阅读说明：本技术 净化己内酰胺生产废水的阴、阳离子交换树脂和废水净化方法 (Anion and cation exchange resin for purifying caprolactam production wastewater and wastewater purification method ) 是由 吕晓东 王义成 冷东斌 张伟 彭慧敏 吴万春 孙明丽 于 2019-10-11 设计创作，主要内容包括：本专利申请提供了一种净化己内酰胺生产废水的阴、阳离子交换树脂和废水净化方法。其阳离子交换树脂由苯乙烯单体系和二乙烯基苯单体系在致孔剂、引发剂和分散剂共同悬浮共聚,后经致孔剂抽提、干燥、筛分和磺化制得,其阴离子交换树脂由苯乙烯单体系和二乙烯基苯单体系在致孔剂、引发剂和分散剂共同悬浮共聚,经致孔剂抽提干燥筛分和氯化、胺化制得。其中的苯乙烯单体系由苯乙烯、对乙基苯乙烯和间乙基苯乙烯组成,二乙烯基苯单体系由对二乙烯基苯和间二乙烯基苯组成。阴、阳离子交换树脂以树脂柱串联结构装填在固定床反应器内,对己内酰胺生产废水实施净化处理。本发明具有净化工艺简单、净化能力稳定而长效、净化效率高的技术效果。(The application provides an anion and cation exchange resin for purifying caprolactam production wastewater and a wastewater purification method. The cation exchange resin is prepared by the common suspension copolymerization of a styrene monomer system and a divinylbenzene monomer system in a pore-foaming agent, an initiator and a dispersant, then the extraction, drying, screening and sulfonation of the pore-foaming agent are carried out, and the anion exchange resin is prepared by the common suspension copolymerization of the styrene monomer system and the divinylbenzene monomer system in the pore-foaming agent, the initiator and the dispersant, the extraction, drying, screening, chlorination and amination of the pore-foaming agent. Wherein the styrene monomer is composed of styrene, p-ethylstyrene and m-ethylstyrene, and the divinylbenzene monomer is composed of p-divinylbenzene and m-divinylbenzene. The anion and cation exchange resins are filled in a fixed bed reactor in a resin column series structure to carry out purification treatment on the caprolactam production wastewater. The invention has the technical effects of simple purification process, stable and long-acting purification capacity and high purification efficiency.)

1. a cation exchange resin for purifying caprolactam production wastewater is prepared by common suspension copolymerization of a styrene monomer system and a divinylbenzene monomer system on a pore-foaming agent, an initiator and a dispersing agent, and then by extraction, drying, screening and sulfonation of the pore-foaming agent, and is characterized in that the suspension copolymerization:

the styrene monomer system comprises 40-60 parts of styrene, 6-12 parts of p-ethylstyrene and 4-8 parts of m-ethylstyrene by weight, the divinylbenzene monomer system comprises 10-15 parts of p-divinylbenzene and 8-12 parts of m-divinylbenzene, 0.4-1.0 part of initiator, 38-42% of pore-forming agent by weight of the total weight of oil phase, 1.0-2.0 parts of dispersant and 400 parts of water by weight, the uniformly mixed oil phase is mixed with the uniform water phase in a polymerization kettle, then the temperature is slowly increased to 80 ℃, the stirring speed is 75 ~ 85 rpm, the suspension copolymerization reaction lasts for 8 ~ 18 hours, the mixture is cooled and discharged, and the discharged copolymerized white balls are alternately washed by hot water and cold water for many times;

drying and sieving to make the water content of the copolymerized white ball be 5-10%, and screening copolymerized white ball whose grain size is 0.3 ~ 0.9.9 mm as sulfonated matrix.

2. The cation exchange resin for purifying caprolactam production wastewater according to claim 1, wherein the extraction is: adding a solvent with the property of dissolving the pore-forming agent into a distillation kettle, heating and distilling, condensing the solvent to flow into an extraction kettle filled with suspension copolymerized white balls, dissolving and extracting the pore-forming agent in the copolymerized white balls, overflowing a mixed solution in the extraction kettle to the distillation kettle, distilling and condensing to flow into the extraction kettle, and circulating until the pore-forming agent of the copolymerized white balls is extracted completely.

