改性树脂制备及其去除饮用供水中余氯机理与工艺研究
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摘要
城市供水中对水的主要消毒方法是水中加氯消毒法,为了抑制水中残余的病原菌、病毒和其他致病生物的再度繁殖,水经过消毒接触一段时间后,应该有适量的剩余氯留在水中,以保证持续的杀菌能力。但是,水中过量的余氯会影响水的口感和气味,破坏水的品质;此外,在消毒过程中,氯与水中残余的有机物产生化学作用,生成一系列氯代烃如三氯甲烷、溴仿、溴二氯甲烷、氯二溴甲烷等,这些物质会对人体产生一定程度的致癌作用;对于以自然水源作为生活用水来源的城市必然要对水加氯消毒后才可使用。因此,对水中过量余氯处理方法的研究是一项很有价值的研究课题。
本文在对已有的余氯去除方法进行分析、研究、探讨的基础上,提出一种基于氧化还原方式的吸附除氯方法,实验以氨基磷酸螯合树脂和D001强酸性阳离子交换树脂为骨架材料,并对这两种材料载Fe~(2+)改性得到两种新型除氯剂,通过固载的Fe~(2+)与水中余氯(Cl_2、ClO~-、HClO)的氧化还原作用将水中的余氯除去。由于这两种材料对Fe~(2+)有很强的螯合和交换能力,除氯过程中,Fe~(2+)不容易被其他的离子重新交换下来;因此,该方法的一个突出特点是选择性高,除去余氯的同时不会对水中的其他离子产生影响,不会带入二次污染,出水水质好,完全能够使出水符合国家饮用水余氯水质标准。获得了一种新的去除余氯的方法,并确定了除氯工艺流程和参数。
本文首先从水中过量余氯导致的副产物的形成,以及副产物对人体的危害几个方面进行讨论,并对目前已有的除氯方法进行比较探讨;然后在对水中余氯已有的测定方法比较分析的基础上,实验确定了一种新的光度分析法,此方法标准配制简单,操作方便,是对已有测定方法的突破;然后在对已有除氯方法分析、讨论的基础上,提出本文的研究思路和方法。以实验为研究手段,对两种除氯剂的改性条件、除氯条件、干扰条件、洗脱条件和一些初步的工艺条件进行了详细探讨。实验结果表明:两种除氯剂的除氯容量都很高,改性氨基磷酸螯合型树脂的除氯容量可达63mg/g以上,比目前常用的除氯方法的除氯容量都高。改性D001阳离子交换树脂的除氯容量可达7mg/g以上,也是一种除氯容量较高的除氯剂;结果分析表明:改性氨基磷酸树脂除氯剂对水中余氯的吸附符合Freundlich公式,可以表示为式(1);改性D001阳离子树脂的吸附等温式符合Langmuir型,可以表示为式(2)。
q_e=1.6315c_e~(1.7444) (1)
q_e=2.97c_e/(1+0.167c_e) (2)
水中的常见离子对除氯效果影响很小。实验中采用微柱动态工艺条件实验,对自来
In urban supply water system, chlorization disinfection in water is adopted widely, in order to restrain the propagate of pathogenic bacteria, virus and other pathogenic organism once again, water is disinfected some time later, there should have a proper quantity chlorine retaining in water to ensure continuous capacity of killing germs. However, the surplus residual chlorine can affect people's taste and smell, destroy the quality of water. Moreover, in the process of disinfection, chlorine can react with organic matter and produce a series of hydrochloric ether such as chloroform, bromoform, bromodichloromethane, chlorodibromomethane and so on, these matters can cause to some extent cancer to human body. Therefore, it's a valuable task to make a study of disposing residual chlorine of water.In this paper, firstly, a detail analysis、 study and discussion of the existing disposing-chlorine method were made, on this condition, a new method based on the way of oxidation and deoxidization was discussed, phosphoramidic acid chelate resin and DOOl cation exchange resin were chosen as framework materials, two kinds of new disposing-chlorine materials could be obtained by loading Fe~(2+) on the skeleton of the materials, the surplus residual chlorine was disposed by taking advantage of chlorine oxidizing Fe~(2+). Because this two materials have a strong capacity of chelateding and exchanging with Fe~(2+), Fe~(2+) is hardly possible to be exchanged by other ions and reentry into water. Thereby, the obvious characteristic of this method is its high selectivity. It will not bring other ions in water in the process of disposing chlorine, it also will not take sequential pollution and can get high quality water. It can completely make the coming-out water coincide with our national drinking water standard, a new disposing-chlorine method is obtained and the technology flow and parameter of disposing-chlorine is determined.In this paper, firstly, the formation of by-product caused by surplus residual chlorine of water and its bad effect on human was discussed, as well as existing method of disposing chlorine was compared and discussed. Secondly, on the ground of analysing and discussing the existing mensurating method, a new analytical photometry was obtained, the standard of the method was simple and the operation was convenient, it made a breakthrough to the existing methods. And then, on the ground of analysing and comparing with the existing disposing-chlorine methods, a new thought and method of disposing chlorine was discussed. Taking experiment as a basic method, the effect of two disposing-chlorine materials under different conditions was discussed in details, such as modification condition, disposing-chlorine condition, disturbing condition, cleansing condition, as well as some preliminary technology craft condition. The experiment shows
