CN1781965A - Water soluble chelated resin and its synthetic method and use - Google Patents

Abstract

Translated fromChinese

本发明是关于一种能去除重金属离子的水溶性螯合树脂、其合成方法和应用。利用环氧树脂中的环氧端基与过量有机二胺反应，再通过环氧氯丙烷扩链，合成了含有双酚－A疏水单元的聚胺大分子，聚胺与CS₂在碱性条件下反应生成带有二硫代氨基甲酸盐螯合基团的水溶性高分子。引入疏水单元不但可以增加聚胺大分子的反应活性，更重要的是为了增加螯合树脂的疏水性，使重金属离子可以在很低的浓度下与螯合树脂作用产生沉淀物质，缩短沉淀时间，提高沉淀效果，降低残留离子浓度。本发明提供的螯合树脂主要用于电镀废水中的Cu²⁺、Ni²⁺、Zn²⁺、Cr³⁺等重金属离子的快速除去，保证废水排放达到国家一级标准(＜0.5ppm)。The invention relates to a water-soluble chelating resin capable of removing heavy metal ions, its synthesis method and application. The polyamine macromolecule containing bisphenol-A hydrophobic unit was synthesized by reacting the epoxy end group in the epoxy resin with excess organic diamine, and then extended by epichlorohydrin. The polyamine and CS₂ were synthesized under alkaline conditions. The following reaction generates a water-soluble polymer with a dithiocarbamate chelating group. The introduction of hydrophobic units can not only increase the reactivity of polyamine macromolecules, but more importantly, in order to increase the hydrophobicity of chelating resins, so that heavy metal ions can interact with chelating resins at very low concentrations to produce precipitated substances, shortening the precipitation time, Improve the precipitation effect and reduce the residual ion concentration. The chelating resin provided by the invention is mainly used for rapid removal of Cu²⁺ , Ni²⁺ , Zn²⁺ , Cr³⁺ and other heavy metal ions in electroplating wastewater, so as to ensure that the wastewater discharge reaches the national first-class standard (<0.5ppm).

Description

Translated fromChinese

一种水溶性螯合树脂和其合成方法及其应用A kind of water-soluble chelating resin and its synthetic method and its application

技术领域technical field

本发明涉及一种水溶性螯合树脂，以及其合成方法和利用该液体树脂来除去工业废水中的重金属离子的应用。The invention relates to a water-soluble chelating resin, its synthesis method and the application of using the liquid resin to remove heavy metal ions in industrial waste water.

背景技术Background technique

现代工业发展带来的环境污染日益加重，保护环境是当前社会关注的重要课题。排放重金属离子的产业包括电镀、印刷电路板、化工以及金属冶炼等，重金属离子主要包括铜、镍、铬、铅、锰、钴、铁、锌、以及六价铬等，当此类重金属离子如进入水源后，将使饮用水及水产品受到严重污染，使用后在人体中发生可怕的病变。为防范于未然，有必要提供一种高效、方便的重金属处理方法，这正是本发明所研究的课题。The environmental pollution caused by the development of modern industry is increasing day by day, and protecting the environment is an important topic of current social concern. Industries that emit heavy metal ions include electroplating, printed circuit boards, chemicals, and metal smelting. Heavy metal ions mainly include copper, nickel, chromium, lead, manganese, cobalt, iron, zinc, and hexavalent chromium. When such heavy metal ions are After entering the water source, drinking water and aquatic products will be seriously polluted, and terrible pathological changes will occur in the human body after use. For taking precautions, it is necessary to provide an efficient and convenient heavy metal treatment method, which is the subject of the present invention.

目前处理重金属废水主要依靠化学处理法。如中和沉淀法是使重金属离子与碱反应生成不溶于水的氢氧化物沉淀，硫化物沉淀法则是使重金属离子与硫离子反应生成不溶于水的金属硫化物沉淀。这些沉淀物质可以简单地用过滤办法除去。实践中发现，中和沉淀法和硫化物沉淀法都有一定的不足，特别是对铜离子始终无法达到满意的效果。At present, the treatment of heavy metal wastewater mainly relies on chemical treatment. For example, the neutralization precipitation method is to make heavy metal ions react with alkali to form a water-insoluble hydroxide precipitate, and the sulfide precipitation method is to make heavy metal ions and sulfide ions react to form a water-insoluble metal sulfide precipitate. These precipitated materials can be removed simply by filtration. It has been found in practice that both the neutralization precipitation method and the sulfide precipitation method have certain deficiencies, especially for copper ions, which have always been unable to achieve satisfactory results.

