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CN-121988370-A - Solid catalyst and preparation method and application thereof

CN121988370ACN 121988370 ACN121988370 ACN 121988370ACN-121988370-A

Abstract

The invention provides a solid catalyst, a preparation method and application thereof. The solid catalyst comprises a Y-type molecular sieve and ferric oxide loaded on the Y-type molecular sieve, wherein the specific surface area of the solid catalyst is more than 640m 2 /g, and the total pore volume is more than 0.36cm 3 /g. The catalyst of the invention can be used for degrading dimethyl sulfoxide wastewater, has high TOC removal rate of the dimethyl sulfoxide wastewater and does not bring secondary pollution.

Inventors

  • LI RENJIE
  • SUN XIAOXUE
  • WANG DEJU
  • ZHAO SHEN
  • ZUO YU

Assignees

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

Dates

Publication Date
20260508
Application Date
20241108

Claims (10)

  1. 1. A solid catalyst comprising a Y-type molecular sieve and iron oxide supported on the Y-type molecular sieve, the solid catalyst having a specific surface area of >640m 2 /g and a total pore volume of >0.36cm 3 /g.
  2. 2. The solid catalyst according to claim 1, wherein the iron content of the Y-type molecular sieve is 4-7wt%, preferably 5-6.5wt%, and/or The iron oxide exists in the surface and pore channels of the solid catalyst in a hexacoordinated form.
  3. 3. The solid catalyst according to claim 1 or 2, wherein the Y-type molecular sieve comprises one or more of NaY molecular sieve, USY molecular sieve and HY molecular sieve, and/or The solid catalyst has faujasite crystal structure, and/or The specific surface area of the solid catalyst is 640-700m 2 /g, preferably 650-680m 2 /g, and/or The total pore volume of the solid catalyst is 0.36-0.5cm 3 /g, preferably 0.36-0.4cm 3 /g, and/or The solid catalyst has a micropore volume of 0.25-0.5cm 3 /g, preferably 0.25-0.3cm 3 /g, and/or The average pore diameter of the solid catalyst is 0.5-10nm, preferably 0.5-2nm.
  4. 4. A method for preparing a solid catalyst, comprising the steps of: (1) Soaking the Y-type molecular sieve in ferric nitrate water solution; (2) And respectively carrying out solid-liquid separation, drying and calcination on the impregnated Y-type molecular sieve to obtain the solid catalyst.
  5. 5. The method according to claim 4, wherein the concentration of iron ions in the aqueous solution of ferric nitrate is 0.01-0.5mol/L, preferably 0.05-0.2mol/L; Preferably, each gram of the Y-type molecular sieve is immersed in 10-50mL of aqueous solution of ferric nitrate.
  6. 6. The process according to claim 4 or 5, wherein in step (1), the time of the impregnation is 12-48 hours, preferably 20-28 hours, and/or In step (1), the temperature of the impregnation is 10-40 ℃, preferably 15-35 ℃, and/or In step (2), the calcination temperature is 450-650 ℃, preferably 500-600 ℃, and/or In step (2), the calcination time is 2 to 10 hours, preferably 3 to 6 hours.
  7. 7. Use of a solid catalyst according to any one of claims 1 to 3 or obtained by a process according to any one of claims 4 to 6 in a Fenton reaction.
  8. 8. The use according to claim 7, wherein the solid catalyst is used for treating industrial waste water, Preferably, the solid catalyst is used for treating industrial wastewater containing DMSO.
  9. 9. A method for treating DMSO-containing wastewater, comprising subjecting a mixed solution of DMSO-containing wastewater and hydrogen peroxide to a Fenton reaction in the presence of the solid catalyst according to any one of claims 1 to 3 or the solid catalyst obtained by the production method according to any one of claims 4 to 6.
  10. 10. A process according to claim 9, wherein the DMSO-containing wastewater contains 50-1500mg/L of total organic carbon TOC and/or The pH of the DMSO-containing wastewater is 1.5-8, preferably 2-7, more preferably 2-4, and/or The content of catalyst in the mixed solution is 3-10g/L, and/or The hydrogen peroxide is contained in the mixture in an amount of 1.5 to 6wt%, preferably in a concentration of 25 to 30%, preferably at a rate of 5 to 20mL/h, and/or the Fenton reaction is carried out at a temperature of 50 to 100 ℃, preferably 60 to 80 ℃, more preferably 70 to 80 ℃, and/or The Fenton reaction time is 1-24h, preferably 2-6h, and/or The Fenton reaction is carried out under magnetic stirring, preferably at a rotational speed of 200-500rpm.

