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CN-118324097-B - Working solution for synthesizing hydrogen peroxide by anthraquinone method

CN118324097BCN 118324097 BCN118324097 BCN 118324097BCN-118324097-B

Abstract

The invention discloses a working solution for synthesizing hydrogen peroxide by an anthraquinone method, which comprises a solvent and a working carrier, wherein the solvent comprises 30-95 parts, preferably 60-80 parts, of C 9 ~C 10 aromatic hydrocarbon, 2-20 parts, preferably 5-15 parts, 5-30 parts, preferably 5-15 parts, of diisobutyl methanol and a terephthalamide derivative A, the aromatic hydrocarbon is generally C 9 ~C 10 aromatic hydrocarbon, and the working carrier is one or more of anthraquinone and derivatives thereof. The working solution has good dissolving and mass transferring capacities on hydrogen, anthraquinone and hydroanthraquinone, the hydrogenation efficiency reaches more than 13g/L, the mutual solubility with water is low, the extraction and separation effects are good, the physicochemical properties are stable, the production efficiency of the process for producing hydrogen peroxide by an anthraquinone method can be improved, and the working solution has good industrial application prospect.

Inventors

  • BAI HONGXIN
  • FANG XIANGCHEN
  • LIU QUANJIE
  • JIA LIMING
  • WANG YANG

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20231031
Priority Date
20230110

Claims (17)

  1. 1. The working solution for synthesizing hydrogen peroxide by an anthraquinone method is characterized by comprising a solvent and a working carrier, wherein the solvent comprises aromatic hydrocarbon, diisobutyl methyl alcohol and a terephthalamide derivative A, and the structural formula of the terephthalamide derivative A is as follows: Wherein R 1 、R 2 、R 3 、R 4 is one of alkane substituent, furan, benzyl or arene substituent with 1-8 carbon atoms respectively, 30-95 parts by volume of C 9 ~C 10 arene, 2-20 parts by volume of diisobutyl methanol and 5-30 parts by volume of terephthalamide derivative A.
  2. 2. The working fluid of claim 1, wherein the alkane substituent, furan, benzyl or arene substituent further comprises one or more functional groups selected from the group consisting of alkyl, alkoxy and ester groups.
  3. 3. The working fluid of claim 1, wherein R 1 ~R 4 in the terephthalamide derivative A is an n/iso-alkyl substituent of C 1 ~C 6 , and the total number of carbon atoms of R 1 ~R 4 is not more than 20.
  4. 4. The working fluid of claim 1, wherein the working carrier is one or more of anthraquinone and its derivatives.
  5. 5. The working fluid of claim 1, wherein the working carrier is 2-alkylanthraquinone.
  6. 6. The working solution of claim 1, wherein the preparation method of the terephthalamide derivative A comprises (1) dissolving terephthalamide in an organic solvent A, carrying out dehydration reaction under the action of acyl chloride C, substituting terephthalamide functional groups with chlorine atoms to generate terephthalamide dicarboxylic acid chloride D, separating the acyl chloride after the reaction is finished, further distilling under reduced pressure to separate terephthalamide dicarboxylic acid chloride D, (2) dissolving terephthalamide dicarboxylic acid chloride D in an organic solvent B, adding a proper amount of mixed solution of dialkylamine and triethylamine, carrying out amidation reaction under certain reaction conditions to obtain a crude product of the terephthalamide derivative A, and separating and purifying to obtain the terephthalamide derivative A.
  7. 7. The working fluid of claim 6, wherein in the preparation method of the terephthalamide derivative A, the organic solvent A in the step (1) is selected from one or more of chlorobenzene, dichloromethane, chloroform, N-diethyl formamide or ethyl acetate, and the molar ratio of the organic solvent A to the terephthalic acid is 1:1.5-75.
  8. 8. The working fluid of claim 6, wherein in the preparation method of the terephthalamide derivative A, the acyl chloride C in the step (1) is one or more of phosphoric acid acyl chloride, phosphorous acid acyl chloride or sulfurous acid acyl chloride, and the molar ratio of the acyl chloride C to the terephthaloyl acetic acid is 1:1-20.
  9. 9. The working fluid according to claim 6, wherein in the method for producing the terephthalamide derivative A, the dehydration reaction condition in the step (1) is a reaction condition of 100 to 120 ℃ under normal pressure for 2 to 4 hours.
  10. 10. The working fluid of claim 6, wherein in the preparation method of the terephthalamide derivative A, the dialkylamine in the step (2) is dialkylamine D1 NHR 1 R 2 and dialkylamine D2 NHR 3 R 4 , wherein R 1 、R 2 、R 3 、R 4 is one of furan, aromatic substituent, benzyl or alkane substituent respectively.
  11. 11. The working fluid according to claim 6, wherein in the preparation method of the terephthalamide derivative A, the organic solvent B in the step (2) is selected from chlorobenzene, dichloromethane or chloroform, and the molar ratio of the organic solvent B to terephthaloyl chloride D is 1:1.5-100.
  12. 12. The working fluid according to claim 6, wherein in the preparation method of the terephthalamide derivative A, the molar ratio of the dialkylamine D1, D2 to the terephthaloyl chloride D in the step (2) is 1:1:0.5-1.
  13. 13. The working solution according to claim 6, wherein in the preparation method of the terephthalamide derivative A, the amidation reaction in the step (2) is carried out at 50-120 ℃ under normal pressure, and the reaction solution is reacted in a condensation reflux reactor for 0.5-4 hours to obtain a crude product mixed solution of the terephthalamide derivative A.
  14. 14. The working solution according to claim 6, wherein the step (2) comprises the steps of cooling the crude product mixture containing the terephthalamide derivative A to room temperature, filtering a small amount of insoluble substances generated in the reaction process, washing the reaction solution to neutrality by hydrochloric acid, sodium carbonate solution and deionized water respectively, standing to separate out a lower organic phase, and then separating and purifying by reduced pressure distillation to obtain the terephthalamide derivative A, wherein the washing adopts hydrochloric acid, sodium carbonate solution and deionized water to wash the reaction mixture to neutrality.
  15. 15. An application of the working solution for synthesizing hydrogen peroxide by the anthraquinone method according to any one of claims 1-6 in the hydrogen peroxide preparation process.
  16. 16. A hydrogenation process for producing hydrogen peroxide by an anthraquinone method is characterized in that the working solution of any one of claims 1-6 is adopted in the hydrogenation process.
  17. 17. The hydrogenation process according to claim 16, wherein the reactor is in the form of a fluidized bed, a slurry bed or a fixed bed, the hydrogenation process conditions are that the hydrogenation temperature is 25-80 ℃ and the pressure is 0.1-0.7 MPa, the hydrogenation active component of the hydrogenation catalyst is Pd, the carrier is alumina or silica gel, the auxiliary agent component in the hydrogenation catalyst is one or more of Mo, na, K, ni, mg, au, ca, fe elements, the content of the hydrogenation active component is 0.05-5% and the content of the auxiliary agent is 0.05-3% based on the weight of the hydrogenation catalyst.

