阅读说明：本技术 一种处理焦化废水用的阴离子交换树脂及其制备方法 (Anion exchange resin for treating coking wastewater and preparation method thereof ) 是由 郭为磊 陈动 尹志义 毛进池 刘文飞 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种处理焦化废水用的阴离子交换树脂及其制备方法,孔离子交换树脂聚合白球在溶胀剂、醛类、醇类存在的条件下、在催化剂的催化作用下,通入氯化氢后进行氯甲基化反应,控制球体的氯含量为3-21％；反应结束后水洗球体至无氯离子得到氯球；氯球经后交联-胺化反应后得到阴离子交换树脂,该阴离子交换树脂的比表面积为200-600m<Sup>2</Sup>/g。所述的阴离子交换树脂在处理焦化废水时,在常温常压下进行,焦化废水的流速为1-2BV/h。本发明在制备的树脂过程中不直接使用氯甲醚,且制备的树脂比表面积大,吸附率高,在处理焦化废水过程中使用周期长,在工业生产中有很高的实用价值。(The invention discloses an anion exchange resin for treating coking wastewater and a preparation method thereof, wherein a porous ion exchange resin polymeric white ball is subjected to chloromethylation reaction after hydrogen chloride is introduced under the presence of a swelling agent, aldehydes and alcohols and under the catalytic action of a catalyst, and the chlorine content of the ball is controlled to be 3-21%; after the reaction is finished, washing the sphere with water until no chloride ions exist to obtain a chlorine sphere; the chlorine ball is subjected to post-crosslinking-amination reaction to obtain anion exchange resin, and the specific surface area of the anion exchange resin is 200-600m 2 (ii) in terms of/g. The anion exchange resin is carried out at normal temperature and normal pressure when treating the coking wastewater, and the flow rate of the coking wastewater is 1-2 BV/h. The method does not directly use chloromethyl ether in the process of preparing the resin, and the prepared resin has large specific surface area, high adsorption rate, long service cycle in the process of treating the coking wastewater and high practical value in industrial production.)

1. A preparation method of anion exchange resin for treating coking wastewater is characterized by comprising the following steps: introducing hydrogen chloride into the macroporous ion exchange resin polymerized white spheres in the presence of a swelling agent, aldehydes and alcohols under the catalytic action of a catalyst, and then carrying out a chloromethylation reaction, wherein the chlorine content of the spheres is controlled to be 3-21%; after the reaction is finished, washing the sphere with water until no chloride ions exist to obtain a chlorine sphere; and (3) carrying out post-crosslinking-amination reaction on the chlorine spheres to obtain the anion exchange resin, wherein the anion exchange resin is the anion exchange resin with high specific surface area.

2. The preparation method according to claim 1, wherein the mass ratio of the macroporous ion exchange resin polymeric white spheres, the swelling agent, the aldehydes, the alcohols, the catalyst and the hydrogen chloride is 1-1.5: 4-5: 0.5-0.9: 0.15-0.25: 0.5-1.0: 0.3-0.5.

3. The preparation method according to claim 1, wherein the chloromethylation reaction is carried out at a reaction temperature of 30-50 ℃.

4. The method according to claim 1, wherein the swelling agent is any one of dichloroethane, nitrobenzene, dichloromethane, chloroform or carbon tetrachloride, or a mixture of two or more thereof in any ratio.

5. The method according to claim 1, wherein the aldehyde is a mixture of two or more selected from the group consisting of formaldehyde solution, trioxymethylene and paraformaldehyde mixed at an arbitrary ratio.

6. The method according to claim 1, wherein the alcohol is methanol or formaldehyde diglycol.

7. The method according to claim 1, wherein the catalyst is any one of anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous zinc chloride and anhydrous stannic chloride, or a mixture of two or more of them in any ratio.

8. An anion exchange resin for treating coking wastewater prepared by the preparation method of any one of claims 1 to 7, characterized in that the anion exchange resin is used for treating coking wastewaterThe specific surface area of the exchange resin is 200-600m²/g。

9. Use of the anion exchange resin of claim 8 for treating coking wastewater.

10. The use of claim 9, wherein the anion exchange resin is used for treating the coking wastewater at normal temperature and normal pressure, and the flow rate of the coking wastewater is 1-2 BV/h.

