【作者】 王强；

【导师】 庞素艳；

【作者基本信息】 哈尔滨理工大学 ， 化学工程与技术， 2015， 硕士

【摘要】 卤代酚类化合物作为水环境中普遍存在的典型嗅味物质一直是水处理领域的研究热点。卤代酚类化合物具有难降解和水溶性强的特点，而且对生物具有一定的毒害作用。KMnO4用于去除水中卤代酚类化合物具有比较突出的优势，一方面能够氧化卤代酚类化合物的酚羟基不饱和官能团，另一方面KMnO4在氧化过程中不会产生有毒有害副产物，与次氯酸、臭氧氧化过程中生成氯代、溴代副产物相比具有明显的优势。因此，本文研究了KMnO4降解卤代酚类有机污染物的反应动力学、环境因素（阳离子、络合剂）的影响和氧化耦合产物的生成机理。在不同pH假一级动力学实验条件下（pH=4~10，KMnO4浓度>>卤代酚浓度），利用高效液相色谱（HPLC）对卤代酚类有机污染物的浓度进行测定，研究了KMnO4氧化降解卤代酚（碘酚、溴酚和氟酚）的动力学规律。研究结果表明，KMnO4能够有效的氧化降解含有不饱和官能团的卤代酚类化合物，遵循二级反应动力学规律，二级反应速率常数k (M-1s-1)受pH影响较大。在pH=4、5条件下，KMnO4氧化降解卤代酚化合物出现自催化现象，即反应过程中生成的锰氧化物对KMnO4氧化降解卤代酚化合物起到催化作用。KMnO4氧化卤代酚化合物二级反应速率常数k随pH出现先增大后减小现象，即KMnO4对卤代酚化合物的氧化与卤代酚化合物的pKa有关，当pH小于pKa时，氧化速率随pH升高而升高，当pH大于pKa时，氧化速率随pH升高反而降低。假一级动力学实验条件下，研究了阳离子、络合剂对KMnO4氧化降解卤代酚动力学规律的影响。研究结果表明，常见阳离子（Ca2+、Mg2+）对KMnO4氧化降解卤代酚化合物几乎没有影响。因此，在实际工程中运用KMnO4作为氧化剂去除水中的卤代酚类有机物时就不用考虑水中常见阳离子的影响。络合剂（EDTA、NTA、焦磷酸）对KMnO4氧化卤代酚有机物具有明显的促进作用。络合剂的促进作用遵循中间价态锰理论，即络合剂可以加强KMnO4氧化卤代酚有机物过程中生成Mn(III)的稳定性，抑制了Mn(III)的自分解，继而发挥了Mn(III)的氧化能力。采用三重四级杆串联线性离子阱液相质谱仪（AB SCIEX QTRAP5500，LC-MS/MS）对KMnO4氧化产物进行分析测定。研究中利用建立的LC-MS/MS-PIS（Br-m/z79和81）子找母质谱方法对KMnO4氧化2,4-二溴苯酚（2,4-DBrP）的产物进行检测，测得3个主要含溴氧化耦合产物。(1)产物I的质量数为497/499/501/503（m/z79），推测由两个2,4-DBrP自由基通过邻位C-O耦合产生，为一种多溴联苯醚（2’-OH-BDE-68）；(2)产物II的质量数为497/499/501/503（m/z79），与产物I为同分异构体，推测由两个2,4-DBrP自由基通过邻位C-邻位C耦合产生；(3)产物III的质量数为419/421/423（m/z79），推测由两个2,4-DBrP自由基通过脱1个溴产生，结构中含有1个羟基和3个溴。理论上的聚合产物并没有全部检测到，主要是由于酚氧自由基的氧化耦合速率不同，则形成耦合产物的产率不同。更多还原

【Abstract】 As a typical odor subtance existing in the water, halogenated phenoliccompounds has been a hot research in the field of water treatment. It no only havethe biodegradable and water-soluble strong features, but also to have some toxiceffects of biological. Permanganate used for removal of halogenated phenoliccompounds has more prominent advantages. on the one hand, it can oxidationphenolic hydroxyl unsaturated functional groups of halogenated phenoliccompounds. On the other hand, permanganate does not produce toxic or harmfulby-products in the oxidation process and has obvious advantages comparedhapochlorous and ozone that could produce chlorinated and brominated by-products.Therefore, the reactions kinetics and the influence of environmentalfactors(cationtic or complexing agent) about the permanganate degradation ofhalogenated phenols organic pollutants in this paper. Besides, the mechamism aboutoxidative coupling product also been studied.The halogenated phenolic organic pollutants concentration were determined byhigh performance liquid in condition of false first order kinetics experiment and indifferent pH. In this paper, we select typical iodine phenol, bromophenol andfluorine phenol as the goal of organic pollutants. The research shows thatpermanganate can be applied effevtively to oxidative degradation halogenatedphenol conpounds which contain some unsaturated functional groups. The reactionfollowed a generalized second-order rate law and have a strong pH-dependent. Itwas found that the oxidation of halogenated phenol compounds displayedautocatalisis in the condition of pH=4and5suggesting the catalytic role of in situformed manganese oxides. Besides, the rate values of permanganate andhalogenated phenol conpounds showed an abnormal trend. The phenomenon can beinterpreted as permanganate oxidatation of halogenated phenol conpounds areassociated with the pKaof halogenated phenol conpounds. In the condition of pHless than pKa,the oxidation increased with pH. However, the oxidation decreased with pH when the pH is greated than the pKa.The role of cation and complexing agent on the degradation of phenoloxidation kinitics by permanganate were studied in condition of false first orderkinetics experiment. The presence of common cation ions (Ca2+、Mg2+) have littleimpact on the reaction, so when using permanganate as an oxidant to remove thehalogenated phenol conpounds, we don’t have to consider the effect of comoncations in water. However, ligands can significantly promote the oxidation ofhalogenated phenol conpounds by permanganate.Ligands promote parity statesfollow manganese valence theory that complexing agents can enhance the stabilityof Mn(III) during permanganate oxidation of halogenated phenol organic matter,and then played oxidation ability.With Triple level four rods series linear ion trap mass spectrometer in liquidphase, the oxidation products of permangante were analyzed and determined. Anovel and powerful precursor ion scan (PIS) approach was used for selectivedetection of brominated oxidation products by liquid chromatography/electrosprayionization-triple quadrupole mass spectrometry (LC-MS/MS-PIS). Results showedthat can been measured three main brominated dimeric products.(1) The massnumber for the first product is497/499/501/503（m/z79）.It can be inferred that as akind of polybrominated diphenyl either(2’-OH-BDE-68) is producted by two C-Ofree radicals coupling of each2,4-DBrP.(2) As isomers with the first product, themass number for second product is497/499/501/503(m/z79). It can be supposedthat can be coupling produce through two C-O free radicals coupling of each2,4-DBrP.(3) the third product is also coupling product which is producted throughtwo2,4-DBrP take off a bromine consisting of a hydroxyl group and three bromine.Due to the different rate of oxidative coupling of phenolic oxygen free radicals andthe yield of coupled product, polymerization product was not detected in all.更多还原