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CN-117548152-B - Method and apparatus for separating and recovering anthracene alkylation catalyst

CN117548152BCN 117548152 BCN117548152 BCN 117548152BCN-117548152-B

Abstract

The invention relates to the technical field of alkylanthracene production, in particular to a method for separating and recycling an anthracene alkylation catalyst and a device for separating and recycling the anthracene alkylation catalyst. The method comprises the steps of sequentially extracting, electrodialysis and reduced pressure distillation of an acid oil mixture containing an anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with purity of more than or equal to 98wt%, wherein the reduced pressure distillation comprises reduced pressure distillation-I and reduced pressure distillation-II. The method sequentially adopts the technical means of extraction, electrodialysis and reduced pressure distillation, and combines the coupling of the extraction, the electrodialysis and the reduced pressure distillation, so that the recovered anthracene alkylation catalyst has high purity and high yield.

Inventors

  • QIAN JIANGUO
  • ZHANG YI
  • ZHOU LINA
  • ZHENG BO
  • SHI PENG
  • ZONG BAONING

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20220804

Claims (20)

  1. 1. A method for separating and recovering an anthracene alkylation catalyst is characterized by comprising the steps of sequentially extracting, electrodialysis and reduced pressure distillation of an acid oil mixture containing the anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with purity of more than or equal to 98 wt%; wherein the reduced pressure distillation comprises reduced pressure distillation-I and reduced pressure distillation-II; The method comprises the following steps: (1) Mixing the acid oil mixture with water and extracting to obtain an aqueous solution containing anthracene alkylation catalyst as an extraction phase; (2) Carrying out electrodialysis on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 8 wt%; (3-I) subjecting the concentrated aqueous alkylation catalyst solution to reduced pressure distillation-I to obtain a crude anthracene alkylation catalyst having a water content of less than or equal to 0.1wt% and a water content of less than or equal to 0.1wt% of the catalyst; (3-II) subjecting the crude anthracene alkylation catalyst to reduced pressure distillation-II to obtain the recovered anthracene alkylation catalyst and impurities having a catalyst content of less than or equal to 0.1 wt%.
  2. 2. The process of claim 1, wherein in step (1), the concentration of anthracene alkylation catalyst in the acid oil mixture is 80-95wt%.
  3. 3. The process of claim 2, wherein in step (1), the concentration of anthracene alkylation catalyst in the acid oil mixture is 85-90wt%.
  4. 4. The process of claim 1, wherein the anthracene alkylation catalyst is selected from liquid acid catalysts.
  5. 5. The process of claim 4 wherein the anthracene alkylation catalyst is selected from the group consisting of C 1 -C 5 alkyl sulfonic acids and/or C 1 -C 5 perfluoro substituted alkyl sulfonic acids.
  6. 6. The method of claim 5, wherein the anthracene alkylation catalyst is selected from at least one of methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, perfluoromethane sulfonic acid, perfluoroethane sulfonic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonic acid.
  7. 7. The process of claim 1 wherein in step (1) the weight ratio of acid oil mixture to water calculated as anthracene alkylation catalyst is 1:5-30.
  8. 8. The process of claim 7 wherein in step (1) the weight ratio of acid oil mixture to water calculated as anthracene alkylation catalyst is 1:10-20.
  9. 9. The method of claim 1, wherein in step (1), the mixing conditions include a temperature of 20-100 ℃ and a time of 0.25-1h.
  10. 10. The method of claim 9, wherein in step (1), the mixing conditions include a temperature of 30-80 ℃ and a time of 0.3-0.8h.
  11. 11. The process according to claim 1, wherein the conditions of extraction comprise a temperature of 20-100 ℃ and a time of 0.5-3h.
  12. 12. The process of claim 11, wherein the conditions of extraction comprise a temperature of 30-80 ℃ and a time of 0.5-1h.
  13. 13. The method of claim 1, wherein in the step (2), the electrodialysis condition comprises a current density of 1-10000A/m 2 , a voltage of 0-80V, and a time of 2-10h.
  14. 14. The method of claim 13, wherein in step (2), the electrodialysis conditions include a current density of 100-5000A/m 2 , a voltage of 5-50V, and a time of 3-8h.
  15. 15. The process of claim 1, wherein the concentrated aqueous anthracene alkylation catalyst solution has a concentration of 8-20wt%.
  16. 16. The method of claim 15, wherein the concentrated aqueous anthracene alkylation catalyst solution has a concentration of 8-15wt%.
  17. 17. The process according to claim 1, wherein in the step (3-I), the conditions of the reduced pressure distillation-I include a liquid phase temperature of 50 to 100 ℃, a gas phase temperature of 25 to 75 ℃, a pressure of 0 to 5kPa, and an overhead reflux ratio of 0.2 to 5.
  18. 18. The process according to claim 17, wherein in the step (3-I), the conditions of the reduced pressure distillation-I include a liquid phase temperature of 60 to 80 ℃, a gas phase temperature of 40 to 60 ℃, a pressure of 1 to 3kPa, and an overhead reflux ratio of 0.4 to 3.
  19. 19. The process according to claim 1, wherein in step (3-II), the conditions of reduced pressure distillation-II include a liquid phase temperature of 150 to 250 ℃, a gas phase temperature of 100 to 200 ℃, a pressure of 0.1 to 4kPa, and an overhead reflux ratio of 0.1 to 4.
  20. 20. The process according to claim 19, wherein in step (3-II), the conditions of reduced pressure distillation-II include a liquid phase temperature of 180 to 220 ℃, a gas phase temperature of 130 to 180 ℃, a pressure of 0.5 to 2kPa, and an overhead reflux ratio of 0.2 to 2.