近年来，高分子螯合剂开始被用于处理重金属离子废水，它对金属离子的沉淀效果优于传统的小分子沉淀剂。具有代表性的是一类含有大量二硫代甲酸根(-CSS^-)螯合基团的水溶性高分子。从目前已知的文献来看，绝大部分的工作集中在两个方面：一是提高螯合树脂的分子量，二是增加螯合基团的数量。虽然文献报导此类螯合树脂具有很好的使用效果，但是在实际应用中发现，使用后的铜离子浓度一般无法达到国家一级标准，并且会出现沉淀不彻底(经常需要高分子絮凝剂辅助沉淀)、水质变红、有机物二次污染等问题。究其原因，这些螯合树脂都是强亲水性聚电解质，要想使其沉淀必须有充足金属离子的螯合作用。可是当废水中的离子浓度较低时，大分子链上只有部分螯合基团与离子作用，而未发生螯合作用的部分作为亲水基团却起到增溶效果，整个分子仍不会沉淀，结果不但达不到除污的效果反而会造成二次污染。总的来说，这些水溶性强的螯合剂对使用操作要求较高，除污不够彻底，有待于进一步改进。如专利公告号为CN1323747A的《高分子重金属捕集沉淀剂》(黄翠萍，2001)，就采用混合的化学试剂来沉淀一些金属离子，其中就包含了高分子螯合剂，也存在类似不足。In recent years, polymer chelating agents have been used to treat heavy metal ion wastewater, and their precipitation effect on metal ions is better than that of traditional small molecule precipitants. A representative one is a class of water-soluble polymers containing a large number of dithioformate (-CSS^- ) chelating groups. From the presently known literature, most of the work concentrates on two aspects: the one is to improve the molecular weight of chelating resin, and the 2nd is to increase the quantity of chelating group. Although the literature reports that this type of chelating resin has a good use effect, it is found in practical applications that the copper ion concentration after use generally cannot reach the national first-level standard, and the precipitation will not be complete (often requiring the assistance of polymer flocculants) Precipitation), red water quality, secondary pollution of organic matter and other issues. Trace it to its cause, these chelating resins are all strong hydrophilic polyelectrolytes, must have the chelation of sufficient metal ion in order to make it precipitate. However, when the concentration of ions in the wastewater is low, only part of the chelating groups on the macromolecular chain interact with the ions, and the part that has not undergone chelation acts as a hydrophilic group to solubilize, and the whole molecule still does not Precipitation, the result will not only fail to achieve the effect of decontamination but will cause secondary pollution. Generally speaking, these highly water-soluble chelating agents have high requirements for operation, and the decontamination is not thorough enough, which needs further improvement. Such as patent notification number CN1323747A "polymer heavy metal trapping precipitant" (Huang Cuiping, 2001), just adopt mixed chemical reagents to precipitate some metal ions, wherein just comprised polymer chelating agent, also there is similar deficiency.

发明内容Contents of the invention

本发明所要解决的首要技术问题是针对现有背景技术而提供一种操作方便、沉淀彻底、效果好的水溶性螯合树脂。The primary technical problem to be solved by the present invention is to provide a water-soluble chelating resin with convenient operation, thorough precipitation and good effect in view of the existing background technology.

本发明所要解决的另一个技术问题是提供一种容易合成、使用方便、沉淀效果好的用来制备上述水溶性螯合树脂的合成方法。Another technical problem to be solved by the present invention is to provide a kind of synthetic method that is easy to synthesize, easy to use, and good precipitation effect is used for preparing above-mentioned water-soluble chelating resin.

本发明所要解决的再一个技术问题是提供一种上述水溶性螯合树脂的应用。Another technical problem to be solved by this invention is to provide a kind of application of above-mentioned water-soluble chelating resin.

