阅读说明：本技术 活性炭载铁铜催化剂及制备方法及用途 (Active carbon carried iron-copper catalyst and its preparation method and use ) 是由 张安龙 魏文霞 高俊玲 杨子新 李文涛 王辰风 孙庆 于 2019-11-12 设计创作，主要内容包括：本发明属于催化剂技术领域,具体涉及一种活性炭载铁铜催化剂及制备方法及用途。所述活性炭载铁铜催化剂以活性炭为载体,Fe<Sup>2+</Sup>、Cu<Sup>2+</Sup>为活性组分,采用浸渍法将Fe<Sup>2+</Sup>、Cu<Sup>2+</Sup>负载到载体上,经干燥焙烧后制得活性炭载铁铜催化剂；其中,Fe<Sup>2+</Sup>为硫酸亚铁溶液,Cu<Sup>2+</Sup>为硫酸铜溶液。本发明制备的活性炭载铁铜催化剂首次用于造纸废水的非均相Fenton处理中,并获得较好的处理效果,本发明制备的二元催化剂,通过铜的加入,与铁相互协调,促进反应的发生,提高催化剂的活性。(The invention belongs to the technical field of catalysts, and particularly relates to an activated carbon-supported iron-copper catalyst, and a preparation method and application thereof. The activated carbon-carried iron-copper catalyst takes activated carbon as a carrier and Fe 2+ 、Cu 2+ As active component, Fe is impregnated by dipping 2+ 、Cu 2+ Loading the carrier, drying and roasting to obtain the activated carbon-loaded iron-copper catalyst; wherein, Fe 2+ As ferrous sulfate solution, Cu 2+ Is a copper sulfate solution. The activated carbon-carried iron-copper catalyst prepared by the invention is firstly used in the heterogeneous Fenton treatment of papermaking wastewater, and obtains better treatmentThe binary catalyst prepared by the invention is coordinated with iron by adding copper, thereby promoting the reaction and improving the activity of the catalyst.)

1. The preparation method of the activated carbon-carried iron-copper catalyst is characterized in that the activated carbon is used as a carrier, and Fe²⁺、Cu²⁺As active component, Fe is impregnated by dipping²⁺、Cu²⁺Loading the carrier, drying and roasting to obtain the activated carbon-loaded iron-copper catalyst; wherein, Fe²⁺As ferrous sulfate solution, Cu²⁺Is a copper sulfate solution.

2. The preparation method of the activated carbon-supported iron-copper catalyst according to claim 1, wherein the activated carbon is 60-80 mesh activated carbon.

3. The method for preparing an activated carbon-supported iron-copper catalyst according to claim 2, wherein the activated carbon is pretreated according to the following method: cleaning the activated carbon with ultrapure water until the water solution is not turbid, carrying out suction filtration, washing off impurities and fragments, drying the activated carbon, placing the dried activated carbon in a sulfuric acid solution with the volume fraction of 50-70%, placing the sulfuric acid solution in a shaking table at 20-35 ℃ for soaking for 10-14 h, washing the soaked carrier with the ultrapure water, adjusting the pH of a last washing solution containing the carrier to 4-5, carrying out suction filtration, and drying the precipitate to obtain the activated carbon carrier.

4. The preparation method of the activated carbon-supported iron-copper catalyst according to claim 3, wherein the ratio of the dried activated carbon to the sulfuric acid solution is 20-30 g: 70-80 mL.

5. The preparation method of the activated carbon-supported iron-copper catalyst according to claim 3, wherein the activated carbon carrier is placed in a ferrous sulfate-copper sulfate mixed solution, the ferrous sulfate concentration in the ferrous sulfate-copper sulfate mixed solution is 10-13 g/100mL, the copper sulfate concentration in the ferrous sulfate-copper sulfate mixed solution is 5-8 g/100mL, and the activated carbon carrier is soaked in a shaking table at the temperature of 20-35 ℃ for 10-14 hours; and (3) cleaning the soaked activated carbon with ultrapure water, performing suction filtration, drying, calcining the obtained solid at 400-500 ℃ for 2-3 h in a nitrogen atmosphere, and thus obtaining the activated carbon iron-copper-loaded catalyst.

