本文選題：高鹽氯酚廢水 + Co/PMS�。� 參考：《東華大學》2017年博士論文

【摘要】：氯酚廢水主要來源于煉油、煉焦、造紙、醫(yī)藥、印染、化工等行業(yè),其排放量大,對環(huán)境造成極大的威脅,因而氯酚廢水的無害化處理成為國內外學者關注的熱點問題。近年來,基于硫酸根自由基(SO4·-)的高級氧化技術因其反應速度快、限制條件少,處理效率高等優(yōu)點,被認為是未來可能應用于處理氯酚類等有機污染物的新型技術。但是,在對氯酚廢水成分的考察中發(fā)現(xiàn),其成分通常較為復雜,除含有高濃度的酚類污染物外,又含有大量的鹽分。高濃度的鹽不僅會對有機物降解動力學產生影響,且生成的活性物種與有機物反應還可能產生毒性更大的有機鹵代物(AOX),在高級氧化體系大規(guī)模運用之前,我們需對其進行謹慎評估。因此,開展高級氧化體系處理高鹽氯酚廢水時有機鹵代物的生成機制以及毒性評價研究具有十分重要的意義。本文選擇了幾種典型的氯酚,包括2,4,6-三氯酚(TCP)、鄰間對氯苯酚(2-CP、3-CP、4-CP)、2,4,6-三溴酚(TBP)、4-溴-2-氯-苯酚(BCP),研究了它們在含鹽體系中的氧化降解行為,重點分析了它們在基于單過氧硫酸氫鹽(PMS)和過二硫酸鹽(PS)的高級氧化體系中形成的AOX及其轉化機制。此外,還系統(tǒng)的評估了氯離子的存在對氯酚降解過程中AOX生成及生物毒性的影響。主要結論如下:(1)對比Co/PMS和UV/H_2O_2體系降解TCP發(fā)現(xiàn),Cl-的存在對Co/PMS體系中AOX的生成影響顯著,AOX生成量隨著Cl-濃度(0~300mM)的增加而升高;在UV/H_2O_2體系中,Cl-濃度的升高對體系中AOX生成量幾乎無影響。在酸性條件下,兩個體系中AOX生成量均會隨pH降低而升高。對比Cl-存在時的體系中的中間產物發(fā)現(xiàn),均會檢測到多種高毒性有機氯代副產物,如2,3,4,6-四氯苯酚、2,3,4,5-四氯苯酚和2,3,5,6-四氯苯酚等。采用發(fā)光細菌法對污染物降解前后的生物毒性進行分析,Cl-的存在使Co/PMS體系中溶液的生物毒性明顯增強且在180 min反應時間內一直保持在較高的毒性范圍。無論是否添加Cl-,UV/H_2O_2體系中溶液的急性毒性隨反應時間逐漸降低。(2)利用UV/PS體系降解單氯酚(MCPs)的研究表明,PS濃度與MCPs的降解性能具有正相關作用;向體系中加入0~300 mM的Cl-對MCPs的降解速率無明顯影響。通過對中間產物定性和定量分析,無論體系中是否添加Cl-,均會檢測到多種高毒性有機氯代副產物,且在4-CP的降解中檢測到更多種類的有毒有機鹵代物。在此基礎上對4-CP在UV/PS體系中的降解途徑進行了推測。在AOX的測定中發(fā)現(xiàn),Cl-的存在對UV/PS體系中AOX影響顯著,尤其是對4-CP。AOX值在60 min內隨反應時間變化逐漸下降,但是從60 min開始,這種減小趨勢明顯減弱,呈現(xiàn)出一種反常的增加現(xiàn)象。通過對UV/PS降解MCPs過程中急性生物毒性的分析可知,溶液對發(fā)光細菌的抑制率隨時間逐漸增加,急性毒性逐漸增強。(3)通過外加Cl-和微量Br-來模擬鹵素離子在高鹽廢水處理時可能發(fā)生的反應及其環(huán)境意義。研究發(fā)現(xiàn),PMS可以與鹵素離子(Cl-、Br-)發(fā)生雙電子轉移反應,使Cl-和Br-分別被氧化為活性氯物種Cl2/HOCl和HOBr/OBr-,而這些活性鹵代物種可以促使鹵代酚發(fā)生降解,且鹵素離子濃度的增加有利于鹵代酚的降解。在酸性條件下,pH的增加有利于鹵代酚的降解,同時pH也會影響中間產物的種類。在PMS/Br-體系中,4 h內TCP的礦化率僅為2.3%;在PMS/Cl-體系中,TBP的礦化率隨反應時間而升高,但在4 h內的礦化率也只有22.9%。通過GC-MS和UPLC-QTOF-MS對中間產物定性和定量分析,鹵代酚降解過程中會生成多種高毒性有機鹵代物,包括多氯代苯酚、多溴代苯酚、氯溴同體的芳香類物質,且多數(shù)有毒有機副產物自生成開始直至測定結束都維持在很高的水平。即使是微量的Br-(0.1 m M)也能夠導致多種有毒有機溴代產物的產生。本研究對基于PMS高級氧化體系在含鹽廢水方面的實際應用具有一定的指導意義。在評價PMS高級氧化體系對含鹽廢水的處理效果時,除了考慮氯離子的影響外,溴離子的影響也不容忽視。(4)選取既含有氯取代基又有溴取代基的BCP作為模型污染物,開展了其在Co/PMS體系中的降解研究。研究表明,BCP的降解速率隨著底物濃度的升高而下降,隨著PMS濃度、Co2+濃度以及溶液初始pH的升高而增大。不同濃度的Cl-對BCP的降解速率有不同的影響(雙重作用):當氯離子濃度小于5 mM時BCP降解速率隨Cl-濃度的增加而逐漸降低,外加氯離子抑制了反應的進行。接下來,反應速率常數(shù)會隨著氯離子濃度(5~50 m M)的繼續(xù)增加緩慢提高,在50 mM之后,反應速率常數(shù)增加更為明顯,此時外加氯離子對反應呈現(xiàn)促進作用。隨著Cl-濃度增加,BCP的礦化度受到明顯抑制。通過GC-MS產物鑒定可知,在氯離子存在下,隨著BCP的降解,生成了多種氯代副產物,但是未發(fā)現(xiàn)有多溴代物的生成。這可能與鹵取代基的電負性相關(FClBrI),即鹵代基的電負性越強,鹵代有機物越容易氧化脫鹵。
[Abstract]:Chlorophenol wastewater mainly comes from oil refining, coking, papermaking, medicine, printing and dyeing, chemical industry and other industries. It has a large emission and a great threat to the environment. Therefore, the harmless treatment of chlorophenol wastewater has become a hot issue for scholars both at home and abroad. In recent years, the advanced oxidation technology based on the radical sulfate radical (SO4 -) has a fast reaction speed and limit the strip. It is considered to be a new technology for the treatment of chlorophenols and other organic pollutants in the future. However, in the investigation of the composition of chlorophenol wastewater, it is found that the composition is usually more complex and contains a large amount of salt in addition to high concentration of phenolic pollutants. High concentration of salt will not only degrade organic matter. The reaction of the active species to the organic matter may produce more toxic organic halogen (AOX). Before the large-scale application of the advanced oxidation system, we need to evaluate it carefully. Therefore, the formation mechanism and toxicity evaluation of organic halogen in high chlorophenol wastewater treatment by advanced oxidation system Some typical chlorophenols, including 2,4,6- three chlorophenol (TCP), adjacent perchlorophenol (2-CP, 3-CP, 4-CP), 2,4,6- three bromophenol (TBP), 4- bromine -2- chloride phenol (BCP), are selected in this paper. Their oxidation degradation behavior in the salt containing system is studied. The emphasis is on their analysis based on the single peroxisate (PMS) and over two. AOX and its transformation mechanism in the high oxidation system of sulfate (PS). Furthermore, the effects of the existence of chlorine ions on the formation of AOX and the biological toxicity of chlorophenol degradation are systematically evaluated. The main conclusions are as follows: (1) the existence of Cl- is significant to the formation of AOX in Co/PMS system, AOX, as compared with the Co/PMS and UV/H_2O_2 system, AOX. The amount of formation increased with the increase of Cl- concentration (0~300mM); in the UV/H_2O_2 system, the increase of Cl- concentration had little effect on the AOX production in the system. Under the acidic condition, the AOX generation in the two systems would all increase with the decrease of pH. The intermediate products in the system when the Cl- existed, found that all kinds of high toxic organochlorine could be detected. By-products, such as 2,3,4,6- four chlorophenol, 2,3,4,5- four Chlorophenol and 2,3,5,6- four chlorophenol, were used to analyze the biological toxicity of the pollutants before and after the degradation of pollutants. The existence of Cl- significantly enhanced the biological toxicity of the solution in the Co/PMS system and kept in a higher toxicity range in the 180 min reaction time. In addition Cl-, the acute toxicity of the solution in the UV/H_2O_2 system decreased with the reaction time. (2) the study on the degradation of monchlorophenol (MCPs) by the UV/PS system showed that the concentration of PS had a positive correlation with the degradation performance of MCPs, and the Cl- of 0~300 mM to the system had no obvious effect on the degradation rate of MCPs. The qualitative and quantitative analysis of intermediate products had no effect. If Cl- is added to the system, a variety of highly toxic organochlorinated by-products can be detected, and more kinds of toxic organic halogenates are detected in the degradation of 4-CP. On this basis, the degradation pathway of 4-CP in the UV/PS system is speculated. In the AOX determination, the existence of Cl- has a significant influence on AOX in the UV/PS system, especially in the UV/PS system. The 4-CP.AOX value decreased with the reaction time in 60 min, but the decrease trend was obviously weakened from 60 min, which showed an abnormal increase. Through the analysis of the acute biological toxicity of UV/PS degradation in MCPs, the inhibition rate of the solution to luminescent bacteria was gradually increased with time, and the acute toxicity increased gradually. (3 ) by adding Cl- and micro Br- to simulate the possible reaction of halogen ions in the treatment of high salt waste water and its