本发明解决首要技术问题所采用的技术方案为：一种水溶性螯合树脂，其特征在于The technical solution adopted by the present invention to solve the primary technical problem is: a water-soluble chelating resin, characterized in that

为具有以下结构通式的聚合物，is a polymer having the following general structure,

其中EPOX代表环氧树脂链段，其结构可表示为：Among them, EPOX represents the epoxy resin segment, and its structure can be expressed as:

m是从1到5的整数m is an integer from 1 to 5

x+y＝1，0＜x＜1，0＜y＜1。x+y=1, 0<x<1, 0<y<1.

非常有益的是，上述的聚合物其环氧树脂与乙二胺重量比为3∶1至4∶1的范围，从而保证水相中重金属离子的浓度始终在0.5ppm以下，使处理过的污水满足国家排放标准。It is very beneficial that the weight ratio of epoxy resin and ethylenediamine of the above-mentioned polymer is in the range of 3:1 to 4:1, so as to ensure that the concentration of heavy metal ions in the water phase is always below 0.5ppm, so that the treated sewage Meet the national emission standards.

有益的是，上述的聚合物其粘度在16-50Pa.s范围。Advantageously, the aforementioned polymers have a viscosity in the range of 16-50 Pa.s.

本发明解决另一个技术问题所采用的技术方案为：一种制备上述水溶性螯合树脂的合成方法，其特征步骤依次为：将乙二胺与坏氧树脂按重量比为2/1～1/4逐渐混合，混合时放热，在70～80℃反应完全，得到预聚物，逐渐滴加扩链剂环氧氯丙烷，环氧氯丙烷与乙二胺重量比为1∶0.5～1∶10，在85～95℃下反应充分得到聚胺树脂；所述的聚胺树脂在碱性条件下与二硫化碳反应，生成含二硫代氨基甲酸钠的螯合树脂，反应的pH值控制在9～12，温度为30～40℃。The technical solution adopted by the present invention to solve another technical problem is: a kind of synthetic method for preparing the above-mentioned water-soluble chelating resin, and its characteristic steps are as follows: the ratio by weight of ethylenediamine and bad oxygen resin is 2/1～1 /4 Mix gradually, heat is released during mixing, and the reaction is complete at 70-80°C to obtain a prepolymer, and the chain extender epichlorohydrin is gradually added dropwise, and the weight ratio of epichlorohydrin to ethylenediamine is 1:0.5-1 : 10, fully react to obtain polyamine resin at 85～95 ℃; Described polyamine resin reacts with carbon disulfide under alkaline condition, generates the chelating resin containing sodium dithiocarbamate, and the pH value of reaction is controlled at 9 ～12, the temperature is 30～40℃.

有益的是，上述的二硫化碳与乙二胺摩尔之比为2∶1，反应结束后体系中少量未反应的二硫化碳最后通过氮气吹扫除去，通过简便方法使其反应尽可能完全，同时，快速地处理掉多余的二硫化碳。It is beneficial that the molar ratio of the above-mentioned carbon disulfide to ethylenediamine is 2: 1. After the reaction, a small amount of unreacted carbon disulfide in the system is finally removed by nitrogen purging, and the reaction is as complete as possible by a simple method, and at the same time, quickly Dispose of excess carbon disulfide.

非常有益的是，反应所添加氢氧化钠的量与二硫化碳等摩尔，为控制螯合剂在反应过程中有较好的溶解性能，一般控制氢氧化钠的浓度控制在30～35％之间，反应结束后螯合剂的pH值为12。It is very beneficial that the amount of sodium hydroxide added in the reaction is equimolar to carbon disulfide. In order to control the chelating agent to have better solubility in the reaction process, the concentration of sodium hydroxide is generally controlled between 30% and 35%. The pH of the chelating agent was 12 after finishing.

本发明解决再一个技术问题所采用的技术方案为：上述的水溶性螯合树脂的应用，其特征在于螯合树脂在含重金属离子的废水上环保处理上应用。The technical solution adopted by the present invention to solve another technical problem is: the application of the above-mentioned water-soluble chelating resin, which is characterized in that the chelating resin is used in the environmental protection treatment of waste water containing heavy metal ions.

上述的重金属离子包括铜、镍、铬、铅、锰、钴、铁、锌或六价铬等金属离子。The above-mentioned heavy metal ions include metal ions such as copper, nickel, chromium, lead, manganese, cobalt, iron, zinc or hexavalent chromium.