6. The preparation method of the activated carbon-supported iron-copper catalyst according to claim 5, wherein the ratio of the activated carbon carrier to the ferrous sulfate-copper sulfate mixed solution is 8-15 g: 60-80 mL, and the rotating speed of the shaking table is 150-250 r/min.

7. The method for preparing an activated carbon-supported iron-copper catalyst according to claim 5, wherein the ferrous sulfate concentration in the ferrous sulfate-copper sulfate mixed solution is 10g/100mL, and the copper sulfate concentration is 5g/100 mL.

8. The activated carbon-supported iron-copper catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the activated carbon-supported iron-copper catalyst according to claim 8 in the treatment of papermaking wastewater.

10. The use of the activated carbon-supported iron copper catalyst in the treatment of papermaking wastewater according to claim 9, wherein the activated carbon-supported iron copper catalyst is used in a heterogeneous Fenton reaction for reducing COD and chroma in papermaking wastewater.

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to an activated carbon-supported iron-copper catalyst, and a preparation method and application thereof.

Background

The papermaking wastewater has the characteristics of large discharge amount, high concentration of organic pollutants, poor biodegradability and the like. The papermaking wastewater can not be discharged after reaching the standard after being subjected to conventional biochemical treatment, and needs to be subjected to advanced treatment. The Fenton method is commonly used for the advanced treatment of papermaking wastewater due to the advantages of simple process, fast reaction and the like. However, since the Fenton method is used for a long time, the problems that the pH range of the reaction of the traditional Fenton method is narrow, the loss of the catalyst is serious and the like are found, so that the treatment cost is high, and the treatment effect cannot meet the standard of standard emission. In order to solve the problem that the papermaking wastewater treated by the traditional Fenton method cannot meet the standard discharge, heterogeneous Fenton catalysis becomes a research hotspot.

The heterogeneous Fenton is different from the traditional Fenton in the preparation of the catalyst, the heterogeneous Fenton catalyst is solid, an active component is generally an iron compound, and the solid catalyst can reduce the loss of the catalyst and improve the reaction efficiency. Therefore, the preparation of the novel catalyst is the main core for improving the heterogeneous Fenton treatment effect. At present, the research on treating papermaking wastewater by heterogeneous Fenton is less, the active components of the heterogeneous Fenton catalyst for treating the papermaking wastewater are mostly single elements, the active components are mostly iron oxides, and the catalytic effect has certain limitation. Therefore, the development of multi-element heterogeneous Fenton catalysts is particularly necessary.

Disclosure of Invention

The activated carbon-supported iron-copper catalyst is a multi-component multi-element catalyst, and compared with the traditional Fenton catalyst, the activated carbon-supported iron-copper catalyst has the advantages that the catalytic efficiency is improved, and the pH application range is widened.

The invention aims to provide a preparation method of an activated carbon-supported iron-copper catalyst, which takes activated carbon as a carrier and Fe^{2 +}、Cu²⁺As active component, Fe is impregnated by dipping²⁺、Cu²⁺Loading the carrier, drying and roasting to obtain the activated carbon-loaded iron-copper catalyst; wherein, Fe²⁺As ferrous sulfate solution, Cu²⁺Is a copper sulfate solution.

Preferably, in the preparation method of the activated carbon-supported iron-copper catalyst, the activated carbon is 60-80 meshes of activated carbon.

Preferably, in the preparation method of the activated carbon-supported iron-copper catalyst, the activated carbon is pretreated according to the following method: cleaning the activated carbon with ultrapure water until the water solution is not turbid, carrying out suction filtration, washing off impurities and fragments, drying the activated carbon, placing the dried activated carbon in a sulfuric acid solution with the volume fraction of 50-70%, placing the sulfuric acid solution in a shaking table at 20-35 ℃ for soaking for 10-14 h, washing the soaked carrier with the ultrapure water, adjusting the pH of a last washing solution containing the carrier to 4-5, carrying out suction filtration, and drying the precipitate to obtain the activated carbon carrier.

