阅读说明：本技术 一种用于污水处理离子交换树脂的制备方法 (Preparation method of ion exchange resin for sewage treatment ) 是由 钱平 蔡小华 刘金彪 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种用于污水处理离子交换树脂的制备方法,涉及树脂领域,所述用于污水处理离子交换树脂的制备方法如下：S1、准备乙酰化苯乙烯20份、偶氮二异丁氰2份、二乙烯基二甲苯8份、四氧化三铁220份、γ三氧化二铁80份、明胶5份、二甲基二烯丙基氯化铵0.5份；S2、将乙酰化苯乙烯与偶氮二异丁氰及二乙烯基二甲苯进行混合,反应温度控制在60～100度,反应时间控制在1小时,得到乙酰化苯乙烯聚合液。本发明的用于污水处理离子交换树脂通过硫酸盐化反应使产物对于污水有较好的经济效应,相对于市售的常用同类产品而言,质量/体积交换容量能力相仿,但价格较低,具有极好的经济效应,再生后的质量/体积交换容量性能保存程度较好。(The invention discloses a preparation method of ion exchange resin for sewage treatment, which relates to the field of resin, and comprises the following steps: s1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride; s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 60-100 ℃ and the reaction time at 1 hour to obtain the acetylated styrene polymer solution. The ion exchange resin for sewage treatment of the invention has better economic effect on sewage through sulfation reaction, compared with the common similar products sold in the market, the ion exchange resin has similar mass/volume exchange capacity, but lower price, excellent economic effect and better preservation degree of the regenerated mass/volume exchange capacity.)

1. A preparation method of ion exchange resin for sewage treatment is characterized in that: the preparation method of the ion exchange resin for sewage treatment comprises the following steps:

s1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature to be 60-100 ℃, and controlling the reaction time to be 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 30-90% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

2. The method for preparing the ion exchange resin for sewage treatment according to claim 1, wherein the ion exchange resin comprises: the chemical formula of the acetylated styrene is shown as a formula (1).

3. The method for preparing the ion exchange resin for sewage treatment according to claim 1, wherein the ion exchange resin comprises: the gelatin can be replaced by corn starch mixed with water or other similar products.

4. The method for preparing the ion exchange resin for sewage treatment according to claim 1, wherein the ion exchange resin comprises: the mass percentage concentration of the aqueous solution of the gelatin is 2%.

5. The method for preparing the ion exchange resin for sewage treatment according to claim 1, wherein the ion exchange resin comprises: the particle size of the ferroferric oxide and the gamma ferric oxide is controlled within 20 nanometers, and the plus-minus error is within 10 nanometers.

Technical Field

The invention relates to the field of resin, in particular to a preparation method of ion exchange resin for sewage treatment.

Background

Ion exchange resins can be further classified into styrene resins and acrylic resins according to the types of the matrixes, the types of chemically active groups in the resins determine the main properties and types of the resins, and in practical use, the resins are often converted into other ion types for operation so as to meet various requirements.

The quality/volume exchange capacity performance of various resins sold in the market is obviously reduced after regeneration, so that the sewage treatment cost is increased, and the purchase cost of various resins sold in the market is extremely high due to high price.

Disclosure of Invention

The invention aims to: in order to solve the problems of high cost and large performance damage after regeneration of the existing sewage treatment, a preparation method of the ion exchange resin for sewage treatment is provided.

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an ion exchange resin for sewage treatment comprises the following steps:

s1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature to be 60-100 ℃, and controlling the reaction time to be 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 30-90% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Preferably, the acetylated styrene is of formula (1).

Preferably, the gelatin may be replaced by corn starch mixed with water or the like.

Preferably, the refluxing solvent is a mixed solvent of isopropanol and acetonitrile.

Preferably, the aqueous solution of gelatin has a mass percent concentration of 2%.

Preferably, the particle size of the ferroferric oxide and the gamma ferric oxide is controlled within 20 nanometers and the plus-minus error is within 10 nanometers.

Compared with the prior art, the invention has the beneficial effects that:

the ion exchange resin for sewage treatment of the invention has better economic effect on sewage through sulfation reaction, compared with the common similar products sold in the market, the ion exchange resin has similar mass/volume exchange capacity, but lower price, excellent economic effect and better preservation degree of the regenerated mass/volume exchange capacity.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

S1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 60 ℃ and the reaction time at 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 30% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Example 2

S1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 100 ℃ and the reaction time at 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 30% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Example 3

S1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 60 ℃ and the reaction time at 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 90% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Example 4

S1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 100 ℃ and the reaction time at 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 90% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Example 5

S1, preparing 20 parts of acetylated styrene, 2 parts of azodiisobutyronitrile, 8 parts of divinylxylene, 220 parts of ferroferric oxide, 80 parts of gamma ferric oxide, 5 parts of gelatin and 0.5 part of dimethyl diallyl ammonium chloride;

s2, mixing the acetylated styrene with azodiisobutyronitrile and divinyl xylene, controlling the reaction temperature at 80 ℃ and the reaction time at 1 hour to obtain an acetylated styrene polymer solution;

s3, adding ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride into the acetylated styrene polymer solution to enable the ratio of ferroferric oxide, gamma ferric oxide, gelatin and dimethyl diallyl ammonium chloride to reach 60% of the acetylated styrene polymer solution, carrying out polymerization reaction, controlling the reaction time to be 12 hours, and heating in a step heating mode;

s4, washing the polymerization reaction product, and polymerizing the polymerization reaction product with azodiisobutyronitrile, gelatin and isopropanol again, wherein the reaction time is controlled to be 1 hour;

s5, and mixing the reacted product according to a ratio of 1: adding ferroferric oxide and gamma ferric oxide according to the proportion of 0.5, carrying out polymerization reaction, controlling the reaction temperature at 75 ℃ and the reaction time at 12 hours, and washing after the reaction is finished;

s6, introducing sulfonic acid groups into the washed product to carry out sulfation reaction, thereby obtaining the ion exchange resin.

Example 6

Weak acid heavy metal wastewater discharged from a certain electroplating enterprise is extracted, fully mixed and averagely divided into 7 parts, the resins prepared in the embodiments 1, 2, 3, 4 and 5 of the invention are respectively used for treating sewage, and the mass/volume exchange capacity of the resins is measured by comparing with commercially available resins, namely, domestic 1 and domestic 2, and the results are shown in table 1.

Table 1: results of comparison of the resins obtained in examples 1, 2, 3, 4 and 5 with commercially available resins (Table values in mmol/ml)

As can be seen from Table 1, the mass/volume exchange capacity performance of the resins prepared in examples 3, 4 and 5 of the present invention for the weak acid heavy metal wastewater is similar to that of the commercially available resins, namely, domestic 1 and domestic 2, and both the mass/volume exchange capacity performance of the resins prepared in examples 3 and 4 of the present invention is above 4.2, the mass/volume exchange capacity performance of the resins prepared in examples 3 and 4 of the present invention for the weak acid heavy metal wastewater after primary regeneration is still above 4.0, the mass/volume exchange capacity performance of the resins prepared in example 3 and 4 of the resins prepared in example 3 after secondary regeneration is still 4.0, and the mass/volume exchange capacity performance of the resins prepared in domestic 2 for the weak acid heavy metal wastewater in the primary use is the highest, but the mass/volume exchange capacity performance of the resins prepared in example 3 after primary regeneration for the weak acid heavy metal wastewater is the same as that in example 3, and the mass/volume exchange capacity performance of the resins prepared in example 3 of the resins prepared in Can be similar to the commercial resin, but has good reproducibility, long service life, better economic effect and cost saving.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.