Description

Working solution for synthesizing hydrogen peroxide by anthraquinone method Technical Field The invention belongs to the technology for preparing hydrogen peroxide by an anthraquinone process, and particularly relates to a working solution for synthesizing hydrogen peroxide by an anthraquinone process. Background At present, more than 99% of hydrogen peroxide products worldwide are produced by an anthraquinone process, wherein 2-alkylanthraquinone is used as a working fluid carrier, the anthraquinone working fluid is circularly and alternately subjected to catalytic hydrogenation and automatic oxidation reactions, and then the hydrogen peroxide products with different concentrations can be obtained after extraction, refining and concentration. The working fluid is used as the 'blood' of the anthraquinone process and has a decisive influence on the production efficiency of each production unit. On the premise that the physicochemical properties of the working solution completely meet the industrial requirements, the industrial generally takes the quality of H 2O2 (namely, the number of H 2O2 grams per liter of working solution can be prepared) generated by single-pass conversion of the unit volume of working solution as an important index for evaluating the productivity. Because of the large molecular polarity difference of anthraquinone and its hydrogenation products, a single solvent is difficult to fully meet the above requirements of working fluid, and the working fluid solvent system is generally formed by compounding a nonpolar anthraquinone solvent and a polar hydro-anthraquinone solvent. The existing working solution solvent system has lower solubility to anthraquinone and hydroanthraquinone, which results in low anthraquinone conversion rate, lower hydrogenation efficiency, further causes large working solution circulation volume in the device, small operation elasticity, and larger working solution density and viscosity, which results in poor extraction and separation effects, severely limits the product quality of hydrogen peroxide, causes low quality grade of hydrogen peroxide product, and has high anthraquinone consumption, thus being incapable of meeting the requirement of high-purity hydrogen peroxide product. CN1552618A discloses an arene, trioctyl phosphate and methylcyclohexyl acetate (AR/TOP/MCHA) ternary working solution, compared with the AR/TOP traditional working solution, the solubility of an AR/TOP/MCHA system to 2-ethylanthraquinone can be improved by 30g/L, and the hydrogenation efficiency of the working solution can be improved to 9-9.5 g/L. CN1583546A discloses that the three-element working solution of arene, trioctyl phosphate and tetrabutyl urea (AR/TOP/TBU) has the solubility of hydroanthraquinone improved by about 10% compared with the AR/TOP working solution, and the hydrogenation efficiency of the working solution is slightly improved. CN101798065A discloses an arene, trioctyl phosphate and N-phenyl-N-ethyl benzamide ternary working solution, compared with an AR/TOP working solution, the solubility of the ternary working solution to hydro-anthraquinone is improved by about 10-20%, and the hydrogenation efficiency can reach 11-12 g/L. EP0287421 discloses an arene+N-phenyl N-ethyl benzamide (AR/BEA) binary working solution, the solubility of the system to anthraquinone and hydroanthraquinone is obviously improved, but the density of the working solution formed by the system and anthraquinone is higher, the water solubility is high, the effect of hydrogen peroxide extraction and separation is poor, carbon residue in a hydrogen peroxide product is higher, the application effect is poor, U.S. Pat. No. 3,62 discloses an arene+N-phenyl N-ethyl benzamide binary working solution, a solvent system has good solubility to 2-alkylanthraquinone and 2-alkylhydroanthraquinone, good hydrogenation efficiency can be achieved, and good oxidation stability is achieved, but the layering and demulsification time of the solvent system and water are long, the separation efficiency of an extraction tower is seriously influenced, and the hydrogenation efficiency of a catalyst in a hydrogenation process is influenced by the entrained water of the working solution in severe cases, so that the application effect is poor, and the application requirements of hydrogen peroxide industry cannot be met. CN111071993a discloses working fluid solvent molecules of the following bisamide structureThe solvent and the solvent system formed by aromatic hydrocarbon have good solubility to both 2-alkylanthraquinone and 2-alkylhydroanthraquinone, can achieve good hydrogenation efficiency, has shorter layering and demulsification time with water, can well meet the use requirements of industry, but has to be improved in terms of solvent degradation loss. Disclosure of Invention Aiming at the defects of the prior art, the invention provides the working solution for synthesizing the hydrogen peroxide by the anthraquinone p