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CN-118125666-B - Wastewater treatment process for production of p-aminophenol

CN118125666BCN 118125666 BCN118125666 BCN 118125666BCN-118125666-B

Abstract

The invention discloses a wastewater treatment process for production of para-aminophenol, and belongs to the technical field of para-aminophenol wastewater treatment. The method is characterized in that graphene, anion exchange resin and hyperbranched polyetheramine are used as raw materials to prepare an adsorption material, so that wastewater is subjected to first-step treatment, TOC and metal ion content are reduced, then Fenton technology is used for second-step treatment, hydrogen peroxide and ferrous ions react to generate hydroxyl free radicals with strong oxidability, so that organic chemical bonds which are difficult to degrade are attacked, COD (chemical oxygen demand) in the wastewater is reduced, harm to the environment is reduced, the wastewater is filtered in a ceramic membrane, the ceramic membrane has good performance in the aspect of wastewater treatment, pollutants can be separated from the wastewater stably for a long time in a cross-flow filtration mode, and the wastewater treatment technology for producing the p-aminophenol is completed.

Inventors

  • GUI HUA
  • JIN FEI
  • YANG LEI
  • XIONG GANG
  • TAN LINGJIE
  • JI DESHENG
  • GAO WEI
  • YAO XIANG

Assignees

  • 安徽东至广信农化有限公司

Dates

Publication Date
20260505
Application Date
20240411

Claims (9)

  1. 1. The wastewater treatment process for producing the p-aminophenol is characterized by comprising the following steps of: S1, pouring graphene oxide into an ethanol solution, performing ultrasonic dispersion in an ice-water bath, adding hyperbranched polyetheramine, stirring for 6-8 hours at a temperature of 85-95 ℃, cooling, washing and drying to obtain hyperbranched polyetheramine grafted graphene oxide; Grinding hyperbranched polyetheramine grafted graphene oxide into acetone, performing ultrasonic dispersion by using ice bath, pouring into a pretreated anion exchange resin, stirring for 10-20h at 55-65 ℃, cooling, and drying to obtain an adsorption material; s2, adjusting the pH value of the wastewater for producing the para-aminophenol to 8-9 by using a sodium hydroxide solution, adding an adsorption material, standing for 1-2h, and filtering by using a filter membrane of 0.45 mu m to obtain primary wastewater; S3, regulating the pH value of the obtained primary wastewater to 2-3 by using sulfuric acid solution, entering a primary Fenton reactor, adding ferrous sulfate for the first time under the condition of room temperature, adding hydrogen peroxide, reacting for 3-6 hours to obtain secondary wastewater, entering the secondary Fenton reactor, adding ferrous sulfate for the second time under the condition of room temperature, reacting for 1-3 hours, regulating the pH value to 8-9 by using sodium hydroxide solution, precipitating, enabling filtrate to enter a ceramic membrane, and filtering to finish the wastewater treatment process for producing the p-aminophenol; The preparation method of the pretreated anion exchange resin comprises soaking anion exchange resin in distilled water for 20-36h, respectively soaking in 4% hydrochloric acid solution and 2% sodium hydroxide solution for 20-36h, washing to neutrality, and vacuum filtering to obtain pretreated anion exchange resin; The pi-pi electron conjugation effect on hyperbranched polyetheramine grafted graphene oxide realizes efficient adsorption of phenol, and the anion exchange resin further removes phenol ions of the solution through ion exchange, so that a synergistic effect is generated by combining.
  2. 2. The wastewater treatment process for producing p-aminophenol according to claim 1, wherein the mass ratio of graphene oxide to hyperbranched polyetheramine is 1:25-40.
  3. 3. The wastewater treatment process for producing para-aminophenol according to claim 1, wherein the mass ratio of the hyperbranched polyetheramine grafted graphene oxide to the pretreated anion exchange resin is 1:3-5.
  4. 4. The process for treating wastewater from the production of para-aminophenol according to claim 1, wherein the anion exchange resin comprises any one or more of KIP209, NG-6, KIP 210.
  5. 5. The process for treating wastewater for p-aminophenol production according to claim 1, wherein the molar ratio of the first input of ferrous sulfate to the second input of ferrous sulfate to hydrogen peroxide is 0.2:0.8:1.2-2, and the ratio of the primary wastewater to hydrogen peroxide is 1L:0.5g.
  6. 6. The process for treating wastewater for p-aminophenol production according to claim 1, wherein the pore diameter of the ceramic membrane is 40-80nm, the flow rate of the filtered membrane surface is 3-4.6m/s, and the temperature of the wastewater during filtration is 8-12 ℃.
  7. 7. The process for treating wastewater for producing para-aminophenol according to claim 1, wherein the hyperbranched polyetheramine comprises the steps of: Adding polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and 2, 4-diaminobutyric acid into absolute ethyl alcohol, stirring at 58-70 ℃ for 9-12h, distilling under reduced pressure, pouring into an organic solvent for washing, and drying in vacuum for 12-18h to obtain hyperbranched polyetheramine.
  8. 8. The process for treating wastewater for p-aminophenol production according to claim 7, wherein the molar ratio of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 2, 4-diaminobutyric acid is 0.8-1.2:0.8-1.2:1, and the polypropylene glycol diglycidyl ether has a number average molecular weight of 640.
  9. 9. The process for treating wastewater from the production of para-aminophenol according to claim 7, wherein the organic solvent comprises any one or more of cyclohexane, n-hexane, and n-heptane.