3. Cation exchange resin for purifying caprolactam production wastewater according to claim 1, wherein the sulfonation is: mixing the white copolymer balls subjected to extraction, drying and screening treatment with 98% of sulfuric acid sulfonating agent, wherein the mass ratio of the white copolymer balls to the sulfonating agent is 1: 8-12, stirring the white copolymer balls and the sulfonating agent for 0.5-2 h for full mixing, sulfonating at the reaction temperature of 100-120 ℃ for 8-20h, cooling after the reaction is finished, placing the sulfonated resin in a washing column, washing the sulfonated resin to be neutral by using deionized water, and separating the sulfonated resin with the water content of 45-55%, so that the sulfonated resin is the cationic resin for purifying caprolactam production wastewater.

4. An anion exchange resin for purifying caprolactam production wastewater is prepared by common suspension copolymerization of a styrene monomer system and a divinylbenzene monomer system in a pore-foaming agent, an initiator and a dispersant, and then performing extraction, drying, screening, chlorination and amination through the pore-foaming agent, and is characterized in that the suspension copolymerization is prepared by common suspension copolymerization of the styrene monomer system and the divinylbenzene monomer system in the pore-foaming agent, the initiator and the dispersant, wherein the styrene monomer system comprises 40-60 parts by weight of styrene, 6-12 parts by weight of p-ethylstyrene and 4-8 parts by weight of m-ethylstyrene, the divinylbenzene monomer system comprises 10-15 parts by weight of p-divinylbenzene and 8-12 parts by weight of m-divinylbenzene, the initiator is 0.4-1.0 part by weight, the pore-foaming agent is 38-42% of the total weight of an oil phase, the dispersant is 1.0-2.0 parts by weight, the water is 300 parts by weight, the uniformly mixed oil phase is mixed with a uniform water phase in a polymerization kettle, the uniform water phase is slowly heated to 80 ℃, the stirring speed is 75 ~ revolutions per minute, the suspension copolymerization reaction is 8- ~ hours, the material is cooled, the material is discharged, the white ball is washed by hot water and the white ball is washed for multiple times, and the white ball is screened, and the copolymerization white ball is 0;

said chlorination

Adding the screened copolymerized white balls and chloromethyl ether into a chlorination reaction kettle, performing chlorination reaction for 2 hours at the temperature of ~ 35 ℃ at 30 ℃, then adding a zinc chloride catalyst accounting for 10-20% of the mass of the copolymerized white balls, raising the temperature to 45 ℃ and ~ 48 ℃ for continuous reaction for 10-20 hours, and cooling to below 30 ℃ after the reaction to obtain chlorine balls;

said amination

Dipping the chlorine ball into a mixed solution of dimethylamine and water, wherein the weight ratio of dimethylamine: water: and the mass ratio of the copolymerized chlorine balls is 20:4:5, the mixture is stirred uniformly after being stabilized for 30min, then the temperature is raised to 45 ℃, the temperature is kept for 8 hours, and finally the anion exchange resin for purifying the caprolactam production wastewater is obtained after washing.

5. Application rightA method for purifying wastewater from caprolactam production by using the cation exchange resin of any one of claims 1 to 3 and the anion exchange resin of claim 4, characterized in that the method comprises: the anion exchange resin and the cation exchange resin are serially filled in a fixed bed reactor through resin columns, the caprolactam production wastewater flows through the anion exchange resin and the cation exchange resin filled in the reactor, the temperature in the reactor is 40-60 ℃ at normal pressure, and the airspeed is not more than 20h^-1Purifying caprolactam production wastewater.

6. The process for purifying waste water from caprolactam production as claimed in claim 5, wherein the space velocity is 5.0 to 20 hours^-1。

Technical Field

The present patent application relates to ion exchange resins, and more particularly to polymeric ion exchange resins and methods of using the ion exchange resins for the purification of caprolactam production wastewater.

Background

Caprolactam is an important monomer raw material for producing nylon-6, and is also widely applied to the fields of plastics, fibers, films and the like. In the production process of caprolactam, functional agents such as strong oxidant, ammonia, concentrated sulfuric acid, cyclohexanone and the like are used, and a lot of side reactions exist, so that the components of the production wastewater are extremely complex, the production wastewater comprises various pollutants such as tert-butyl alcohol, toluene, cyclohexanone, cyclohexanol, cyclohexanone oxime, caprolactam, nitrate, sulfate and the like, the COD (chemical oxygen demand) of the wastewater is high, the wastewater is one of eight kinds of production wastewater which are difficult to treat in the petrochemical industry, and great pressure is brought to the environmental-friendly discharge of enterprises.