that both of the disposing-chlorine materials have a high disposing-chlorine capability, with modified phosphoramidic acid chelate resin being 63mg/g, it's higher than all the existing disposing-chlorine materials, and modified D001 resin being 7mg/g, it's also a high capability disposing-chlorine material. The result shows the absorption of modified phosphoramidic acid chelate resin accords with Freundlich isotherm, as follows in formulation (1), the absorption of modified D001 resin conforms to Langmuir isotherm, as follows in formulation (2).qe=1.6315ce1-7444 (1)qe= 2-97c< (2)l+0.167ceThe other ions in water have little effect on disposing-chlorine process. In the experiment, a minitype adsorption column was used for dynamic technics condition experiment, disposing-chlorine effect under tap water simulating practice situation and different regenerate condition were discussed. Furthermore, the preliminary technology design was given in the paper according to experiment results. Lastly, some fundamental principle in the process of disposing-chlorine was discussed, which include the following part: the basic theory of adsorption, adsorption isothermal equation, the process of adsorption and exchanging in the column as well as its mathematical model. In addition, a theoretic analysis of the experiment data were made in order to make the best practical mode and parameter.Study in this paper shows that the method based on the mode of oxidation and deoxidization which we put forward has obvious advantages, this method has a high disposing-chlorine capability, it is also highly chlorine selective, other ions in water have little interference to disposing-chlorine effects, it can dispose the surplus residual chlorine in water to below 0.5mg/L and coincide with our national drinking water standard. For technology consideration, this method loads the disposing-chlorine material in a column and takes the way of solid-liquid separation, it is easy to handle and hardly take any sequential pollution. It is a kind of prospective method in the disposing-chlorine of drinking water and industry wastewater.
本文在对已有的余氯去除方法进行分析、研究、探讨的基础上,提出一种基于氧化还原方式的吸附除氯方法,实验以氨基磷酸螯合树脂和D001强酸性阳离子交换树脂为骨架材料,并对这两种材料载Fe~(2+)改性得到两种新型除氯剂,通过固载的Fe~(2+)与水中余氯(Cl_2、ClO~-、HClO)的氧化还原作用将水中的余氯除去。由于这两种材料对Fe~(2+)有很强的螯合和交换能力,除氯过程中,Fe~(2+)不容易被其他的离子重新交换下来;因此,该方法的一个突出特点是选择性高,除去余氯的同时不会对水中的其他离子产生影响,不会带入二次污染,出水水质好,完全能够使出水符合国家饮用水余氯水质标准。获得了一种新的去除余氯的方法,并确定了除氯工艺流程和参数。
本文首先从水中过量余氯导致的副产物的形成,以及副产物对人体的危害几个方面进行讨论,并对目前已有的除氯方法进行比较探讨;然后在对水中余氯已有的测定方法比较分析的基础上,实验确定了一种新的光度分析法,此方法标准配制简单,操作方便,是对已有测定方法的突破;然后在对已有除氯方法分析、讨论的基础上,提出本文的研究思路和方法。以实验为研究手段,对两种除氯剂的改性条件、除氯条件、干扰条件、洗脱条件和一些初步的工艺条件进行了详细探讨。实验结果表明:两种除氯剂的除氯容量都很高,改性氨基磷酸螯合型树脂的除氯容量可达63mg/g以上,比目前常用的除氯方法的除氯容量都高。改性D001阳离子交换树脂的除氯容量可达7mg/g以上,也是一种除氯容量较高的除氯剂;结果分析表明:改性氨基磷酸树脂除氯剂对水中余氯的吸附符合Freundlich公式,可以表示为式(1);改性D001阳离子树脂的吸附等温式符合Langmuir型,可以表示为式(2)。
q_e=1.6315c_e~(1.7444) (1)
q_e=2.97c_e/(1+0.167c_e) (2)
水中的常见离子对除氯效果影响很小。实验中采用微柱动态工艺条件实验,对自来
In urban supply water system, chlorization disinfection in water is adopted widely, in order to restrain the propagate of pathogenic bacteria, virus and other pathogenic organism once again, water is disinfected some time later, there should have a proper quantity chlorine retaining in water to ensure continuous capacity of killing germs. However, the surplus residual chlorine can affect people's taste and smell, destroy the quality of water. Moreover, in the process of disinfection, chlorine can react with organic matter and produce a series of hydrochloric ether such as chloroform, bromoform, bromodichloromethane, chlorodibromomethane and so on, these matters can cause to some extent cancer to human body. Therefore, it's a valuable task to make a study of disposing residual chlorine of water.In this paper, firstly, a detail analysis、 study and discussion of the existing disposing-chlorine method were made, on this condition, a new method based on the way of oxidation and deoxidization was discussed, phosphoramidic acid chelate resin and DOOl cation exchange resin were chosen as framework materials, two kinds of new disposing-chlorine materials could be obtained by loading Fe~(2+) on the skeleton of the materials, the surplus residual chlorine was disposed by taking advantage of chlorine oxidizing Fe~(2+). Because this two materials have a strong capacity of chelateding and exchanging