasting temperature is 200-400 ℃, the roasting temperature rising rate is 0.5-3 ℃/min, and the time is 3-20h.
The second aspect of the invention provides a modified polymeric mesoporous material catalyst prepared by the preparation method.
According to the invention, the specific surface area of the modified polymeric mesoporous material catalyst is 100-300m 2 Per gram, pore volume of 0.2-0.8cm 3 /g, average pore size of 1-4nm; preferably, the specific surface area of the modified polymer mesoporous material catalyst is 171-250m 2 Per gram, pore volume of 0.3-0.5cm 3 And/g, the average pore diameter is 1.9-2.8nm.
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 inventionThe esterification conditions include: the temperature is 40-150deg.C, preferably 60-120deg.C; the pressure is 0.01-5.0MPa, preferably 0.1-3.0MPa; the mass airspeed of the methacrylic acid is 0.01 to 30h -1 Preferably 0.1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.01 to 50h -1 Preferably 0.1-30h -1 。
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the XRD pattern of the sample was obtained on an X' Pert MPD X-ray powder diffractometer manufactured by Philips company, cu ka radiation, λ= 0.154178nm, scan range 2θ=0.5 ° to 10 °. The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model. High resolution transmission electron microscopy pictures of the samples were obtained on a TecnaiF20 high resolution transmission electron microscope manufactured by feiphiips company, netherlands.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymers (P123) used in the examples and comparative examples were purchased from Sigma-Aldrich Chemistry company.
The other reagents used in the examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
The embodiment aims at describing the modified polymer mesoporous material catalyst prepared by the invention.
(1) Preparation of polymeric mesoporous materials
10g of phenol, 25 g of 38% formaldehyde aqueous solution and 250 g of 0.1mol/L sodium hydroxide solution are sequentially added into a 1000ml three-port bottle, heated, stirred and stirred at 72 ℃ for 1.5 hours, cooled to room temperature, 280 g of 10% P123 aqueous solution is added into the three-port bottle, heated to 64 ℃, stirred and reacted for 120 hours, then heated to 72 ℃, stirred and reacted for 48 hours, cooled to room temperature, centrifugally separated to obtain a solid sample, and the solid sample is put into an oven at 80 ℃ to be dried for 15 hours to obtain the raw powder of the polymeric mesoporous material. And heating the raw powder of the polymeric mesoporous material to 350 ℃ according to the heating rate of 1 ℃/min in flowing air atmosphere, and roasting at 350 ℃ for 8 hours to remove the template agent to obtain the polymeric mesoporous material A.
The specific surface area of the polymeric mesoporous material A is 317m 2 Per gram, pore volume of 0.6cm 3 And/g, average pore diameter of 3.4nm.
FIG. 1 (a) is an XRD spectrum of a polymeric mesoporous material A. The XRD spectrum can obviously show that the polymerized mesoporous material A has diffraction signals in small angle areas, which proves that the material has a good ordered mesoporous structure.
FIG. 2 (a) is a pore size distribution diagram 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 transmission electron microscope image of the polymeric mesoporous material a. The graph shows that the material has ordered cubic and hexagonal blending mesoporous pore canal structure.
(2) Preparation of esterification catalyst
10g of polymeric mesoporous material, 13g of p-toluenesulfonic acid and 110g of ethanol are mixed and heated to 120 ℃ with stirring for reaction for 10h. After the reaction, the mixture was cooled to room temperature, and the reaction was continued with stirring for 20 hours. After the reaction is finished, a solid product is obtained through suction filtration and separation. Drying at 100 ℃ for 8 hours, and roasting at 250 ℃ for 4 hours to obtain the modified polymeric mesoporous material catalyst A.
The specific surface area of the modified polymeric mesoporous material catalyst A is 234m 2 Per gram, pore volume of 0.5cm 3 And/g, average pore diameter of 2.5nm.
