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CN-122006802-A - Supported acidic catalyst, and preparation method and application thereof

CN122006802ACN 122006802 ACN122006802 ACN 122006802ACN-122006802-A

Abstract

The invention relates to the field of fine chemical engineering, and relates to a supported acidic catalyst, and a preparation method and application thereof. The catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a mesoporous carbon material, the active component is lanthanum paratoluenesulfonate, and the content of the mesoporous carbon material is 25-55wt%, preferably 31-49 wt%, more preferably 35-44 wt%, and the content of the lanthanum paratoluenesulfonate is 45-75wt%, preferably 51-69 wt%, more preferably 56-65 wt%, based on the total weight of the loaded acidic catalyst. The supported acidic catalyst provided by the invention has the advantages of stable structure, good high temperature resistance, no toxicity, no deformation and no swelling in the reaction process, easy recovery after the reaction, mild process conditions when being used for the synthetic reaction of the oleate, and low requirements on reaction devices. The oleic acid conversion rate is high, and the oleic acid ester selectivity is high.

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 (13)

  1. 1. A supported acidic catalyst, characterized in that the catalyst comprises a carrier and an active component supported on the carrier; The carrier is a mesoporous carbon material, the active component is lanthanum paratoluenesulfonate, and the content of the mesoporous carbon material is 25-55wt%, preferably 31-49 wt%, more preferably 35-44 wt%, and the content of the lanthanum paratoluenesulfonate is 45-75wt%, preferably 51-69 wt%, more preferably 56-65 wt%, based on the total weight of the supported acidic catalyst.
  2. 2. The supported acidic catalyst according to claim 1, wherein the mesoporous carbon material is a high specific surface area mesoporous carbon material having a specific surface area of 2500-3500m 2 /g, preferably 2800-3000m 2 /g, a pore volume of 1.0-2.5cm 3 /g, preferably 2.0-2.5cm 3 /g, and an average pore diameter of 10-14nm, preferably 13-14nm.
  3. 3. The supported acidic catalyst according to claim 1, wherein the specific surface area of the supported acidic catalyst is 1100-2000m 2 /g, the pore volume is 1.2-1.5cm 3 /g, and the average pore diameter is 7-11nm.
  4. 4. A process for the preparation of a supported acidic catalyst as claimed in any one of claims 1 to 3, comprising the steps of: (1) Mixing mesoporous carbon material and lanthanum salt, and performing ball milling treatment to obtain a catalyst intermediate; (2) And (3) carrying out contact reaction on the catalyst intermediate and a p-toluenesulfonic acid aqueous solution to obtain a solid product, and washing, drying and roasting to obtain the supported acidic catalyst.
  5. 5. The preparation method according to claim 4, wherein in the step (1), the lanthanum salt is at least one of lanthanum carbonate, lanthanum nitrate and lanthanum chloride.
  6. 6. The preparation method according to claim 4, wherein in the step (1), the mixing weight ratio of the mesoporous carbon material and lanthanum salt is 1 (0.5-4), preferably 1 (1.0-2.5).
  7. 7. The method according to claim 4, wherein in the step (1), the ball milling treatment is carried out under conditions of a ball mill rotation speed of 300-500r/min, a temperature of 30-80 ℃ and a time of 2-10 hours.
  8. 8. The production process according to claim 4, wherein in the step (2), the aqueous p-toluenesulfonic acid solution has a mass concentration of 2 to 20wt%, preferably 5 to 15wt%.
  9. 9. The process according to claim 4, wherein in step (2), the weight ratio of the catalyst intermediate to the aqueous p-toluenesulfonic acid solution is 1 (5-30), preferably 1 (6-15).
  10. 10. The process according to claim 4, wherein in the step (2), the conditions of the contact reaction include a temperature of 70 to 140 ℃, preferably 90 to 120 ℃, for a time of 2 to 10 hours, preferably 3 to 8 hours.
  11. 11. The production method according to claim 4, wherein in the step (2), the filtration is at least one of gravity filtration, pressure filtration, vacuum filtration and centrifugal filtration; the drying conditions include a temperature of 80-150deg.C, preferably 100-130deg.C, and a time of 2-20 hr, preferably 3-12 hr; The conditions for the calcination include a temperature of 200-300 ℃, preferably 220-280 ℃, and a time of 1-10 hours, preferably 2-5 hours.
  12. 12. Use of a supported acidic catalyst according to any one of claims 1-3 in an oleate synthesis reaction, preferably wherein the oleate is methyl oleate.
  13. 13. A preparation method of oleic acid ester is characterized by comprising the steps of carrying out contact reaction on oleic acid, low-carbon alcohol and a catalyst; Preferably, the conditions for the contact reaction include a temperature of 40-100 ℃, preferably 50-80 ℃, a pressure of 0.01-5.0MPa, preferably 0.1-3.0MPa, a weight ratio of catalyst to oleic acid to lower alcohol of 1:2-50:1-10, preferably 1:5-20:2-5, a time of 1-12h, preferably 2-8h, and the lower alcohol is preferably an alcohol of C 1 -C 4 , more preferably methanol.

Description

Supported acidic catalyst, and preparation method and application thereof Technical Field The invention relates to the field of fine chemical engineering, in particular to a supported acidic catalyst, a preparation method thereof and application of the catalyst in oleate synthesis reaction. Background Methyl oleate is an important organic chemical product, is mainly used as a surface active basic raw material, leather and rubber softener, fluorescent-free slurry lubricant for petroleum exploration, plastic plasticizer, water repellent agent and toughening agent of resin, and is also commonly used for organic synthesis. In addition, methyl oleate may be used as an intermediate for detergents, emulsifiers, wetting agents and stabilizers, and is widely used in various emulsified products, as well as a solvent for fragrances and as a lubricant for spray products. At present, the traditional process for industrially producing methyl oleate uses inorganic acid or organic acid (for example, concentrated sulfuric acid, concentrated hydrochloric acid or p-toluenesulfonic acid) as a catalyst to catalyze the esterification reaction of oleic acid and methanol to produce methyl oleate. The inorganic acid or organic acid catalyst has the advantages of low price, but has the defects of serious environmental pollution, high requirements on equipment materials, more side reactions, more byproducts, difficult separation and purification of the obtained products, and the like. In recent years, the production process of the oleic acid ester in China is continuously developed, the production capacity of the oleic acid ester is continuously improved, the solid acid or the cation exchange resin is used as a catalyst for synthesizing the methyl oleate, the process is greatly developed, and the process is widely applied to industrial production. The solid catalyst has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, the reaction speed of the catalyst is slower, and the yield of the ester is lower. The cation exchange resin has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, the cation exchange resin itself has poor heat resistance (generally suitable for esterification reactions at temperatures of 150 ℃ or less), a small specific surface area and a small pore volume, and is susceptible to swelling, and has poor reactivity as a supported acidic catalyst and low ester yield. Compared with the resin catalyst, the hydrogen zeolite molecular sieve has a certain pore channel structure and surface acidity, and is suitable for catalyzing esterification reaction. However, the zeolite molecular sieve has smaller pore canal size (0.5-0.7 nm), can inhibit the diffusion of macromolecular products in the reaction, has smaller number of acid sites on the surface of the zeolite molecular sieve, and has lower efficiency of catalyzing the esterification reaction. Along with the increasing demand of methyl oleate, the synthesis of methyl oleate by adopting a green environment-friendly process has wide prospect. At present, the immobilized esterification catalyst is more and more paid attention to in ester synthesis reaction. For researchers, development of an esterification catalyst with excellent performance, improvement of reaction efficiency and inhibition of by-product generation are important working directions in the future. Disclosure of Invention The invention aims to solve the problems of excessive side reactions and serious environmental pollution of a homogeneous acid catalyst used in the existing oleate production process, and the problems of poor catalytic activity, low ester selectivity and the like of a solid acid catalyst and an acidic cation exchange resin catalyst. A supported acidic catalyst is provided which is useful in the synthesis of oleate and which provides higher oleic acid conversion and oleate selectivity. In order to achieve the above object, a first aspect of the present invention provides a supported acidic catalyst comprising a carrier and an active component supported on the carrier; The carrier is a mesoporous carbon material, the active component is lanthanum paratoluenesulfonate, and the content of the mesoporous carbon material is 25-55wt%, preferably 31-49 wt%, more preferably 35-44 wt%, and the content of the lanthanum paratoluenesulfonate is 45-75wt%, preferably 51-69 wt%, more preferably 56-65 wt%, based on the total weight of the supported acidic catalyst. The second aspect of the present invention provides a method for preparing the supported acidic catalyst, comprising the steps of: (1) Mixing mesoporous carbon material and lanthanum salt, and performing ball milling treatment to obtain a catalyst intermediate; (2) And (3) carrying out contact reaction on the catalyst intermediate and a p-toluenesulfonic acid aqueous solution to obtain a soli