Disclosure of Invention

The invention aims to solve the problem of purification of caprolactam production wastewater and provides the anion and cation exchange resin for purifying caprolactam production wastewater and the wastewater purification method, which have the advantages of simple purification process, high operation efficiency and long-term stable high purification rate.

1. The application provides a cation exchange resin technical scheme for purifying caprolactam waste water, its main technical content is: a cation exchange resin for purifying caprolactam production wastewater is prepared by common suspension copolymerization of a styrene monomer system and a divinylbenzene monomer system on a pore-foaming agent, an initiator and a dispersing agent, and then by extraction, drying, screening and sulfonation of the pore-foaming agent, and is characterized in that the suspension copolymerization:

the styrene monomer system comprises 40-60 parts of styrene, 6-12 parts of p-ethylstyrene and 4-8 parts of m-ethylstyrene by weight, the divinylbenzene monomer system comprises 10-15 parts of p-divinylbenzene and 8-12 parts of m-divinylbenzene, 0.4-1.0 part of initiator, 38-42% of pore-forming agent by weight of the total weight of oil phase, 1.0-2.0 parts of dispersant and 400 parts of water by weight, the uniformly mixed oil phase is mixed with the uniform water phase in a polymerization kettle, then the temperature is slowly increased to 80 ℃, the stirring speed is 75 ~ 85 rpm, the suspension copolymerization reaction lasts for 8 ~ 18 hours, the mixture is cooled and discharged, and the discharged copolymerized white balls are alternately washed by hot water and cold water for many times;

drying and sieving to make the water content of the copolymerized white ball be 5-10%, and screening copolymerized white ball whose grain size is 0.3 ~ 0.9.9 mm as sulfonated matrix.

The pore-forming agent, the initiator and the dispersing agent in the technical scheme are conventional functional agents in suspension copolymerization of styrene and divinyl benzene, for example, but not limited to, the pore-forming agent is common white oil, the initiator is benzoyl peroxide, and the dispersing agent is alum.

One of the above technical solutions is preferably selected from the following technical solutions, and the extraction is: adding a solvent with the property of dissolving the pore-forming agent into a distillation kettle, heating and distilling, condensing the solvent to flow into an extraction kettle filled with suspension copolymerized white balls, dissolving and extracting the pore-forming agent in the copolymerized white balls, overflowing a mixed solution in the extraction kettle to the distillation kettle, distilling and condensing to flow into the extraction kettle, and circulating until the pore-forming agent of the copolymerized white balls is extracted completely.

One of the technical solutions is preferably selected from the following technical solutions, and the sulfonation is: mixing the white copolymer balls subjected to extraction, drying and screening treatment with 98% of sulfuric acid sulfonating agent, wherein the mass ratio of the white copolymer balls to the sulfonating agent is 1: 8-12, stirring the white copolymer balls and the sulfonating agent for 0.5-2 h for full mixing, sulfonating at the reaction temperature of 100-120 ℃ for 8-20h, cooling after the reaction is finished, placing the sulfonated resin in a washing column, washing the sulfonated resin to be neutral by using deionized water, and separating the sulfonated resin with the water content of 45-55%, so that the sulfonated resin is the cationic resin for purifying caprolactam production wastewater.

The technical scheme is that the anion exchange resin for purifying caprolactam production wastewater is prepared by the following main technical contents of carrying out suspension copolymerization on a styrene monomer system and a divinylbenzene monomer system together in a pore-foaming agent, an initiator and a dispersing agent, then carrying out pore-foaming agent extraction, drying, screening, chlorination and amination, and is characterized in that the suspension copolymerization is carried out, wherein the styrene monomer system and the divinylbenzene monomer system are used for carrying out suspension copolymerization together in a manner that the styrene monomer system and the divinylbenzene monomer system are used for carrying out suspension copolymerization on the pore-foaming agent, the initiator and the dispersing agent, the styrene monomer system comprises 40-60 parts by weight of styrene, 6-12 parts by weight of p-ethylstyrene and 4-8 parts by weight of m-ethylstyrene, the divinylbenzene monomer system comprises 10-15 parts by weight of p-divinylbenzene and 8-12 parts by weight of m-divinylbenzene, the initiator is 0.4-1.0 part by weight, the total weight of 38-42% by weight of an oil phase, the dispersing agent is 1.0-2.0 parts by weight, the water is 400 parts by weight of 300 parts of an oil phase, the uniformly mixed oil phase is mixed with a polymerization kettle, the uniform water phase is slowly heated up to 80 ℃, the stirring speed is 24 hours, the water content is 868.5-75%, the white ball is washed by a cooling reaction, and the white ball is carried out copolymerization reaction for a plurality of polymerization reaction, the white ball is carried out;

