本文選題：Fe-Cu-柱撐粘土(Fe-Cu-PILC)　切入點(diǎn)：氯酚　出處：《西北農(nóng)林科技大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：氯酚是工業(yè)廢水中一種較為常見的有機(jī)污染物,具有高毒性和難生物降解性,其消解一直是環(huán)境治理中的熱點(diǎn)和難點(diǎn)。本文選用環(huán)保高效的催化濕式過氧化氫氧化法對氯酚進(jìn)行催化氧化降解,而此方法的關(guān)鍵在于制備高效的催化劑。該研究通過共沉淀法制備了Fe-Cu-柱撐粘土(Fe-Cu-PILC)催化劑,并以單氯酚、二氯酚、三氯酚作為模式化合物,研究了氯酚中氯原子取代數(shù)目、取代位置對其降解動力學(xué)的影響,還研究了氯酚(CPs)氧化過程中H_2O_2,Cl~-,羥基自由基(·OH)和總有機(jī)碳(TOC)的濃度變化,此外,通過液相色譜-質(zhì)譜(LC-MS)檢測CPs氧化期間形成的中間體,并探討了氯離子的存在對反應(yīng)的影響,也基于費(fèi)米分布函數(shù)對其降解動力學(xué)進(jìn)行非線性擬合。該研究主要得出以下主要結(jié)論:(1)Fe-Cu-PILC/H_2O_2體系氯酚的氧化降解動力學(xué)可用一個(gè)基于費(fèi)米函數(shù)的半經(jīng)驗(yàn)?zāi)Ｐ蛿M合(R20.818),從而求得表觀速率常數(shù)k和半衰期t*。據(jù)此,氯酚降解速率次序?yàn)?-CP3,5-DCP2,3-DCP3,4-DCP2,5-DCP4-CP2-CP2,4-DCP2,4,6-TCP2,6-DCP。(2)苯環(huán)氯原子取代位置、取代數(shù)目均會對氯酚降解產(chǎn)生影響:對于單氯酚,氯原子在芳環(huán)間位時(shí),降解最容易,其次為對位,位于鄰位時(shí)最難降解;對于二氯酚,間位氯原子取代越多,越容易降解,鄰、對位氯原子越多,越難降解。但綜合來看,相對于取代數(shù)目,氯原子取代位置占據(jù)更主要的影響作用:氯原子取代數(shù)目相同時(shí),間位氯越多,降解越快,鄰對位越多,降解越慢。(3)Fe-Cu-PILC/H_2O_2體系中,Cl~-的存在抑制了CPs氧化速率,其中tI從60.2延長到86.9 min,t1/2延長到33.8 min(從88.4到122.2 min)。但是抑制作用只能在鄰位氯酚如2,6-DCP的氧化過程中發(fā)生,其中tI被延長到119.7 min(從233.8到353.5 min),而在間位或?qū)ξ宦确拥难趸^程中幾乎可以忽略不計(jì)。此外,Cl~-的存在不影響CPs的轉(zhuǎn)化(脫氯和羥基化)和深度氧化(礦化)。也就是說,Cl~-的存在沒有改變氧化路徑,如LC-MS所證明的。Cl~-釋放,H_2O_2分解,貽H形成和中間產(chǎn)物鑒定的多重指標(biāo)表明,Cl~-對鄰位氯酚氧化的抑制機(jī)制一方面主要是由于通過與H_2O_2競爭Fe(III)的絡(luò)合抑制H_2O_2分解的限速步驟,另一方面是由于貽H被清除而形成·Cl2-。
[Abstract]:Chlorophenol is a common organic pollutant in industrial wastewater, which is highly toxic and difficult to biodegrade. The degradation of chlorophenol has been a hot and difficult point in environmental treatment. In this paper, the catalytic oxidation degradation of chlorophenol was carried out by catalytic wet hydrogen peroxide oxidation with environmental protection and high efficiency. The key point of this method is to prepare high efficient catalyst. Fe-Cu-pillared clay Fe-Cu-PILC catalyst was prepared by coprecipitation method, and the number of chlorine atoms substituted in chlorophenol was studied with monochlorophenol, dichlorophenol and trichlorophenol as model compounds. The effect of substitution position on the degradation kinetics was also studied. The concentration changes of H _ 2O _ 2Cl _ (-), hydroxyl radical (路OH) and total organic carbon (TOC) during the oxidation of CPs were also studied. In addition, the intermediates formed during the oxidation of CPs were detected by liquid chromatography-mass spectrometry (LC-MS). The influence of chloride ion on the reaction was also discussed. The main conclusions of this study are as follows: the oxidation kinetics of chlorophenol can be fitted by a semi-empirical model based on Fermi function, which can be used to simulate the degradation kinetics of chlorophenol in the system of FeCu-PILC / H _ 2O _ 2. And the apparent rate constant k and the half-life tr are obtained. The degradation rate of chlorophenol is in the order of 3-CP3N 5-DCP2N 4-DCP4-CP2-CP2-CP2-CP2-DCP2-O4-DCP2-DCP2-O4-DCP2-O4-DCP2-O4-DCP2-DCP2) the substitution position of benzene cyclic chlorine atoms, the number of substitutions will affect the degradation of chlorophenols: for mono-chlorophenols, the degradation of monochlorophenol is the easiest when the chlorine atom is in the aromatic ring, followed by the opposite position, and the most difficult to degrade at the adjacent position; For dichlorophenols, the more m-site chlorine atoms are substituted, the easier it is to degrade, and the more para-chlorine atoms are, the more difficult it is to degrade dichlorophenol, but, taken together, relative to the number of substitutions, When the number of chlorine atoms is the same, the degradation rate of CPs is inhibited by the presence of more chlorinated atoms, faster degradation, more adjacent sites, slower degradation, and lower degradation rate in Fe-Cu-PILC / H _ 2O _ 2 system. T I was prolonged from 60.2 to 86.9 min / 1 / 2 to 33.8 min (from 88.4 to 122.2 mins). Ti was extended to 119.7 mins (from 233.8 to 353.5 mins) and was negligible during the oxidation of chlorophenols in the meta or para-position. In addition, the presence of ti-did not affect the conversion (dechlorination and hydroxylation) and deep oxidation (mineralization) of CPs. It means that the presence of Cl- does not change the oxidation path. As proved by LC-MS, the multiple indexes of the decomposition, formation and identification of intermediate products indicate that the inhibition mechanism of the oxidation of o-chlorophenol is mainly due to the inhibition of the decomposition of H _ 2O _ 2 by the complexation with H _ 2O _ 2, and the limiting steps of the decomposition of H _ 2O _ St _ 2 by means of the complexation with H _ 2O _ 2. On the other hand, the formation of 路Cl2-.
【學(xué)位授予單位】：西北農(nóng)林科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X703;O643.3

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