Description

Wastewater treatment process for production of p-aminophenol Technical Field The invention belongs to the technical field of wastewater treatment, and particularly relates to a wastewater treatment process for p-aminophenol production. Background The p-aminophenol is an important organic intermediate, has wide application in the fields of medicines, dyes, rubber and the like, and is also a well-known raw material for preparing the antipyretic analgesic drug paracetamol. The production of p-aminophenol produces a large amount of high-concentration phenol-containing wastewater, and phenols are serious harmful compounds, can produce gene mutation even at a very low concentration, are carcinogenic, are difficult to degrade naturally, remain in the environment for a long period of time, and accumulate in the food chain. Therefore, the concentration of phenol discharged from various countries is strictly limited, and p-aminophenol has double toxicity of aniline and phenol, and can cause dermatitis, hyperferrioxamine, asthma and other diseases by percutaneous absorption, and p-aminophenol is classified as a harmful substance in europe. The wastewater from the production of para-aminophenol can produce a large amount of wastewater containing organic matters, wherein the content of organic matters in the byproduct brine (i.e. NaC l solution) is particularly remarkable, and the wastewater is easy to cause environmental pollution and ecological damage if being directly discharged without treatment. Therefore, the development of an efficient and environment-friendly wastewater treatment process for producing the p-aminophenol has great significance for realizing industrial sustainable development. Chinese patent application No. CN1803641A discloses an integrated process for treating wastewater from p-aminophenol production and recycling resources, wherein the pH value of the wastewater is regulated, the wastewater is subjected to chemical oxidation treatment after the p-aminophenol is selectively adsorbed by amino modified composite functional resin, the content of organic matters in the wastewater is high, and metal ions are difficult to reach the emission standard. Disclosure of Invention The invention aims to provide a wastewater treatment process for p-aminophenol production, which aims to solve the problems that the existing wastewater is high in organic matter content and metal ions are difficult to reach the emission standard after treatment. The aim of the invention can be achieved by the following technical scheme: a wastewater treatment process for producing para-aminophenol comprises the following steps: S1, preparing graphene oxide by adopting a Hummers method, pouring the obtained graphene oxide into an ethanol solution (the mass fraction is 3%), performing ultrasonic dispersion in an ice-water bath with the power of 300-500w and the ultrasonic time of 50-90min, adding hyperbranched polyetheramine, placing the mixture into an oil bath pot with the temperature of 85-95 ℃ for stirring reaction for 6-8h, cooling, washing for 5-8 times, and drying to obtain hyperbranched polyetheramine grafted graphene oxide; Grinding hyperbranched polyetheramine grafted graphene oxide into acetone, performing ultrasonic dispersion with ice bath power of 300-500w and ultrasonic time of 3-4h, pouring into a pretreatment anion exchange resin, stirring at 55-65 ℃ for 10-20h, cooling to 20-35 ℃, and drying in a vacuum oven to obtain an adsorption material; S2, adjusting the pH value of the wastewater for producing the para-aminophenol to 8-9 by using 15wt% sodium hydroxide solution, adding 10g of adsorption material into each liter of the wastewater for producing the para-aminophenol, standing for 1-2h, and filtering by using a filter membrane of 0.45 mu m to obtain primary wastewater; S3, regulating the pH value of the obtained primary wastewater to 2-3 by using 1 mol/L sulfuric acid solution, entering a primary Fenton reactor, adding ferrous sulfate for the first time at 20-35 ℃, adding hydrogen peroxide, reacting for 3-6 hours to obtain secondary wastewater, entering a secondary Fenton reactor, adding ferrous sulfate for the second time at 20-35 ℃, reacting for 1-3 hours, regulating the pH value to 8-9 by using 15% sodium hydroxide solution by mass fraction, precipitating, filtering filtrate in a ceramic membrane, and finishing the wastewater treatment process for producing the p-aminophenol. Further, the mass ratio of the graphene oxide to the hyperbranched polyetheramine is 1:25-40. Further, the mass ratio of the hyperbranched polyetheramine grafted graphene to the pretreated anion exchange resin is 1:3-5. Further, the anion exchange resin comprises any one or more of K IP209, NG-6, KIP 210. Further, the molar ratio of the ferrous sulfate added for the first time to the ferrous sulfate added for the second time to the hydrogen peroxide is 0.2:0.8:1.2-2, and the dosage ratio of the primary wastewater to the hydrogen peroxide i