非常有益的是，上述的螯合树脂其环氧树脂与乙二胺重量比为3∶1至4∶1的范围，作为铜金属离子的沉淀剂，来控制废水铜离子浓度在0.5ppm以下，满足国家一级排放标准。It is very beneficial that its epoxy resin and ethylenediamine weight ratio of the above-mentioned chelating resin are in the range of 3: 1 to 4: 1, as a precipitant for copper metal ions, to control the concentration of copper ions in waste water below 0.5ppm, Meet the national first-level emission standards.

与现有技术相比，本发明的优点在于：在高分子中引入强疏水的链段，使螯合树脂处在一个亲水与疏水的平衡之中，只需极少量的重金属离子的螯合作用为诱导，就可以使高聚物分子由水溶性转化为非水溶性而脱离水相，从而保证水相中重金属离子的浓度始终在0.5ppm以下。利用环氧树脂的强疏水性和高的反应活性，可合成含有疏水链段的聚氨大分子，其疏水性的强弱可以通过环氧树脂加入量的多少来调节，操作比较方便容易。螯合树脂的沉淀效果好、彻底，缩短沉淀时间，提高沉淀效果，降低残留离子浓度，不会造成二次污染，使用方法简便，成本低。Compared with the prior art, the present invention has the advantages of introducing a strong hydrophobic segment into the macromolecule so that the chelating resin is in a balance between hydrophilic and hydrophobic, and only needs a very small amount of heavy metal ion chelation. As an inducement, the polymer molecules can be changed from water-soluble to water-insoluble and separated from the water phase, so as to ensure that the concentration of heavy metal ions in the water phase is always below 0.5ppm. Utilizing the strong hydrophobicity and high reactivity of epoxy resin, polyurethane macromolecules containing hydrophobic segments can be synthesized. The strength of hydrophobicity can be adjusted by the amount of epoxy resin added, and the operation is more convenient and easy. The precipitation effect of the chelating resin is good and thorough, the precipitation time is shortened, the precipitation effect is improved, the concentration of residual ions is reduced, no secondary pollution is caused, the method of use is simple, and the cost is low.

附图说明Description of drawings

图1为螯合剂处理前后铜离子浓度变化情况示意图。Figure 1 is a schematic diagram of the change of copper ion concentration before and after chelating agent treatment.

具体实施方式Detailed ways

以下结合附图实施例对本发明作进一步详细描述。The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

在装有搅拌器、回流冷凝管、滴液漏斗和温度计的四口烧瓶中分别按表1加入不同重量的环氧树脂(牌号E-44)与乙二胺。混合均匀后(有大量热量放出，须冷水冷却)，在70-80℃下反应2小时。待树脂与乙二胺反应完全后，按表1滴加不同量的环氧氯丙烷，在0.5小时内滴完后，再在100℃保温0.5小时，以确保聚合充分。最后得到高温粘稠低温固化的聚胺树脂。聚氨树脂的溶解性与反应物的组成有关，它在水中的溶解度随环氧树脂加入量的增加而减小，同时水的酸度对树脂的溶解性也有较大的影响，聚氨树脂上的仲氨在酸性条件下(pH≤4)容易形成季铵盐，因而水溶性提高。此外，聚氨树脂在有机溶剂甲醇和二甲基甲酰胺中的溶解性也与疏水链段的多少有关，聚氨在甲醇中的溶解性与在水中的一致，在二甲基甲酰胺中的溶解性随环氧树脂用量的增加而提高。说明高聚物分子的疏水性可以由环氧树脂的投料量来控制。In a four-neck flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, add different weights of epoxy resin (brand E-44) and ethylenediamine according to Table 1. After mixing evenly (a large amount of heat is released, cooling with cold water is required), react at 70-80°C for 2 hours. After the reaction between the resin and ethylenediamine is complete, add different amounts of epichlorohydrin dropwise according to Table 1. After the drop is completed within 0.5 hours, keep the temperature at 100°C for 0.5 hours to ensure sufficient polymerization. Finally, a high-temperature viscous low-temperature curing polyamine resin is obtained. The solubility of polyurethane resin is related to the composition of reactants. Its solubility in water decreases with the increase of epoxy resin addition. At the same time, the acidity of water also has a great influence on the solubility of resin. Secondary ammonia easily forms quaternary ammonium salts under acidic conditions (pH ≤ 4), thus improving water solubility. In addition, the solubility of polyurethane resin in organic solvents methanol and dimethylformamide is also related to the number of hydrophobic segments. The solubility of polyurethane in methanol is consistent with that in water, and the solubility of polyurethane in dimethylformamide The solubility increases with the increase of the amount of epoxy resin. It shows that the hydrophobicity of polymer molecules can be controlled by the amount of epoxy resin.