Description

Method and apparatus for separating and recovering anthracene alkylation catalyst Technical Field The invention relates to the technical field of alkylanthracene production, in particular to a method for separating and recycling an anthracene alkylation catalyst and a device for separating and recycling the anthracene alkylation catalyst. Background At present, the technology for producing hydrogen peroxide at home and abroad mainly adopts an anthraquinone method, wherein 2-alkylanthraquinone in the process is used as a carrier in the process, and the quality and the yield of the hydrogen peroxide are directly influenced. The process route for preparing the 2-alkylanthraquinone by oxidizing the 2-alkylanthracene has the advantages of simple process flow, wide raw material sources, small environmental pollution and the like, is considered as a green production process technology, and has wide application prospect. Under the action of acid catalysis, anthracene and alkylating reagent are alkylated, and the reaction product system is treated by separation technology to obtain target product 2-alkylanthracene, and then a specific oxidation technology is adopted to realize the purpose of efficiently preparing 2-alkylanthraquinone from 2-alkylanthracene. The key raw material 2-alkylanthracene of the process can be prepared by a heterogeneous liquid acid alkylation technology, and the technology has the characteristics of simple process flow, low-cost and easily-obtained required acid catalyst, excellent catalytic performance and the like. Both US4255343A, CN111825512A, CN109574779a and CN111825510a disclose processes for the catalytic anthracene alkylation with heterogeneous liquid acids, but neither involves the reuse of the catalyst. The acid-soluble oil is byproduct in the process of catalyzing alkylation by strong acid, so that the acid-soluble oil continuously accumulated in the reaction process reduces acidity and increases viscosity, and further the catalytic activity of the catalyst is reduced. High temperature cracking processes are currently commonly employed in the industry to treat alkylation catalysts. Taking sulfuric acid as an example, firstly, the acid-soluble oil contained in the sulfuric acid is removed through steps of heating, sedimentation, degassing and the like, and then fresh sulfuric acid is generated through procedures of incineration cracking, sulfur dioxide conversion, cooling, sulfuric acid condensation and the like. The obvious disadvantages of the method are high energy consumption, complex procedures and high cost. Therefore, in order to achieve the recycling of the catalyst, efficient separation techniques must be developed. Thus, there is a need for a new process for separating and recovering anthracene alkylation catalyst. Disclosure of Invention The invention aims to solve the problems of complex process, high energy consumption, environmental pollution and the like in the separation and recovery of the existing anthracene alkylation catalyst, low purity and low yield of the recovered anthracene alkylation catalyst and provides a novel method for separating and recovering the anthracene alkylation catalyst and a novel device for separating and recovering the anthracene alkylation catalyst. In order to achieve the above object, the first aspect of the present invention provides a method for separating and recovering an anthracene alkylation catalyst, comprising subjecting an acid oil mixture containing the anthracene alkylation catalyst to extraction, electrodialysis and reduced pressure distillation in this order to obtain a recovered anthracene alkylation catalyst having a purity of not less than 98 wt%; Wherein the reduced pressure distillation comprises reduced pressure distillation-I and reduced pressure distillation-II. Preferably, the method comprises the steps of: (1) Mixing the acid oil mixture with water and extracting to obtain an aqueous solution containing anthracene alkylation catalyst as an extraction phase; (2) Carrying out electrodialysis on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 8 wt%; (3-I) subjecting the concentrated aqueous alkylation catalyst solution to reduced pressure distillation-I to obtain a crude anthracene alkylation catalyst having a water content of less than or equal to 0.1wt% and a water content of less than or equal to 0.1wt% of the catalyst; (3-II) subjecting the crude anthracene alkylation catalyst to reduced pressure distillation-II to obtain the recovered anthracene alkylation catalyst and impurities having a catalyst content of less than or equal to 0.1 wt%. The second aspect of the invention provides a device for separating and recovering anthracene alkylation catalyst, which comprises an extraction unit, an electrodialysis unit and a reduced pressure distillation unit which are sequentially comm