environmental significance. It is found that PMS can have double electron transfer reaction with halogen ions (Cl-, Br-), and Cl- and Br- are oxidized to active chlorine species Cl2/HOCl and HOBr/OBr- respectively, and these active halogenated species can promote halogenation. The degradation of phenol and the increase of halogen ion concentration are beneficial to the degradation of halogenated phenol. Under the acidic condition, the increase of pH is beneficial to the degradation of halogenated phenols, while pH also affects the type of intermediate products. In the PMS/Br- system, the mineralization rate of TCP is only 2.3% in 4 h; in the PMS/Cl- system, the mineralization rate of TBP increases with the reaction time, but within 4 h. The mineralization rate is also only 22.9%. through GC-MS and UPLC-QTOF-MS for the qualitative and quantitative analysis of intermediate products. In the process of halogenated phenol degradation, a variety of highly toxic organic halogenates, including polychlorinated phenol, polybrominated phenol, and chlorinated bromide, are produced, and most of the toxic organic by-products are maintained from the beginning until the end of the determination. A very high level. Even a small amount of Br- (0.1 M M) can lead to the production of a variety of toxic organic brominated products. This study has a certain guiding significance for the practical application of the advanced oxidation system based on PMS in the salt containing wastewater. In evaluating the treatment effect of the PMS advanced oxidation system to the salt containing wastewater, the effect of the chloride ion is considered. In addition, the effect of bromine ion can not be ignored. (4) select BCP containing both chlorine substituent and bromine substituent as model pollutant, and carry out its degradation in Co/PMS system. The study shows that the degradation rate of BCP decreases with the increase of substrate concentration, and increases with the concentration of PMS, Co2+ concentration and the initial pH of the solution. The concentration of Cl- has different effects on the degradation rate of BCP: when the concentration of chlorine ion is less than 5 mM, the degradation rate of BCP gradually decreases with the increase of Cl- concentration, and the addition of chloride ions inhibits the reaction. The reaction rate constant will be slowly increased with the increase of the chloride concentration (5 ~50 m M), and after 50 mM, the reaction rate will be reversed. The increase of rate constant is more obvious. At this time, the addition of chloride ion has a promotion effect on the reaction. With the increase of Cl- concentration, the mineralization degree of BCP is obviously inhibited. Through the identification of GC-MS products, it is known that in the presence of chlorine ion, with the degradation of BCP, a variety of chlorinated by-products have been generated, but no polybrominated products are found. This may be with the halogen. The electronegativity correlation (FClBrI) of the substituents is that the stronger the electronegativity of halogenated groups, the easier the halogenated organic compounds are to oxidize dehalogenation.
【學位授予單位】：東華大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X703

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