with Fe~(2+), Fe~(2+) is hardly possible to be exchanged by other ions and reentry into water. Thereby, the obvious characteristic of this method is its high selectivity. It will not bring other ions in water in the process of disposing chlorine, it also will not take sequential pollution and can get high quality water. It can completely make the coming-out water coincide with our national drinking water standard, a new disposing-chlorine method is obtained and the technology flow and parameter of disposing-chlorine is determined.In this paper, firstly, the formation of by-product caused by surplus residual chlorine of water and its bad effect on human was discussed, as well as existing method of disposing chlorine was compared and discussed. Secondly, on the ground of analysing and discussing the existing mensurating method, a new analytical photometry was obtained, the standard of the method was simple and the operation was convenient, it made a breakthrough to the existing methods. And then, on the ground of analysing and comparing with the existing disposing-chlorine methods, a new thought and method of disposing chlorine was discussed. Taking experiment as a basic method, the effect of two disposing-chlorine materials under different conditions was discussed in details, such as modification condition, disposing-chlorine condition, disturbing condition, cleansing condition, as well as some preliminary technology craft condition. The experiment shows
that both of the disposing-chlorine materials have a high disposing-chlorine capability, with modified phosphoramidic acid chelate resin being 63mg/g, it's higher than all the existing disposing-chlorine materials, and modified D001 resin being 7mg/g, it's also a high capability disposing-chlorine material. The result shows the absorption of modified phosphoramidic acid chelate resin accords with Freundlich isotherm, as follows in formulation (1), the absorption of modified D001 resin conforms to Langmuir isotherm, as follows in formulation (2).qe=1.6315ce1-7444 (1)qe= 2-97c< (2)l+0.167ceThe other ions in water have little effect on disposing-chlorine process. In the experiment, a minitype adsorption column was used for dynamic technics condition experiment, disposing-chlorine effect under tap water simulating practice situation and different regenerate condition were discussed. Furthermore, the preliminary technology design was given in the paper according to experiment results. Lastly, some fundamental principle in the process of disposing-chlorine was discussed, which include the following part: the basic theory of adsorption, adsorption isothermal equation, the process of adsorption and exchanging in the column as well as its mathematical model. In addition, a theoretic analysis of the experiment data were made in order to make the best practical mode and parameter.Study in this paper shows that the method based on the mode of oxidation and deoxidization which we put forward has obvious advantages, this method has a high disposing-chlorine capability, it is also highly chlorine selective, other ions in water have little interference to disposing-chlorine effects, it can dispose the surplus residual chlorine in water to below 0.5mg/L and coincide with our national drinking water standard. For technology consideration, this method loads the disposing-chlorine material in a column and takes the way of solid-liquid separation, it is easy to handle and hardly take any sequential pollution. It is a kind of prospective method in the disposing-chlorine of drinking water and industry wastewater.
引文
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[8] 王荣生等.城市污水厂尾水氯消毒及其余氯控制技术进展.贵州环保科技,2003,9(4)
[9] 世界卫生组织编.饮用水水质准则(第二卷).北京:人民卫生出版社,1986:12
[10] GB5750～85.生活饮用水标准检验法.1985
[11] 中华人民共和国.生活饮用水标准.GB 5749-85
[12] 魏建荣.饮用水中消毒副产物的研究进展,卫生研究,2004,33(1)
[13] 曹瑞钰.氯消毒机理危害及脱氯.中国给水排水,1995(11):36～39
[14] 付婉霞.余氯及其终止液对饮用水致变形影响的试验研究,北京建筑工程学院院报,1996,12(3)
[15] 张淑琪,王根凤,王占生.氯化消毒对自来水致突变性影响研究[J].癌变畸变突变,1999,11(5):224-226
[16] 罗岳平.自来水管道内腐蚀对管网水质的研究影响[J].中国给水排水,1998,14(2):58-60
[17] 王海霞,张信阳.供水管网余氯预测的研究.天津工业大学学报,2003,22(6)
[18] 张艳琴.饮用水的消毒技术及消毒副产物的危害,太原科技,2003(3)
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