Preferably, in the preparation method of the activated carbon-supported iron-copper catalyst, the ratio of the dried activated carbon to the sulfuric acid solution is 20-30 g: 70-80 mL.

Preferably, the preparation method of the activated carbon-supported iron-copper catalyst comprises the steps of placing the activated carbon carrier in a ferrous sulfate-copper sulfate mixed solution, wherein the ferrous sulfate concentration in the ferrous sulfate-copper sulfate mixed solution is 10-13 g/100mL, the copper sulfate concentration in the ferrous sulfate-copper sulfate mixed solution is 5-8 g/100mL, and soaking the activated carbon carrier in a shaking table at the temperature of 20-35 ℃ for 10-14 hours; and (3) cleaning the soaked activated carbon with ultrapure water, performing suction filtration, drying, calcining the obtained solid at 400-500 ℃ for 2-3 h in a nitrogen atmosphere, and thus obtaining the activated carbon iron-copper-loaded catalyst.

Preferably, in the preparation method of the activated carbon-supported iron-copper catalyst, the ratio of the activated carbon carrier to the ferrous sulfate-copper sulfate mixed solution is 8-15 g: 60-80 mL, and the rotating speed of the shaking table is 150-250 r/min.

Preferably, in the preparation method of the activated carbon-supported iron-copper catalyst, the concentration of the ferrous sulfate in the ferrous sulfate-copper sulfate mixed solution is 10g/100mL, and the concentration of the copper sulfate in the mixed solution is 5g/100 mL.

The invention also provides the activated carbon-supported iron-copper catalyst prepared by the preparation method.

The invention also provides a heterogeneous Fenton reaction of the activated carbon-supported iron-copper catalyst in the papermaking wastewater treatment.

Preferably, the activated carbon supported iron-copper catalyst is used for reducing COD and chroma in papermaking wastewater.

Compared with the prior art, the activated carbon-supported iron-copper catalyst and the preparation method and the application thereof have the following beneficial effects:

the activated carbon-supported iron-copper catalyst prepared by the invention is used for heterogeneous Fenton treatment of papermaking wastewater for the first time, and obtains a good treatment effect. The binary catalyst prepared by the invention is coordinated with iron by adding copper, so that the reaction is promoted, and the activity of the catalyst is improved.

(1) The catalyst has good catalytic effect, and can be used for deeply treating papermaking wastewater to obtain effluent COD value reduced from 160mg/L to 36mg/L, chroma reduced from 300 to 15, and discharge standard of GB 3544-2008.

(2) The catalyst has a wide application pH range, the COD of effluent is reduced to below 50mg/L within the reaction pH range of 2-5, the emission standard is met, the application pH range of the traditional Fenton is 3-4, and the reaction pH range is widened compared with that of the traditional Fenton.

(3) The catalyst of the invention does not generate the problem of secondary pollution, no iron mud is generated in the reaction process, the COD removal rate reaches 38.1 percent and the chroma removal rate reaches 80 percent after the catalyst is repeatedly used for five times, and the catalyst still has certain recycling value after the reaction.

Drawings

FIG. 1 is a graph of the effect of different reaction pH on heterogeneous Fenton experiments (example 1 catalyst);

FIG. 2 is a graph of the effect of different reaction pH on a conventional Fenton experiment (conventional Fenton catalyst).

Detailed Description

The present invention is described in detail below with reference to specific examples, but the present invention should not be construed as being limited thereto. The test methods in the following examples, which are not specified in specific conditions, are generally conducted under conventional conditions, and the steps thereof will not be described in detail since they do not relate to the invention.

The invention provides a preparation method of an activated carbon-supported iron-copper catalyst, which takes activated carbon as a carrier and Fe²⁺、Cu²⁺As active component, Fe is impregnated by dipping²⁺、Cu²⁺Loading the carrier, drying and roasting to obtain the active carbon supported iron-copper catalyst. The active carbon is 60-80 mesh active carbon and Fe²⁺As ferrous sulfate solution, Cu²⁺Is a copper sulfate solution.

The preparation method of the activated carbon-supported iron-copper catalyst provided by the invention specifically comprises the following embodiments.