                           表1不同聚胺树脂的溶解性样品   重量/g                 水中溶解性        有机溶剂   环氧树脂   乙二胺   环氧氯丙烷   pH≥9   4＜pH＜9   pH≤4   甲醇   二甲基甲酰胺   聚胺1聚胺2聚胺3聚胺4聚胺5   403020105   1010101010   4.67.310.012.714.1   不溶不溶不溶可溶可溶   不溶不溶可溶可溶可溶   可溶可溶可溶可溶可溶   不溶不溶可溶可溶可溶   可溶可溶可溶不溶不溶Table 1 Solubility of different polyamine resins sample Weight/g Solubility in water Organic solvents epoxy resin Ethylenediamine Epichlorohydrin pH≥9 4<pH<9 pH≤4 Methanol dimethylformamide Polyamine 1 Polyamine 2 Polyamine 3 Polyamine 4 Polyamine 5 403020105 1010101010 4.67.310.012.714.1 insoluble insoluble insoluble soluble soluble insoluble insoluble soluble soluble soluble soluble soluble soluble soluble soluble insoluble insoluble soluble soluble soluble soluble soluble soluble insoluble insoluble

将上述实例得到的聚胺树脂在碱性条件下与二硫化碳反应。其中聚胺1、聚胺2虽不溶解于水中，但是由于亲水基团的存在，能被水所溶胀，同时疏水基团的存在使得聚合物容易吸收二硫化碳，有利于反应的进行。聚胺树脂在与二硫化碳、碱的反应过程中，整个分子的水溶性增加，最终形成水溶性的高分子溶液。具体反应过程如下：The polyamine resin that above-mentioned example obtains is reacted with carbon disulfide under alkaline condition. Although polyamine 1 and polyamine 2 are insoluble in water, they can be swelled by water due to the presence of hydrophilic groups, and the presence of hydrophobic groups makes the polymers easy to absorb carbon disulfide, which is beneficial to the reaction. During the reaction of polyamine resin with carbon disulfide and alkali, the water solubility of the whole molecule increases, and finally forms a water-soluble polymer solution. Concrete reaction process is as follows:

在上述树脂中加入80g去离子水，搅拌均匀，接着按化学剂量比同时滴加浓度为33wt％的氢氧化钠水溶液和二硫化碳，在20分钟内滴加完毕。加完后溶液温度逐渐升至40℃反应2小时，在此过程中不溶于水的聚合物逐渐溶解，最后得到无色或淡黄色的粘稠液体，用去离子水将溶液浓度都调整到35％，测定溶液的黏度。不同螯合剂溶液的粘度见表2。从表2可以看出，高分子水溶液的粘度随着环氧树脂量的增加而升高，这是由于大分子链上的刚性疏水基团增加，会促使高分子在水溶液中的流体力学半径增加，从而导致高分子水溶液的粘度上升。Add 80 g of deionized water to the above resin, stir evenly, then add 33 wt% sodium hydroxide aqueous solution and carbon disulfide dropwise at the same time according to the stoichiometric ratio, and the dropwise addition is completed within 20 minutes. After the addition, the temperature of the solution was gradually raised to 40°C and reacted for 2 hours. During this process, the water-insoluble polymer gradually dissolved, and finally a colorless or light yellow viscous liquid was obtained. The concentration of the solution was adjusted to 35 with deionized water. % to measure the viscosity of the solution. The viscosities of different chelating agent solutions are shown in Table 2. It can be seen from Table 2 that the viscosity of the polymer aqueous solution increases with the increase of the amount of epoxy resin, which is due to the increase of the rigid hydrophobic groups on the macromolecular chain, which will promote the increase of the hydrodynamic radius of the polymer in the aqueous solution , resulting in an increase in the viscosity of the polymer aqueous solution.

