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CN-121972216-A - Catalyst for tartaric acid synthesis and preparation method thereof

CN121972216ACN 121972216 ACN121972216 ACN 121972216ACN-121972216-A

Abstract

The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for tartaric acid synthesis and a preparation method thereof. According to the invention, the TS-1 molecular sieve is used as a matrix, vanadium and niobium are doped into the TS-1 molecular sieve, and further modification of phosphotungstic acid on the surface of the TS-1 molecular sieve doped with vanadium and niobium is adopted, so that the prepared catalyst shows excellent catalytic activity in the process of preparing tartaric acid by using maleic anhydride as a raw material, the prepared tartaric acid has high yield, and the product is easy to separate.

Inventors

  • MENG QINGCHEN
  • YU RUJUN
  • CHEN YANYAN
  • GUAN FENGGANG

Assignees

  • 山东河清化工科技有限公司

Dates

Publication Date
20260505
Application Date
20260128

Claims (10)

  1. 1. The preparation method of the catalyst for tartaric acid synthesis is characterized by comprising the following steps: S1, mixing tetraethyl orthosilicate and an aqueous solution containing tetrapropylammonium hydroxide to form a solution A, and mixing tetrabutyl titanate and isopropanol to form a solution B; s2, mixing ammonium metavanadate, niobium chloride, a solution A and a solution B, fully and uniformly stirring to form a mixed solution, adding ammonium carbonate into the mixed solution, performing hydrothermal crystallization treatment, and then calcining in air to obtain a vanadium-niobium doped TS-1 molecular sieve; S3, dissolving phosphotungstic acid in ethanol to obtain a phosphotungstic acid alcohol solution, and uniformly dispersing quaternary ammonium salt in the phosphotungstic acid alcohol solution to obtain a modified solution; and S4, adding the TS-1 molecular sieve doped with vanadium and niobium into the modified solution, fully stirring, standing for 2-3 hours, filtering, and drying to obtain the catalyst for tartaric acid synthesis.
  2. 2. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the molar ratio of tetrapropylammonium hydroxide to tetraethyl orthosilicate is 0.3-0.5:1, the mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 20-25%, and the molar ratio of isopropanol to tetrabutyl titanate is 60-70:1.
  3. 3. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the molar ratio of ammonium metavanadate, niobium chloride, tetraethyl orthosilicate, tetrabutyl titanate and ammonium carbonate is 0.03-0.05:0.01-0.02:1:0.03-0.05:0.05-0.2.
  4. 4. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the hydrothermal crystallization treatment is carried out at 160-180 ℃ for 28-32 hours.
  5. 5. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the calcination temperature is 500-550 ℃, the calcination time is 2-3 h, and the temperature rising rate is 2-5 ℃ per minute.
  6. 6. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the quaternary ammonium salt is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride or octadecyltrimethylammonium bromide.
  7. 7. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the mass ratio of the quaternary ammonium salt to the phosphotungstic acid alcohol solution in the modified solution is 1:10.
  8. 8. The method for preparing a catalyst for tartaric acid synthesis according to claim 1, wherein the mass concentration of the phosphotungstic acid in the phosphotungstic acid alcohol solution is 10% -20%; The adding ratio of the TS-1 molecular sieve doped with vanadium and niobium to the modifying solution is 1-2 g/10 mL.
  9. 9. The catalyst for tartaric acid synthesis according to any one of claims 1 to 8.
  10. 10. Use of the catalyst of claim 9 in the preparation of tartaric acid from maleic anhydride.

Description

Catalyst for tartaric acid synthesis and preparation method thereof Technical Field The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for tartaric acid synthesis and a preparation method thereof. Background Tartaric acid is commonly used for preparing medicines, mordants, tanning agents and the like, and is a relatively expensive chiral resolving agent which is also relatively more used. It is also a sour agent in food additives, and the sour feeling is better than that of malic acid, lactic acid and the like. The largest application of tartaric acid is beverage additives, which are also raw materials for the pharmaceutical industry. In the mirror making industry, tartaric acid is an important auxiliary agent and a reducing agent, and can control the forming speed of silver mirrors to obtain a very uniform coating. The existing chemical synthesis of tartaric acid mainly uses maleic anhydride as a raw material, hydrogen peroxide as an oxidant and tungstic acid as a catalyst, and is catalyzed and oxidized to generate epoxy succinic acid, then tartaric acid can be obtained through hydrolysis, and then tartaric acid finished products are obtained through cooling, crystallization, separation and drying. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a catalyst for tartaric acid synthesis and a preparation method thereof, wherein the catalyst has excellent catalytic activity in the process of preparing tartaric acid by taking maleic anhydride as a raw material, and the prepared tartaric acid has high yield and is easy to separate. The first aspect of the invention provides a method for preparing a catalyst for tartaric acid synthesis, which comprises the following steps: S1, mixing tetraethyl orthosilicate and an aqueous solution containing tetrapropylammonium hydroxide to form a solution A, and mixing tetrabutyl titanate and isopropanol to form a solution B; s2, mixing ammonium metavanadate, niobium chloride, a solution A and a solution B, fully and uniformly stirring to form a mixed solution, adding ammonium carbonate into the mixed solution, performing hydrothermal crystallization treatment, and then calcining in air to obtain a vanadium-niobium doped TS-1 molecular sieve; S3, dissolving phosphotungstic acid in ethanol to obtain a phosphotungstic acid alcohol solution, and uniformly dispersing quaternary ammonium salt in the phosphotungstic acid alcohol solution to obtain a modified solution; and S4, adding the TS-1 molecular sieve doped with vanadium and niobium into the modified solution, fully stirring, standing for 2-3 hours, filtering, and drying to obtain the catalyst for tartaric acid synthesis. Further, the molar ratio of tetrapropylammonium hydroxide to tetraethyl orthosilicate is 0.3-0.5:1, the mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 20-25%, and the molar ratio of isopropyl alcohol to tetrabutyl titanate is 60-70:1. Further, the molar ratio of the ammonium metavanadate to the niobium chloride to the tetraethyl orthosilicate to the tetrabutyl titanate to the ammonium carbonate is 0.03-0.05:0.01-0.02:1:0.03-0.05:0.05-0.2. Further, the hydrothermal crystallization treatment is carried out at 160-180 ℃ for 28-32 h. Further, the calcination temperature is 500-550 ℃, the calcination time is 2-3 h, and the temperature rising rate is 2-5 ℃ per minute. Further, the quaternary ammonium salt is cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride or stearyl trimethyl ammonium bromide. Further, in the modified solution, the mass ratio of the quaternary ammonium salt to the phosphotungstic acid alcohol solution is 1:10. Further, the mass concentration of the phosphotungstic acid in the phosphotungstic acid alcohol solution is 10% -20%. Further, the adding ratio of the TS-1 molecular sieve doped with vanadium and niobium to the modifying solution is 1-2 g/10 mL. The second aspect of the invention provides a catalyst prepared by the preparation method of the catalyst for tartaric acid synthesis. The third aspect of the invention provides an application of the catalyst in the process of preparing tartaric acid by using maleic anhydride as a raw material. The catalyst can catalyze the reaction in the reaction of preparing tartaric acid by taking maleic anhydride as a raw material and hydrogen peroxide as an oxidant. The catalyst is used in an amount of 2-5% of the mass of maleic anhydride. The beneficial effects obtained by one or more of the technical schemes of the invention are as follows: 1. According to the invention, the TS-1 molecular sieve is taken as a matrix, vanadium and niobium are doped into the TS-1 molecular sieve, so that a synergistic effect can be generated in a molecular sieve structure, the catalytic activity of the catalyst is remarkably enhanced, and the vanadium and niobium are doped and fixed in a framework in the pr