Technical Field

The invention relates to an anion exchange resin for treating coking wastewater and a preparation method thereof, in particular to a preparation method of a special anion exchange resin with high specific surface area for treating coking wastewater.

Background

The anion exchange resin produced in industry is mostly prepared by using styrene-divinylbenzene copolymerized spheres (white spheres) as a skeleton, chloromethylating with chloromethyl ether and then aminating to introduce quaternary ammonium groups or other amine groups. Chloromethyl ether is not only a chloromethylation reagent with higher activity, but also is a good swelling agent for the styrene-divinylbenzene copolymer, and the cost is low. However, since the sixties of the last century, chloromethyl ether and dichloromethyl ether produced by chloromethylation have been found to have a strong carcinogenic effect and are listed as factory banned reagents internationally.

Disclosure of Invention

The invention aims to solve the technical problem of the prior art and provides an anion exchange resin for treating coking wastewater and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of anion exchange resin for treating coking wastewater comprises the following steps: introducing hydrogen chloride into the macroporous ion exchange resin polymerized white spheres in the presence of a swelling agent, aldehydes and alcohols under the catalytic action of a catalyst, and then carrying out a chloromethylation reaction, wherein the chlorine content of the spheres is controlled to be 3-21%; after the reaction is finished, washing the sphere with water until no chloride ions exist to obtain a chlorine sphere; and (3) carrying out post-crosslinking-amination reaction on the chlorine spheres to obtain the anion exchange resin, wherein the anion exchange resin is the anion exchange resin with high specific surface area.

In the technical scheme, the mass ratio of the macroporous ion exchange resin polymeric white spheres to the swelling agent to the aldehydes to the alcohols to the catalyst to the hydrogen chloride is 1-1.5: 4-5: 0.5-0.9: 0.15-0.25: 0.5-1.0: 0.3-0.5.

In the technical scheme, the chloromethylation reaction is carried out at the reaction temperature of 30-50 ℃.

In the above technical scheme, the post-crosslinking-amination reaction is carried out according to the conventional process or the existing process in the field.

In the technical scheme, the macroporous ion exchange resin polymeric white balls are prepared by the traditional process or the existing process in the field, or are commercially available; preferably, the white ball is D201 or D301 white ball produced by Kary environmental protection science and technology corporation.

In the technical scheme, the swelling agent is any one of dichloroethane, nitrobenzene, dichloromethane, trichloromethane or carbon tetrachloride, and a mixture of two or more of dichloroethane, nitrobenzene, dichloromethane, trichloromethane or carbon tetrachloride in any proportion.

In the technical scheme, the aldehyde is any one of formaldehyde solution, trioxymethylene and paraformaldehyde, and a mixture formed by mixing two or more than two of the formaldehyde solution, the trioxymethylene and the paraformaldehyde in any proportion; a formaldehyde solution having a mass concentration of 37% or a formaldehyde solution having a mass concentration of 60% is preferable.

In the technical scheme, the alcohol is methanol or formaldehyde diglycol.

In the technical scheme, the catalyst is any one of anhydrous ferric trichloride, anhydrous aluminum trichloride, anhydrous zinc chloride and anhydrous stannic chloride, and a mixture of two or more of the anhydrous ferric trichloride, the anhydrous aluminum trichloride, the anhydrous zinc chloride and the anhydrous stannic chloride is mixed in any proportion.

The invention also provides the anion exchange resin for treating the coking wastewater, which is prepared by the preparation method and has the specific surface area of 200-600m²/g。

The invention also provides an application of the anion exchange resin in the aspect of treating coking wastewater.

In the technical scheme, the anion exchange resin is carried out at normal temperature and normal pressure when treating the coking wastewater, and the flow rate of the coking wastewater is 1-2 BV/h.

The technical scheme of the invention has the advantages that: the method does not directly use chloromethyl ether in the process of preparing the resin, and the prepared resin has large specific surface area, high adsorption rate, long service cycle in the process of treating the coking wastewater and high practical value in industrial production.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions: