硫酸根自由基的定量分析技术及在高级氧化工艺中的应用
发布时间：2018-12-16 21:45
【摘要】：随着社会进步与经济发展，环境污染问题日益突出。水环境中的污染物种类和数量逐日增加，这对水环境治理与给水处理都提出了挑战。传统给水处理工艺已经不能满足生活生产用水对水质的要求，高级氧化技术逐步引入工程应用中。高级氧化技术是利用高活性的自由基（工程应用以·OH为主）氧化降解水体中的难降解有机物的工艺，其中利用不同活化方法活化过硫酸盐产生硫酸根自由基（SO4-）进行水体原位修复及降解难降解有机物已获得广泛关注。在利用过硫酸盐活化技术进行生产应用中需要考虑系统中的SO4-产率及其对特定水体特定目标物的降解效果。本课题基于这一背景，提出了基于紫外活化过硫酸盐（UV/PDS）的竞争动力学方法与完全捕获法。用这两种方法评估不同活化体系的SO4-产率，同时用于评估不同实际水体背景对SO4-降解特定目标物质的影响。 竞争动力学方法采用苯甲酸（BA）与醇（甲醇、乙醇或叔丁醇）作为竞争体系，其中以BA作为指示剂，醇类作为捕获剂。通过计算BA降解动力学并结合两者的竞争动力学模型可以推求SO4-的产率。实验还基于UV/PDS计算出了甲醇、乙醇、叔丁醇与SO4-的反应速率常数（k(甲醇,SO4-)=1.23×107M-1s-1、k(乙醇, SO4-)=5×107M-1s-1、 k(叔丁醇,SO4-)=2×106M-1s-1）。捕获剂与SO4-反应路径存在差异，，不同pH条件下自由基计算产率有差异。完全捕获法利用SO4-与捕获剂反应的产物产量来表征SO4-的产量。不同捕获剂与SO4-反应路径不同，生成的产物的量有差异。不同pH条件下，应用完全捕获法计算SO4-产率有差异。 在不同的水体中，采用SO4-高级氧化降解污染物的过程，都会受到水体背景成分的干扰而影响降解效率。实验应用竞争动力学与完全捕获法评估不同水体的SO4-捕获速率，其中生活污水地表水地下水自来水。实验还采用竞争动力学表征不同阴离子对SO4-的捕获速率，实验结果表明Cl- NO3- HCO3-。应用竞争动力学表征过渡金属活化过硫酸盐产SO4-产率反映了不同金属的活化效果为Ag(I) Fe(II) Fe(III) Mn(II) Ce(III) Ni(II)。竞争动力学模型能够定量分析SO4-的生成及其对特征水体中的特征目标物降解效果，这对指导生产应用具有很强的实际意义。
[Abstract]:With social progress and economic development, environmental pollution has become increasingly prominent. The species and quantity of pollutants in water environment increase day by day, which brings challenges to water environment treatment and water supply treatment. The traditional water treatment process can not meet the water quality requirements of domestic production water. Advanced oxidation technology has been gradually introduced into engineering applications. Advanced oxidation technology is a process of oxidation and degradation of refractory organic compounds in water using highly active free radicals (OH as the main engineering application). Among them, the activation of persulfate to produce sulfate radical (SO4-) by different activation methods has been paid more attention to in situ remediation and degradation of refractory organic matter. In the production and application of persulfate activation technology, the yield of SO4- in the system and its degradation effect to the specific target in a specific water body should be considered. Based on this background, a competitive kinetic method and a complete capture method based on ultraviolet activated persulfate (UV/PDS) were proposed. These two methods were used to evaluate the SO4- yield of different activation systems and to evaluate the effects of different water background on the degradation of specific target substances by SO4-. In the competitive kinetic method, benzoic acid (BA) and alcohols (methanol, ethanol or tert-butanol) were used as competitive systems, in which BA was used as indicator and alcohols as trapping agent. The yield of BA can be calculated by calculating the degradation kinetics of SO4- and combining the competitive kinetic model of the two models. The reaction rate constants of methanol, ethanol and tert-butanol with SO4- were calculated based on UV/PDS. (k (methanol (SO4-) = 1.23 脳 107M-1s-1K (ethanol, SO4-) = 5 脳 107M-1s-1, k (tert-butanol). SO4-) = 2 脳 106M-1s-1). The reaction paths of trapping agent and SO4- were different, and the yield of free radical under different pH conditions was different. The yield of SO4- was characterized by the product yield of SO4- reaction with trapping agent by complete capture method. Different trapping agent and SO4- reaction path are different, the amount of the product is different. Under different pH conditions, the total capture method is used to calculate the yield of SO4-. In different water bodies, the degradation of pollutants by advanced oxidation of SO4- will be affected by the interference of background components of the water body. Competitive dynamics and complete capture methods were used to evaluate the SO4- capture rate of different water bodies, including domestic sewage surface water and groundwater tap water. The capture rates of different anions to SO4- were also characterized by competitive kinetics. The experimental results showed that Cl- NO3- HCO3-. Competitive kinetics was used to characterize the SO4- yield of transition metal activated persulfate. The results showed that the activation efficiency of different metals was Ag (I) Fe (II) Fe (III) Mn (II) Ce (III) Ni (II). The competitive dynamics model can quantitatively analyze the formation of SO4- and its degradation effect on the characteristic target in the characteristic water, which is of great practical significance for guiding the production and application.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：TU991.2
本文编号：2383092
[Abstract]:With social progress and economic development, environmental pollution has become increasingly prominent. The species and quantity of pollutants in water environment increase day by day, which brings challenges to water environment treatment and water supply treatment. The traditional water treatment process can not meet the water quality requirements of domestic production water. Advanced oxidation technology has been gradually introduced into engineering applications. Advanced oxidation technology is a process of oxidation and degradation of refractory organic compounds in water using highly active free radicals (OH as the main engineering application). Among them, the activation of persulfate to produce sulfate radical (SO4-) by different activation methods has been paid more attention to in situ remediation and degradation of refractory organic matter. In the production and application of persulfate activation technology, the yield of SO4- in the system and its degradation effect to the specific target in a specific water body should be considered. Based on this background, a competitive kinetic method and a complete capture method based on ultraviolet activated persulfate (UV/PDS) were proposed. These two methods were used to evaluate the SO4- yield of different activation systems and to evaluate the effects of different water background on the degradation of specific target substances by SO4-. In the competitive kinetic method, benzoic acid (BA) and alcohols (methanol, ethanol or tert-butanol) were used as competitive systems, in which BA was used as indicator and alcohols as trapping agent. The yield of BA can be calculated by calculating the degradation kinetics of SO4- and combining the competitive kinetic model of the two models. The reaction rate constants of methanol, ethanol and tert-butanol with SO4- were calculated based on UV/PDS. (k (methanol (SO4-) = 1.23 脳 107M-1s-1K (ethanol, SO4-) = 5 脳 107M-1s-1, k (tert-butanol). SO4-) = 2 脳 106M-1s-1). The reaction paths of trapping agent and SO4- were different, and the yield of free radical under different pH conditions was different. The yield of SO4- was characterized by the product yield of SO4- reaction with trapping agent by complete capture method. Different trapping agent and SO4- reaction path are different, the amount of the product is different. Under different pH conditions, the total capture method is used to calculate the yield of SO4-. In different water bodies, the degradation of pollutants by advanced oxidation of SO4- will be affected by the interference of background components of the water body. Competitive dynamics and complete capture methods were used to evaluate the SO4- capture rate of different water bodies, including domestic sewage surface water and groundwater tap water. The capture rates of different anions to SO4- were also characterized by competitive kinetics. The experimental results showed that Cl- NO3- HCO3-. Competitive kinetics was used to characterize the SO4- yield of transition metal activated persulfate. The results showed that the activation efficiency of different metals was Ag (I) Fe (II) Fe (III) Mn (II) Ce (III) Ni (II). The competitive dynamics model can quantitatively analyze the formation of SO4- and its degradation effect on the characteristic target in the characteristic water, which is of great practical significance for guiding the production and application.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：TU991.2
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