【作者】 王婷；

【导师】 刘义青；

【作者基本信息】 西南交通大学 ， 环境科学与工程， 2024， 硕士

【摘要】 随着近年来我国纺织行业的迅速发展,印染废水的排放量也呈现出逐年增加的趋势。印染废水进入水体后,会对环境生态系统和人类健康造成极大危害。传统的印染废水处理技术包括吸附技术、膜分离技术、混凝-絮凝技术和生物化学处理技术,但吸附与污染物的接触时间长,膜分离运行成本高且膜易被污染和堵塞,凝聚-絮凝对可溶性染料无效,生物方法大规模适用性差。与这些传统处理技术相比,高级氧化技术具有更强的氧化能力、更快的反应速度,是处理印染废水最可行的技术。本文以罗丹明B（RhB）作为目标污染物,分别研究了硼酸（BA）、Cl^-和HCO₃^-对Cu（Ⅱ）活化过氧乙酸（PAA）降解RhB的影响,并对各个反应体系中RhB降解机理、pH影响、物质投加量影响、天然水体中常见物质影响、对其他污染物的降解以及对实际水体中RhB的降解等进行了分析探讨。研究表明:（1）BA/Cu（Ⅱ）/PAA体系:pH为8.5条件下,BA可以与Cu（Ⅱ）形成高活性Cu（Ⅱ）-BA络合物进而加速Cu（Ⅱ）还原为Cu（Ⅰ）,从而促进PAA的活化。60 min后RhB降解率达93.9%,体系中的主要活性物质为CH₃C（O）OO·、CH₃C（O）O·,·OH、¹O₂和Cu（Ⅲ）仅起到次要作用。RhB的降解随着Cu（Ⅱ）、PAA和BA浓度的升高而增加,随着RhB初始浓度的升高而逐渐降低。NO₃^-、SO₄^2-对RhB的降解没有影响,但HCO₃^-和FA对RhB降解有明显的抑制,并且抑制作用随着HCO₃^-和FA浓度的升高而增强,Cl^-对RhB降解略有促进。BA/Cu（Ⅱ）/PAA体系对亚甲基蓝（MB）、橙黄G（OG）、盐酸土霉素（OTC）等三种有机污染物也均能够实现高效降解。此外,在沱江河、犀湖、实验室自来水等三种实际水体中,也能高效降解RhB。（2）Cl^-/Cu（Ⅱ）/PAA体系:与BA类似,Cl^-与Cu（Ⅱ）络合形成的高活性Cu（Ⅱ）-Cl_n络合物也能够促进Cu（Ⅱ）的还原,从而促进PAA的活化。pH为8.5条件下,60 min后RhB降解率达85.8%,Cl^-/Cu（Ⅱ）/PAA体系中降解RhB的主要活性物质为CH₃C（O）OO·、CH₃C（O）O·,·OH、¹O₂、HCl O和Cu（Ⅲ）仅起到次要作用。pH为4.0时,60 min后Cl^-/Cu（Ⅱ）/PAA体系中RhB的降解效率达到94.3%,可能主要归因于Cl^-与PAA反应产生的HCl O、Cl·和Cl₂^·-等活性氯物种。RhB的降解随着Cu（Ⅱ）、PAA浓度的升高而增加,随着Cl^-浓度的增加先增强而后减弱,随着RhB初始浓度的升高而逐渐降低。NO₃^-、SO₄^2-对RhB的降解没有影响,而HCO₃^-对RhB降解有明显的促进作用,FA对RhB降解有明显的抑制,并且抑制作用随着FA浓度的升高而增强。此外,Cl^-/Cu（Ⅱ）/PAA体系对MB、OG、OTC等三种有机污染物也均能够实现高效降解。（3）HCO₃^-/Cl^-/Cu（Ⅱ）/PAA体系:pH为8.5条件下,HCO₃^-的加入进一步促进了Cl^-/Cu（Ⅱ）/PAA体系对RhB的降解,RhB的降解速率和最终降解率都显著提高,k_obs由0.0536 min^-1提高至0.177 min^-1,k_obs提高了超过三倍,30 min内降解率由78.3%提高至99.4%,HCO₃^-在该体系中的主要作用是通过与Cu（Ⅱ）形成高活性Cu（Ⅱ）-HCO₃^-络合物进而与Cl^-协同加速Cu（Ⅱ）还原为Cu（Ⅰ）,从而促进PAA的活化,主要活性物质为CH₃C（O）OO·、CH₃C（O）O·和Cu（Ⅲ）,¹O₂和HCl O仅起到次要作用。RhB的降解随着HCO₃^-浓度的增加先升高后降低,随着Cu（Ⅱ）和Cl^-浓度的升高而增加,随着RhB初始浓度的升高而逐渐降低,降解速率随着PAA浓度的提高先升高而后减少。NO₃^-、SO₄^2-对降解的RhB没有影响,FA对RhB降解有明显的抑制,并且抑制作用随着FA浓度的升高而增强。HCO₃^-/Cl^-/Cu（Ⅱ）/PAA体系对MB、OG、OTC也均能够实现高效降解。此外,在沱江河、犀湖、实验室自来水等三种实际水体中,Cu（Ⅱ）/PAA体系对RhB的降解均高于纯水,可能是实际水体中的Cl^-和HCO₃^-等物质促进了Cu（Ⅱ）/PAA体系降解RhB。更多还原