Description

Solid catalyst and preparation method and application thereof Technical Field The invention belongs to the field of catalysts, and particularly relates to a solid catalyst and a preparation method thereof, and application thereof in industrial wastewater treatment, in particular to DMSO-containing wastewater treatment. Background Dimethyl sulfoxide has the advantages of high polarity, good solubility, good thermal stability and the like, can dissolve various organic solvents, and is known as a universal solvent. In the process of producing and using dimethyl sulfoxide, dimethyl sulfoxide wastewater inevitably occurs, and the wastewater has the characteristics of high toxicity, high organic matter content, strong peculiar smell, poor biodegradability and the like, and is a research difficulty in the field of water treatment. Because dimethyl sulfoxide wastewater has poor biodegradability and is difficult to directly treat by a biochemical method, the dimethyl sulfoxide is degraded by adopting a catalytic oxidation technology at present. The hydroxyl radical generated by decomposing hydrogen peroxide has strong oxidizing property and is widely used in the field of wastewater treatment. CN206799207U discloses a photocatalytic oxidation device for treating dimethyl sulfoxide wastewater. According to the method, hydrogen peroxide in the Fenton reagent is decomposed by ultraviolet light to generate hydroxyl free radicals with strong oxidability, and dimethyl sulfoxide is oxidized and degraded. The method has simple process and the COD removal rate can reach 85 percent. CN118047504a discloses a process for treating dimethyl sulfoxide wastewater by a homogeneous Fenton method, which pretreats the dimethyl sulfoxide wastewater by a high-frequency electromagnetic water treatment device to enhance the activity of water molecules, further optimize the medicament feeding process and strengthen the degradation effect of the dimethyl sulfoxide, but only the degradation rate of the dimethyl sulfoxide is mentioned, and the change of indexes such as TOC or COD is not illustrated. The two methods can realize higher degradation rate of dimethyl sulfoxide, but a large amount of iron ions can be introduced into the solution by adopting a homogeneous Fenton method, and the removal of the iron ions can certainly increase the post-treatment cost. CN207811493U discloses a multistage treatment device for wastewater containing dimethyl sulfoxide, which combines various methods such as photocatalysis technology, electrocatalytic technology, biochemical technology, membrane separation technology and the like. The method comprises the steps of firstly pretreating dimethyl sulfoxide wastewater by a photocatalysis method, then introducing the dimethyl sulfoxide wastewater into a micro-electrolyzer for electrochemical treatment to improve biochemistry, removing iron ions by a method of adjusting pH value and adding a flocculating agent, and finally degrading organic matters by a biochemical method. The process is complex and the removal effect of dimethyl sulfoxide is not illustrated in the examples. The existing dimethyl sulfoxide catalytic oxidation technology mostly adopts a photocatalysis technology and a homogeneous Fenton technology for degradation, the method has higher requirements on chromaticity of wastewater, iron ions are introduced into the wastewater, so that subsequent separation is difficult, the treatment cost is increased, and the existing dimethyl sulfoxide wastewater treatment technology still has the defects that the treatment performance needs to be further improved. Disclosure of Invention Aiming at the problems existing in the prior art, the invention aims to provide a supported solid catalyst, a preparation method and application thereof. The supported molecular sieve catalyst prepared by the method has the advantages of simple operation, easy separation, wide pH response range, good reusability and the like, can be used for degrading dimethyl sulfoxide wastewater, has high TOC removal rate and does not bring secondary pollution. Meanwhile, the catalyst has long single-use time, is easy to regenerate, and the catalytic reaction effect after regeneration is equivalent to that of a fresh catalyst. In order to achieve the above object, the present invention provides the following technical solutions. In a first aspect, the invention provides a solid catalyst comprising a Y-type molecular sieve and iron oxide supported on the Y-type molecular sieve, the solid catalyst having a specific surface area of >640m 2/g and a total pore volume of >0.36cm 3/g. In some embodiments, the solid catalyst has a specific surface area of 640-700m 2/g, e.g., 640m2/g、650m2/g、660m2/g、670m2/g、680m2/g、690m2/g、700m2/g or any value therebetween. In some preferred embodiments, the specific surface area of the solid catalyst is 650-680m 2/g. In some embodiments, the total pore volume of the solid catalyst is from 0.36 to 0.5cm 3/g, e.g., 0.35cm3/