               表2不同螯合剂的反应组成及其水溶液的粘度样品   环氧树脂与乙二胺重量比   环氧氯丙烷(ml)   二硫化碳(ml)   NaOH溶液(ml)   粘度(Pa.s)   螯合剂1螯合剂2螯合剂3   4∶13∶12∶1   3.96.18.5   19.819.819.8   35.638.341.0   40.529.821.1   螯合剂4螯合剂5   1∶10.5∶1   10.811.9   19.819.8   43.845.1   17.816.2The reaction composition of table 2 different chelating agents and the viscosity of its aqueous solution sample Weight ratio of epoxy resin to ethylenediamine Epichlorohydrin (ml) Carbon disulfide (ml) NaOH solution (ml) Viscosity(Pa.s) Chelating agent 1 Chelating agent 2 Chelating agent 3 4:13:12:1 3.96.18.5 19.819.819.8 35.638.341.0 40.529.821.1 Chelating agent 4 Chelating agent 5 1:10.5:1 10.811.9 19.819.8 43.845.1 17.816.2

注：粘度测定温度为25℃；乙二胺的重量为10g。Note: The viscosity measurement temperature is 25°C; the weight of ethylenediamine is 10g.

为了测定不同螯合树脂的沉淀性能，配制不同铜离子浓度的水溶液，只加入螯合树脂，不加其他任何种类的絮凝剂和助凝剂，观察在1分钟内能否出现螯合物沉淀。表3中列出的是出现沉淀的所需的最低铜离子浓度，低于该浓度时无论怎样加入螯合树脂都不会在1分钟内出现沉淀。螯合树脂中疏水基团的含量越高，越接近疏水/亲水的平衡点，其沉淀性也越好。反之，疏水基团的含量越少，意味着亲水基团越多，形成螯合物沉淀所需的铜离子越多。事实上，螯合剂1和螯合剂2在水相中处于一种分相状态，即疏水基团相互缔合形成疏水微区，少量的铜离子就会使体系因发生凝胶而沉淀。In order to measure the precipitation performance of different chelating resins, prepare aqueous solutions with different concentrations of copper ions, add only chelating resins, without adding any other flocculants and coagulants, and observe whether chelate precipitation occurs within 1 minute. Listed in table 3 is the required minimum concentration of copper ions that precipitate occurs, no matter how the chelating resin is added when lower than this concentration, precipitation will not occur within 1 minute. The higher the content of hydrophobic groups in the chelating resin, the closer to the balance point of hydrophobic/hydrophilic, and the better its precipitability. Conversely, the less the content of hydrophobic groups, the more hydrophilic groups, and the more copper ions required for chelate precipitation. In fact, chelating agent 1 and chelating agent 2 are in a phase-separated state in the water phase, that is, hydrophobic groups associate with each other to form hydrophobic microdomains, and a small amount of copper ions will cause the system to precipitate due to gelation.

      表3能使铜离子出现沉淀的最低浓度   树脂种类   Cu²⁺最低沉淀浓度/ppm   螯合剂1   0.10   螯合剂2   0.50   螯合剂3   1.0   螯合剂4   2.5   螯合剂5   3.0Table 3 The minimum concentration that can cause copper ions to precipitate Resin type Cu²⁺ minimum precipitation concentration/ppm Chelating agent 1 0.10 Chelating agent 2 0.50 Chelating agent 3 1.0 Chelating agent 4 2.5 Chelating agent 5 3.0

以螯合剂2进行重金属离子沉淀实验。取100mlpH值为5的电镀废水，其内分别含有8ppm的铜、锌、镍、镉、锰、铅、铬离子，加入不同体积浓度为5wt％的螯合剂2，每加入一次就取一次清液样品，用原子吸收分析仪测定其中残存的重金属离子浓度。结果如表4所示，该螯合剂对这些金属离子都有去除的效果，加入5ml后残留离子的浓度都可以保持在0.5ppm以下。The heavy metal ion precipitation experiment was carried out with chelating agent 2. Take 100ml of electroplating wastewater with a pH value of 5, which contains 8ppm of copper, zinc, nickel, cadmium, manganese, lead, and chromium ions, and add chelating agent 2 with a different volume concentration of 5wt%, and take a clear solution every time you add it Samples were measured with an atomic absorption analyzer for the concentration of heavy metal ions remaining therein. The results are shown in Table 4, the chelating agent has the effect of removing these metal ions, and the concentration of residual ions can be kept below 0.5ppm after adding 5ml.