FIG. 1 (b) is an XRD spectrum of a modified polymeric mesoporous material catalyst A. As is evident from the XRD pattern, the polymeric mesoporous material catalyst a retains the typical mesoporous structure after modification.
FIG. 2 (b) is a pore size distribution diagram of the modified polymeric mesoporous material catalyst A. The pore size distribution diagram shows that the pore canal of the catalyst is still very uniform, and the most probable pore size is between 2 and 3 nm.
(3) Evaluation of the Property of the methacrylation reaction
The catalyst was evaluated for its methacrylation reaction performance 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 -1 The weight space velocity of methanol is 1.6h -1 The reaction time was 50 hours. After cooling the product was analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatography column and hydrogen flame detector (FID), and quantitative analysis was performed using a calibration factor with programmed temperature. The reaction results are shown in Table 3.
Examples 2 to 3
The embodiment aims at describing the modified polymer mesoporous material catalyst prepared by the invention.
The preparation conditions of the polymeric mesoporous materials of step (1) in example 1 were changed to obtain polymeric mesoporous materials B and C. The specific surface areas, pore volumes and average pore diameters of the polymeric mesoporous materials B and C are listed in table 1.
The preparation conditions of the modified polymeric mesoporous material catalyst of step (2) in example 1 were changed to obtain modified polymeric mesoporous material catalysts B and C. The specific surface area, pore volume and average pore size of the modified polymeric mesoporous material catalysts B and C are listed in table 2.
Catalysts B and C were tested for their catalytic performance according to the method of evaluation of the methacrylation reaction performance of step (3) in example 1. The results of the catalyst reactivity 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: step (1) and step (2) in example 1 were omitted, and the catalytic performance of the porcelain ball (non-catalyst) was tested according to the method for evaluating the methacrylation reaction performance of step (3) in example 1.
The results of the evaluation of the reactivity 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: step (1) and step (2) in example 1 were omitted, and the catalytic performance of the resin catalyst was tested according to the method for evaluating the methacrylation reaction performance of step (3) in example 1.
The results of the evaluation of the reactivity are shown in Table 3.
Comparative example 3
The embodiment aims at describing the modified polymer mesoporous material catalyst prepared by the invention.
A modified polymeric mesoporous material catalyst was prepared in the same manner as in example 1, except that: changing the preparation condition of the modified polymeric mesoporous material catalyst in the step (2) in the example 1 to obtain a modified polymeric mesoporous material catalyst D.
The specific surface area, pore volume and average pore size of the modified polymeric mesoporous material catalyst D are listed in table 2.
Catalyst D was tested for its catalytic performance according to the method of evaluating the methacrylation reaction performance of step (3) in example 1. The results of the catalyst reactivity evaluation are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
From Table 3, it can be seen that the modified mesoporous polymeric material catalyst provided by the invention can directly convert methacrylic acid and methanol to methyl methacrylate. The modified mesoporous polymeric 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%.
As can be seen from the data of comparative example 1 and comparative example 1, if ceramic balls are used instead of the modified polymeric mesoporous material catalyst to be charged into the reactor, the conversion of methacrylic acid is extremely low, and no methyl methacrylate is produced.
As can be seen from the data of comparative examples 1 and 2, the conversion of methacrylic acid of the modified polymeric mesoporous material catalyst was improved by about 10% and the selectivity of methyl methacrylate was also improved by 2% or more, as compared with the resin catalyst.
The data of comparative example 1 and comparative example 3 show that if the conditions selected during modification of the polymeric mesoporous material are outside the scope of the claims, the catalyst prepared has poor performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (21)
1. The preparation method of the modified polymeric mesoporous material catalyst is characterized by comprising the following steps of:
(1) Mixing and contacting a polymeric mesoporous material, p-toluenesulfonic acid and a solvent to obtain a mixture; the specific surface area of the polymeric mesoporous material is 200-500m 2 Per gram, pore volume of 0.3-1.0cm 3 /g, average pore size of 2-5nm;
(2) Cooling, separating, drying and roasting the mixture to obtain a modified polymeric mesoporous material catalyst;
the preparation method of the polymeric mesoporous material comprises the following steps:
(S1) mixing phenol, formaldehyde aqueous solution and sodium hydroxide aqueous solution for first contact to obtain a product;
(S2) carrying out second contact on the product and the template agent aqueous solution, and then drying and roasting to obtain the polymeric mesoporous material.
2. The preparation method of claim 1, wherein the weight ratio of the polymeric mesoporous material, the p-toluenesulfonic acid and the solvent is 1: (0.2-20): (1-50).
3. The preparation method according to claim 2, wherein the weight ratio of the polymeric mesoporous material, p-toluenesulfonic acid and solvent is 1: (0.5-10): (2-20).
4. The preparation method according to any one of claims 1 to 3, wherein the specific surface area of the polymeric mesoporous material is 294 to 317m 2 Per gram, pore volume of 0.5-0.6cm 3 And/g, the average pore diameter is 3.4-3.8nm.
5. The production method according to claim 1, wherein in step (1), the conditions of the contact include: the temperature is 60-180 ℃ and the time is 1-30h.
6. The production method according to claim 5, wherein in the step (1), the conditions of the contact include: the temperature is 90-150 ℃ and the time is 5-20h.
7. The production method according to claim 1, wherein in the step (2), the conditions of the calcination treatment include: the temperature is 200-400 ℃ and the time is 2-10h.
8. The production method according to claim 7, wherein in the step (2), the conditions of the calcination treatment include: the temperature is 220-300 ℃ and the time is 3-8h.
9. The production method according to claim 1, wherein, in the step (S1), the concentration of the aqueous formaldehyde solution is 20 to 50%; the concentration of the sodium hydroxide aqueous solution is 0.05-0.2mol/L.
10. The production method according to claim 1, wherein the weight ratio of the phenol, the aqueous formaldehyde solution and the aqueous sodium hydroxide solution is 1: (0.5-10): (5-50).
11. The method of manufacturing according to claim 1, wherein the conditions of the first contact include: the temperature is 50-100deg.C, and the time is 1-3h.
12. The production method according to claim 1, wherein in the step (S2), the concentration of the aqueous template solution is 5 to 20%.
13. The preparation method according to claim 1, wherein the weight ratio of the phenol to the aqueous template solution is 1: (10-50).
14. The production method according to claim 1, wherein the conditions of the second contact include: firstly, contacting for 50-250h under the temperature condition of 50-90 ℃; then the mixture is contacted for 24 to 100 hours under the temperature condition of 60 to 100 ℃.
15. The production method according to claim 1, wherein the conditions of calcination include: the roasting temperature is 200-400 ℃, the roasting temperature rising rate is 0.5-3 ℃/min, and the time is 3-20h.
16. A modified polymeric mesoporous material catalyst prepared by the method of any one of claims 1-15.
17. The modified polymeric mesoporous material catalyst of claim 16, wherein the modified polymeric mesoporous material catalyst ratioSurface area of 100-300m 2 Per gram, pore volume of 0.2-0.8cm 3 And/g, the average pore diameter is 1-4nm.
18. The modified polymeric mesoporous material catalyst of claim 17, having a specific surface area of from 171 to 250m 2 Per gram, pore volume of 0.3-0.5cm 3 And/g, the average pore diameter is 1.9-2.8nm.
19. Use of a modified polymeric mesoporous material catalyst according to any one of claims 16 to 18 in the esterification of methacrylic acid with methanol.
20. The use of claim 19, wherein the esterification reaction conditions comprise: the temperature is 40-150 ℃; the pressure is 0.01-5.0MPa; the mass airspeed of the methacrylic acid is 0.01 to 30h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.01 to 50h -1 。
21. The use of claim 20, wherein the esterification reaction conditions comprise: the temperature is 60-120 ℃; the pressure is 0.1-3.0Mpa; the mass airspeed of the methacrylic acid is 0.1 to 10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.1 to 30h -1 。
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