【Abstract】 With the rapid development of China’s textile industry in recent years,the discharge of printing and dyeing wastewater has shown an increasing trend year by year.Printing and dyeing wastewater can cause great harm to the environmental ecosystem and human health when it enters the water body.Traditional printing and dyeing wastewater treatment technologies include adsorption,membrane separation,coagulation-flocculation and biochemical treatment technologies,but adsorption has a long contact time with pollutants,membrane separation has high operating costs and membranes are susceptible to contamination and clogging,coagulation-flocculation is ineffective for soluble dyes,and biological methods are poorly suited on a large scale.Compared with these traditional treatment technologies,advanced oxidation technology has stronger oxidation capacity,faster reaction speed,and is the most feasible technology for treating printing and dyeing wastewater.In this paper,the effects of boric acid（BA）,Cl^-and HCO₃^-on the degradation of RhB by Cu（Ⅱ）-activated peracetic acid（PAA）were investigated with Rhodamine B（RhB）as the target pollutant,and the degradation mechanism of RhB in each reaction system,the effects of pH,the effects of substance addition,the effects of substances commonly found in natural waters,the degradation of other pollutants,and the degradation of RhB in the actual water were analysed and discussed.The study shows that:（1）BA/Cu（Ⅱ）/PAA system:at pH 8.5,BA can form a highly active Cu（Ⅱ）-BA complex with Cu（Ⅱ）and then accelerate the reduction of Cu（Ⅱ）to Cu（Ⅰ）,which promotes the activation of PAA.The degradation rate of RhB reaches 93.9%after 60 min,and the main active substances in the system are CH₃C（O）OO·and CH₃C（O）O·,·OH,¹O₂ and Cu（Ⅲ）only play a minor role.The degradation of RhB increased with the concentration of Cu（Ⅱ）,PAA and BA,and decreased gradually with the initial concentration of RhB.NO₃^-and SO₄^2-had no effect on the degradation of RhB,but HCO₃^-and FA had significant inhibition on RhB degradation,and the inhibition increased with the increase of HCO₃^-and FA concentrations,and Cl^-slightly promoted RhB degradation.The BA/Cu（Ⅱ）/PAA system was also able to achieve high efficiency degradation of three organic pollutants,including methylene blue（MB）,orange yellow G（OG）,and oxytetracycline hydrochloride（OTC）.In addition,RhB was also efficiently degraded in three actual water bodies,such as Tuojiang River,Rhinoceros Lake,and laboratory tap water.（2）Cl^-/Cu（Ⅱ）/PAA system:similar to BA,the highly active Cu（Ⅱ）-Cl_n complex formed by the complexation of Cl^-with Cu（Ⅱ）was also able to promote the reduction of Cu（Ⅱ）,thus promoting the activation of PAA.At pH 8.5,the degradation rate of RhB reached 85.8%after60 min,and the main active substances for the degradation of RhB in the Cl^-/Cu（Ⅱ）/PAA system were CH₃C（O）OO·and CH₃C（O）O·,·OH,¹O₂,HCl O and Cu（Ⅲ）only played a minor role.The degradation efficiency of RhB in the Cl^-/Cu（Ⅱ）/PAA system reached 94.3%after 60min at pH 4.0,which may be mainly attributed to the reactive chlorine species,such as HCl O,Cl·,and Cl₂^·-,produced by the reaction of Cl^-with PAA.The degradation of RhB increased with the increase of the concentrations of Cu（Ⅱ）,PAA concentration,first enhanced and then weakened with the increase of Cl^-concentration,and gradually decreased with the increase of the initial concentration of RhB.NO₃^-and SO₄^2-had no effect on the degradation of RhB,while HCO₃^-had a significant promotion effect on RhB degradation,and FA had a significant inhibition on RhB degradation and the inhibition effect was enhanced with the increase of FA concentration.In addition,the Cl^-/Cu（Ⅱ）/PAA system was also able to achieve efficient degradation of all three organic pollutants,including MB,OG,and OTC.（3）HCO₃^-/Cl^-/Cu（Ⅱ）/PAA system:under the condition of pH 8.5,the addition of HCO₃^-further promoted the degradation of RhB in the Cl^-/Cu（Ⅱ）/PAA system,and the degradation rate and the final degradation rate of RhB were significantly increased,with the kobs increased from 0.0536 min^-1 to 0.177 min^-1,and the kobs increased more than three times.The main role of HCO₃^-in this system was to accelerate the reduction of Cu（Ⅱ）to Cu（I）through the formation of highly active Cu（Ⅱ）-HCO₃^-complex with Cu（Ⅱ）and then synergistically with Cl^-,thus promoting the activation of PAA,with the main activators being CH₃C（O）OO·,CH₃C（O）O·and Cu（III）,¹O₂and HCl O playing only a minor role.The degradation of RhB increased and then decreased with the increase of HCO₃^-concentration,increased with the increase of Cu（Ⅱ）and Cl^-concentration,and gradually decreased with the increase of the initial concentration of RhB,and the rate of degradation increased and then decreased with the increase of the PAA concentration.NO₃^-and SO₄^2-had no effect on the degraded RhB,and FA inhibited RhB degradation significantly,and the inhibition increased with the increase of FA concentration.The HCO₃^-/Cl^-/Cu（Ⅱ）/PAA system was also able to achieve high efficiency in the degradation of MB,OG,and OTC.In addition,the degradation of RhB by the Cu（Ⅱ）/PAA system was higher than that of pure water in three actual water bodies,including Tuojiang River,Rhinoceros Lake,and laboratory tap water,which may be due to the fact that the substances such as Cl^-and HCO₃^-in the actual water bodies promoted the degradation of RhB by the Cu（Ⅱ）/PAA system.更多还原