the chlorination:

adding the screened copolymerized white balls and chloromethyl ether into a chlorination reaction kettle, performing chlorination reaction for 2 hours at the temperature of ~ 35 ℃ at 30 ℃, then adding a zinc chloride catalyst accounting for 10-20% of the mass of the copolymerized white balls, raising the temperature to 45 ℃ and ~ 48 ℃ for continuous reaction for 10-20 hours, and cooling to below 30 ℃ after the reaction to obtain chlorine balls;

the amination comprises the following steps:

dipping the chlorine ball into a mixed solution of dimethylamine and water, wherein the weight ratio of dimethylamine: water: and the mass ratio of the copolymerized chlorine balls is 20:4:5, the mixture is stirred uniformly after being stabilized for 30min, then the temperature is raised to 45 ℃, the temperature is kept for 8 hours, and finally the anion exchange resin for purifying the caprolactam production wastewater is obtained after washing.

The application provides a wastewater purification method for purifying caprolactam production wastewater by using the anion exchange resin and the cation exchange resin. The method for purifying the caprolactam production wastewater comprises the following steps: the anion exchange resin and the cation exchange resin are filled in a fixed bed reactor in a layered manner, the wastewater generated in the caprolactam production flows through the anion exchange resin and the cation exchange resin filled in the reactor, and the reactor is filled with the anion exchange resin and the cation exchange resin at normal pressure, 40-60 ℃ and airspeed of not more than 20h^-1（5.0-20h^-1) Purifying caprolactam production wastewater.

The technical scheme of the anion and cation exchange resin for purifying caprolactam production wastewater and the wastewater purification method disclosed by the application changes the conventional polymerization monomer polymerization process method of the copolymer of the ion exchange resin, the polymerization monomer is combined with ethyl styrene, m-ethyl styrene, p-divinylbenzene and m-divinylbenzene, and through the disclosed suspension copolymerization process, the copolymerized white ball matrix framework has spatial meshing, the stability of the white ball matrix structure is improved, and the preferable pore-forming agent dosage and stirring speed are matched, so that the abrasion resistance of the copolymerized white ball matrix is improved, the pore structure of resin balling is optimized, the pore structure of the white ball matrix is very uniform, and pores with the pore diameter of 10-25nm account for more than 78% of the total pore volume. The combined action of the comprehensive technical means ensures the high activity and the high stability of the sulfonated resin and the chlorinated aminated resin, the wear-resisting rate of the anion-cation exchange resin reaches 92 percent, and the ball finishing rate after grinding reaches more than 85 percent, overcomes the technical problems that the ion exchange resin adopting the conventional polymerization process is used for purifying the wastewater generated in caprolactam production, micropores are blocked due to the inclusion of a large amount of and various oligomers in the wastewater impurities, and the adsorption capacity of the resin is rapidly inactivated, and has stable and long-acting purification capacity. According to the wastewater purification method, the anion exchange resin and the cation exchange resin bear different partial duties and have combined action, the anion exchange resin finishes the removal of nitrate in the wastewater, the cation exchange resin finishes the removal of substances such as ammonia nitrogen and the like, and the actual caprolactam wastewater purification application effect proves that the COD of the wastewater jointly purified and removed reaches more than 93 percent and the removal rate of the nitrate reaches more than 96 percent. The technical problem of caprolactam waste water purification treatment who has puzzled enterprise and technical staff has always been solved to this patent application scheme, easily realizes water environmental protection and discharges, its purification process is simple, have higher airspeed operation, high-efficient COD rate and nitrate, the high technological effect that is showing of purification efficiency.

Detailed Description

The technical content of the present patent application will be described by using each example and anion-cation exchange resin of each example in the purification treatment of wastewater from caprolactam production.