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CN-122006819-A - Enhanced acidic resin catalyst and preparation method and application thereof

CN122006819ACN 122006819 ACN122006819 ACN 122006819ACN-122006819-A

Abstract

The invention belongs to the field of fine chemical engineering, and relates to an enhanced acidic resin catalyst, a preparation method and application thereof. The enhanced acid resin catalyst comprises a strong acid type cation exchange resin and Lewis acid complexed with sulfonic acid groups on the strong acid type cation exchange resin, wherein the surface acid amount of the enhanced acid resin catalyst is 1.0-2.0mmol/g, preferably 1.2-1.9mmol/g, more preferably 1.4-1.8mmol/g, and the content of the Lewis acid calculated as metal ions in the enhanced acid resin catalyst is 0.3-1.5mmol/g, preferably 0.5-1.3mmol/g, more preferably 0.7-0.11mmol/g. The catalyst provided by the invention is used for the methacrylate reaction, and can obtain higher methacrylic acid conversion rate and methacrylate selectivity.

Inventors

  • LIU HONGMEI
  • SHAO YUN
  • JIANG SHAN
  • LIU DONGBING

Assignees

  • 中国石油化工股份有限公司
  • 中石化(北京)化工研究院有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (14)

  1. 1. A reinforced acidic resin catalyst, wherein the reinforced acidic resin catalyst comprises a strong acid type cation exchange resin and a Lewis acid complexed with sulfonic acid groups on the strong acid type cation exchange resin; Wherein the surface acid amount of the enhanced acidic resin catalyst is 1.0-2.0mmol/g, preferably 1.2-1.9mmol/g, more preferably 1.4-1.8mmol/g, and the content of Lewis acid calculated as metal ion in the enhanced acidic resin catalyst is 0.3-1.5mmol/g, preferably 0.5-1.3mmol/g, more preferably 0.7-0.11mmol/g.
  2. 2. The enhanced acid resin catalyst of claim 1, wherein the strong acid cation exchange resin is selected from at least one of the group consisting of D008 ion exchange resin, D009 ion exchange resin, and DA340 ion exchange resin.
  3. 3. The reinforced acidic resin catalyst of claim 1, wherein the Lewis acid is lanthanum chloride and/or titanium tetrachloride.
  4. 4. The reinforced acidic resin catalyst according to claim 3, wherein the Lewis acid is lanthanum chloride or titanium tetrachloride, and the content of La 3+ is 0.1-0.7mmol/g, preferably 0.2-0.6mmol/g, more preferably 0.3-0.5mmol/g, and the content of Ti 4+ is 0.2-0.8mmol/g, preferably 0.3-0.7mmol/g, more preferably 0.4-0.6mmol/g.
  5. 5. The reinforced acidic resin catalyst according to claim 1, wherein the strong acid type cation exchange resin is a strong acid type cation exchange resin obtained by swelling treatment and sulfonation reinforcing treatment.
  6. 6. The enhanced acid resin catalyst of claim 5, wherein the sulfonated enhanced strong acid cation exchange resin is prepared by a preparation process comprising the steps of: (a) Carrying out a first contact reaction on the strong acid type cation exchange resin and an organic solvent, and filtering to obtain a swelled strong acid type cation exchange resin; (b) And carrying out a second contact reaction on the swelled strong acid type cation exchange resin and a sulfonating agent, and filtering to obtain the sulfonated reinforced strong acid type cation exchange resin.
  7. 7. The reinforced acidic resin catalyst according to claim 6, wherein in step (a), the organic solvent is selected from at least one of methanol, ethanol, and isopropanol; the weight ratio of the strong acid type cation exchange resin to the organic solvent is 1 (1-20), preferably 1 (2-10); The conditions of the first contact reaction comprise the temperature of 10-60 ℃ and the time of 0.5-6h; the filtration is gravity filtration or suction filtration bottle filtration.
  8. 8. The reinforced acidic resin catalyst of claim 6, wherein in step (b), the sulfonating agent is at least one of concentrated sulfuric acid, sulfamic acid, and sodium sulfite; The weight ratio of the swelled strong acid cation exchange resin to the sulfonating agent is 1 (1-10), preferably 1 (2-6); The conditions of the second contact reaction comprise the temperature of 70-120 ℃ and the time of 2-12h; The filtration is vacuum filtration or centrifugal filtration.
  9. 9. The method for preparing the reinforced acidic resin catalyst according to any one of claims 1 to 8, comprising the steps of: and (3) carrying out contact reaction on the strong acid type cation exchange resin and a Lewis acid solution to obtain a solid reactant, and filtering, washing and drying the solid reactant to obtain the enhanced acid resin catalyst.
  10. 10. The production method according to claim 9, wherein the solvent of the Lewis acid solution is selected from at least one of methanol, ethanol and isopropanol.
  11. 11. The production method according to claim 10, wherein the Lewis acid comprises lanthanum chloride and titanium tetrachloride, and the mass concentration of lanthanum chloride in the Lewis acid solution is 1.0 to 6.0wt%, and the mass concentration of titanium tetrachloride is 1.0 to 5.0wt%.
  12. 12. The process according to claim 9, wherein the weight ratio of the amount of the strong acid cation exchange resin to the Lewis acid solution is 1 (2-30), preferably 1 (4-20); the conditions of the contact reaction comprise that the temperature is 10-50 ℃ and the time is 2-8h; the drying conditions include a temperature of 50-120 ℃, preferably 70-100 ℃, for a period of 1-20 hours, preferably 2-10 hours; The filtration is at least one of gravity filtration, pressure filtration, vacuum filtration, and centrifugal filtration.
  13. 13. Use of the reinforced acidic resin catalyst according to any one of claims 1-8 in a methacrylate synthesis reaction, preferably wherein the methacrylate is methyl methacrylate.
  14. 14. A method for preparing methacrylic acid ester is characterized by comprising the steps of carrying out contact reaction on methacrylic acid, low-carbon alcohol and a catalyst; Preferably, the conditions for the contact reaction include a temperature of 40-150 ℃, preferably 60-120 ℃, a pressure of 0.01-5.0MPa, preferably 0.1-3.0MPa, a mass space velocity of methacrylic acid of 0.01-30h -1 , preferably 0.1-10h -1 , a mass space velocity of lower alcohols of 0.01-50h -1 , preferably 0.1-30h -1 , preferably alcohols of C 1 -C 4 , more preferably methanol.