       表4螯合树脂沉淀重金属离子的效果   试剂体积/ml   铜   锌   镍   镉   锰   铅   铬   1.0   2.42   3.52   3.56   2.15   4.23   2.84   3.78   3.0   0.36   0.40   0.31   0.50   1.57   0.58   1.18   5.0   0.18   0.23   0.19   0.30   0.48   0.28   0.24   7.0   0.06   0.10   0.12   0.08   0.10   0.02   0.43   9.0   0.02   0.05   0.05   0.02   0.05   0.04   0.11The effect of table 4 chelating resin precipitation heavy metal ion Reagent volume/ml copper zinc nickel cadmium manganese lead chromium 1.0 2.42 3.52 3.56 2.15 4.23 2.84 3.78 3.0 0.36 0.40 0.31 0.50 1.57 0.58 1.18 5.0 0.18 0.23 0.19 0.30 0.48 0.28 0.24 7.0 0.06 0.10 0.12 0.08 0.10 0.02 0.43 9.0 0.02 0.05 0.05 0.02 0.05 0.04 0.11

我们首次引入了最低沉淀浓度作为评价螯合树脂沉淀效果的重要指标，所谓最低沉淀浓度是指诱导螯合树脂在一分钟内产生沉淀的最低铜离子浓度。如果某种螯合树脂的最低沉淀浓度小于0.5ppm，那么使用这种螯合树脂就可以保证铜离子浓度达到国家一级标准。在处理重金属离子废水的实际操作过程中，离子浓度总是在一定的范围内波动变化的，再加上废水池体积较大，受扩散速率的限制，池内局部浓度也会不一致，而通常螯合剂的加入量是不会随之改变的。为此我们对螯合树脂的性能做动态试验，即改变离子的浓度而保持螯合剂的加入量不变，在一段时间内观察残存离子浓度的变化。For the first time, we introduced the minimum precipitation concentration as an important indicator for evaluating the precipitation effect of chelating resins. The so-called minimum precipitation concentration refers to the minimum copper ion concentration that induces the precipitation of chelating resins within one minute. If the minimum precipitation concentration of a certain chelating resin is less than 0.5ppm, then the use of this chelating resin can ensure that the copper ion concentration reaches the national first-level standard. In the actual operation process of treating heavy metal ion wastewater, the ion concentration always fluctuates within a certain range. In addition, the volume of the wastewater pool is large, and the local concentration in the pool will be inconsistent due to the limitation of the diffusion rate. Usually, the chelating agent The amount added will not change accordingly. For this reason, we do dynamic tests on the performance of chelating resins, that is, changing the concentration of ions while keeping the amount of chelating agent added constant, and observing the changes in the concentration of residual ions within a period of time.

动态模拟试验：以电镀厂排放的不合格废水为实验对象，使用螯合树脂2处理20Kg废水，先将废水pH值调节至8.5，加入螯合剂使浓度达到20ppm，搅拌10min后沉淀完全，取上层清液用原子吸收方法测定铜离子浓度。得到如图1的结果，说明使用了螯合剂后，废水中铜离子浓度均低于0.5ppm，已经达到国家一级排放标准。Dynamic simulation test: take the unqualified wastewater discharged from the electroplating factory as the experimental object, use chelating resin 2 to treat 20Kg wastewater, first adjust the pH value of the wastewater to 8.5, add a chelating agent to make the concentration reach 20ppm, stir for 10 minutes and then precipitate completely, take the upper layer The concentration of copper ions in the serum was determined by atomic absorption method. The results shown in Figure 1 are obtained, which shows that after using the chelating agent, the concentration of copper ions in the wastewater is lower than 0.5ppm, which has reached the national first-level discharge standard.

