本文選題：四溴雙酚A + 十溴二苯醚��； 參考：《哈爾濱工業(yè)大學》2015年碩士論文

【摘要】：溴系阻燃劑(BFRs)是一類新興的持久性有機污染物,其中多溴聯(lián)苯醚(PBDEs)、四溴雙酚A(TBBPA)和六溴環(huán)十二烷(HBCD)是最主要的三種,在PBDEs中十溴二苯醚(BDE-209)的使用量最大。PBDEs、TBBPA和HBCD在東江支流工業(yè)排水中被檢出。目前針對溴系阻燃劑去除的實用技術不多,缺乏多種溴系阻燃劑存在下的的去除技術方案。本文選取TBBPA、BDE-209和HBCD為研究對象,用氧化法和光降解法對這三種典型溴系阻燃劑進行去除研究,探索適用于實際水體中去除典型溴系阻燃劑的技術方案。研究結果表明,臭氧和高錳酸鉀氧化對TBBPA均有較好的去除效果。臭氧氧化TBBPA速率很快,較大的臭氧投加量、堿性條件、高溫、較小的底物初始濃度有利于TBBPA的去除。但臭氧過量投加時會產(chǎn)生溴酸鹽。高錳酸鉀氧化TBBPA的反應速率也很快,去除率隨高錳酸鉀濃度的增加而增大,隨pH值、底物初始濃度的增加而減小。高錳酸鉀過量時,高錳酸鉀氧化TBBPA的反應對TBBPA是一級反應。但臭氧和高錳酸鉀氧化對BDE-209和HBCD均無去除效果。254 nm紫外光降解可以很好的對BDE-209和TBBPA進行去除。兩者初始濃度均為0.3μmol/L時,分別在反應120 min和60 min可以實現(xiàn)完全去除。為進一步提高光降解反應速率,在同一紫外光源照射下加入Na_2SO_3,對BDE-209和TBBPA進行去除研究。兩者的去除率較單獨UV下均有所提高。UV和UV/Na_2SO_3對典型溴系阻燃劑的降解反應均符合一級反應動力學方程。同時用254 nm紫外光降解對HBCD進行了去除研究,結果表明,反應速率較為緩慢。針對較難去除的HBCD,又采用了185 nm紫外光對其進行降解。結果表明,HBCD初始濃度為0.3μmol/L時,在79 W/185 nm紫外光照射下僅需2 h可降解完全。同時對TBBPA和BDE-209也進行了降解研究,結果表明,21 W/185nm紫外光照射下兩者分別僅需20 min和40 min可降解完全。通過上述各方法對典型溴系阻燃劑TBBPA、BDE-209和HBCD的去除研究可以得出,當實際水體中只有TBBPA時,優(yōu)先選用高錳酸鉀氧化技術;當水體中存在BDE-209時,優(yōu)先選用Na_2SO_3/UV(254 nm)高級還原技術;當存在HBCD時,選用185 nm紫外光降解。
[Abstract]:Brominated flame retardants (BFRs) are a class of emerging persistent organic pollutants, of which polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) are the most important ones. Decabromodiphenyl ether (BDE-209) was used most in PBDEs. TBBPA and HBCD of PBDEs were detected in industrial drainage of Dongjiang tributaries. At present, there are few practical technologies for removal of bromine flame retardants, and there is a lack of removal technology in the presence of many bromine flame retardants. In this paper, TBBPA-BDE-209 and HBCD were selected as the research objects, the removal of these three typical bromine flame retardants was studied by oxidation and photodegradation methods, and the technical scheme suitable for removing typical bromine flame retardants in actual water was explored. The results showed that both ozone and potassium permanganate oxidation had better removal effect on TBBPA. The rate of TBBPA oxidized by ozone is very fast, and the removal of TBBPA is facilitated by large amount of ozone, alkaline condition, high temperature and small initial concentration of substrate. But when ozone is overdosed, bromate is produced. The reaction rate of potassium permanganate oxidation of TBBPA is also very fast. The removal rate increases with the increase of potassium permanganate concentration, and decreases with the increase of pH value and the initial concentration of substrate. In excess of potassium permanganate, the oxidation of TBBPA by potassium permanganate is a first order reaction. However, ozone and potassium permanganate oxidation had no removal effect on BDE-209 and HBCD. 254nm UV photodegradation could effectively remove BDE-209 and TBBPA. When the initial concentration of both was 0.3 渭 mol / L, the complete removal could be achieved at the reaction time of 120 min and 60 min, respectively. In order to further improve the photodegradation reaction rate, NaAs _ 2SO _ 3s _ 3 was added under the same ultraviolet light source to study the removal of BDE-209 and TBBPA. The removal rates of both of them were higher than those under UV alone. The degradation of typical bromine flame retardants by UV and UV / Na _ 2SO _ 3 were in accordance with the first-order reaction kinetics equation. At the same time, the removal of HBCD by 254 nm UV photodegradation was studied. The results showed that the reaction rate was relatively slow. For HBCD which is difficult to be removed, 185 nm UV light was used to degrade it. The results show that when the initial concentration of HBCD is 0.3 渭 mol / L, it can be degraded completely in only 2 hours under the irradiation of 79 W / 185 nm ultraviolet light. The degradation of TBBPA and BDE-209 was also studied. The results showed that the degradation of TBBPA and BDE-209 required only 20 min and 40 min under UV irradiation of 21 W / 185nm, respectively. The removal of typical bromine flame retardant TBBPA-BDE-209 and HBCD by the above methods shows that potassium permanganate oxidation technology is preferred when there is only TBBPA in actual water, and Na2SO3 / UV (254 nm) advanced reduction technology is preferred when BDE-209 exists in water body. In the presence of HBCD, 185 nm UV light was used for degradation.
【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：X52

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