Description

Enhanced acidic resin catalyst and preparation method and application thereof Technical Field The invention belongs to the field of fine chemical engineering, and particularly relates to an enhanced acidic resin catalyst, a preparation method thereof and application of the catalyst in methacrylate synthesis reaction. Background As an important organic chemical product and an important organic chemical raw material, the industrial production level and the production capacity of Methyl Methacrylate (MMA) have important influence on the development of chemical industry in China. MMA is mainly used in industries such as organic glass (PMMA), paint, textile, adhesive, leather, papermaking, floor polishing, unsaturated resin, 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. The development of the methacrylate catalyst with independent intellectual property rights and the matched process are the development demands of MMA production industry in China. Esterification catalysts are the core technology for MMA production. The traditional catalyst used to catalyze the esterification of methacrylic acid with methanol is concentrated sulfuric acid. The catalyst has high catalytic activity and low cost, but the characteristics of strong oxidizing property, dehydration property, dissolution of the concentrated sulfuric acid in a reaction system and the like also bring trouble to equipment corrosion and subsequent treatment. Therefore, it is still of positive interest to find a catalyst which combines strong catalytic activity, high selectivity and easy separation from the reaction system. Esterification catalysts for heterogeneous reactions are currently a relatively active area of research. At present, the reported catalyst capable of replacing concentrated sulfuric acid comprises strong acid type ion exchange resin, heteropolyacid, ionic liquid, solid super acid and the like, so that a good effect is obtained. Although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like. Compared with other catalysts, strong acid ion exchange resins have attracted extensive attention due to the advantages of insolubility in the reaction system, good stability, high selectivity, lower cost, easy separation, etc. The strong acid cation exchange resin is a high molecular material containing acidic groups, and is not easy to corrode production equipment because the strong acid cation exchange resin essentially belongs to a solid catalyst, so that the strong acid cation exchange resin has a large application in industrial production. However, the effective acidic sites that can be provided by strongly acidic cation exchange resin acids in the reaction are lower than those of homogeneous acidic catalysts, and the rate of catalytic esterification is slower. The main active center of the strong acid cation exchange resin is a sulfonic acid group, and the sulfonic acid group can fall off and be dissolved in a reaction system during the catalytic reaction, so that the stability of the catalyst is poor. Therefore, it is necessary to strengthen and solidify the acid center of the strong acid type cation exchange resin to improve the esterification catalytic activity thereof. Disclosure of Invention The invention aims to solve the problems of low methacrylic acid conversion rate and low methacrylic acid yield of an acid resin catalyst in the existing methacrylic acid ester production process, and provides an enhanced acid resin catalyst, a preparation method and application thereof. In order to achieve the above object, a first aspect of the present invention provides a reinforced acidic resin catalyst comprising a strong acid type cation exchange resin and a Lewis acid complexed with sulfonic acid groups on the strong acid type cation exchange resin; Wherein the surface acid amount of the enhanced acidic resin catalyst is 1.0-2.0mmol/g, preferably 1.2-1.9mmol/g, more preferably 1.4-1.8mmol/g, and the content of Lewis acid calculated as metal ion in the enhanced acidic resin catalyst is 0.3-1.5mmol/g, preferably 0.5-1.3mmol/g, more preferably 0.7-0.11mmol/g. The second aspect of the present invention provides a method for preparing the enhanced acidic resin catalyst, comprising the steps of: and (3) carrying out contact reaction on the strong acid type cation exchange resin and a Lewis acid solution