Claims (10)

Translated fromChinese

1、一种水溶性螯合树脂，其特征在于为具有以下结构通式的聚合物，1, a kind of water-soluble chelate resin, it is characterized in that having the polymer of following general structural formula,其中EPOX代表环氧树脂链段，其结构可表示为：Among them, EPOX represents the epoxy resin segment, and its structure can be expressed as:m是从1到5的整数m is an integer from 1 to 5x+y＝1，0＜x＜1，0＜y＜1。x+y=1, 0<x<1, 0<y<1.2、根据权利要求1所述的水溶性螯合树脂，其特征在于所述的聚合物其环氧树脂与乙二胺重量比为3∶1至4∶1的范围。2. The water-soluble chelating resin according to claim 1, characterized in that the weight ratio of epoxy resin to ethylenediamine of the polymer is in the range of 3:1 to 4:1.3、根据权利要求1或2所述的水溶性螯合树脂，其特征在于所述的聚合物粘度在16-50Pa.s范围。3. The water-soluble chelating resin according to claim 1 or 2, characterized in that the viscosity of the polymer is in the range of 16-50 Pa.s.4、一种权利要求1所述的水溶性螯合树脂的合成方法，其特征在于步骤依次为：4, a kind of synthetic method of water-soluble chelating resin as claimed in claim 1 is characterized in that step is successively:(1)将乙二胺与环氧树脂按重量比为2/1～1/4逐渐混合，混合时放热，在70～80℃反应完全，得到预聚物，逐渐滴加扩链剂环氧氯丙烷，环氧氯丙烷与乙二胺重量比为1∶0.5～1∶10，在85～95℃下反应充分得到聚胺树脂；(1) Gradually mix ethylenediamine and epoxy resin at a weight ratio of 2/1 to 1/4, exotherm during mixing, and react completely at 70 to 80°C to obtain a prepolymer, and gradually add chain extender rings Oxychloropropane, the weight ratio of epichlorohydrin to ethylenediamine is 1: 0.5 to 1: 10, and the polyamine resin is fully reacted at 85 to 95 ° C;(2)所述的聚胺树脂在碱性条件下与二硫化碳反应，生成含二硫代氨基甲酸钠的螯合树脂，反应的pH值控制在9～12，温度为30～40℃。(2) The polyamine resin reacts with carbon disulfide under alkaline conditions to generate a chelating resin containing sodium dithiocarbamate, the pH value of the reaction is controlled at 9 to 12, and the temperature is 30 to 40°C.5、根据权利要求4所述的合成方法，其特征在于所述的硫化碳与乙二胺摩尔之比为2∶1，反应结束后体系中少量未反应的二硫化碳最后通过氮气吹扫除去。5. The synthesis method according to claim 4, characterized in that the molar ratio of carbon sulfide to ethylenediamine is 2:1, and a small amount of unreacted carbon disulfide in the system is finally removed by nitrogen purging after the reaction is completed.6、根据权利要求4所述的合成方法，其特征在于所述的反应其添加的氢氧化钠的用量与二硫化碳为等摩尔。6. The synthesis method according to claim 4, characterized in that the amount of sodium hydroxide added in the reaction is equimolar to that of carbon disulfide.7、根据权利要求4所述的合成方法，其特征在于所述的反应其控制氢氧化钠的浓度在30～35wt％之间，反应结束后螯合剂的pH值为12。7. The synthesis method according to claim 4, characterized in that in the reaction, the concentration of sodium hydroxide is controlled between 30% and 35% by weight, and the pH value of the chelating agent is 12 after the reaction.8、一种权利要求1所述的水溶性螯合树脂的应用，其特征在于螯合树脂在含重金属离子的废水上环保处理上应用。8. The application of the water-soluble chelating resin according to claim 1, characterized in that the chelating resin is used in the environmental protection treatment of wastewater containing heavy metal ions.9、根据权利要求8所述的水溶性螯合树脂的应用，其特征在于在所述的重金属离子包括铜、镍、铬、铅、锰、钴、铁、锌或六价铬等金属离子。9. The application of the water-soluble chelating resin according to claim 8, characterized in that the heavy metal ions include metal ions such as copper, nickel, chromium, lead, manganese, cobalt, iron, zinc or hexavalent chromium.10、根据权利要求9所述的水溶性螯合树脂的应用，其特征在于在所述的螯合树脂其环氧树脂与乙二胺重量比为3∶1至4∶1的范围，作为铜金属离子的沉淀剂，来控制废水铜离子浓度在0.5ppm以下。10, the application of water-soluble chelating resin according to claim 9 is characterized in that its epoxy resin and ethylenediamine weight ratio are the scope of 3: 1 to 4: 1 in described chelating resin, as copper Precipitating agent for metal ions to control the concentration of copper ions in wastewater below 0.5ppm.