本文關鍵詞：典型有機殺菌藥物在環(huán)境中由OH引發(fā)的降解機理及動力學研究　出處：《山東大學》2015年碩士論文　論文類型：學位論文

  更多相關文章： 有機殺菌藥物 OH自由基 三氯生 速率常數(shù) 林丹 左氧氟沙星 高級氧化技術

【摘要】：有機化學藥物在當今人類的生產和生活中用量巨大,這些化學藥物起到了抗菌殺菌的作用,對人類和農作物的健康具有重要意義,但同時也大量排放到環(huán)境當中,在大氣、水、土壤中不斷被檢測到。這類物質在環(huán)境中能夠進一步遷移、轉化和富集,危害生態(tài)安全和人類健康。目前環(huán)境中的藥物污染表現(xiàn)出了難降解,在環(huán)境中存在形式多樣,以及降解環(huán)境復雜的特點。個人護理用品(PPCPs)和具有POPs性質的農藥作為新型有機污染藥物被廣泛關注。本文選取個人護理用品添加劑三氯生、抗生素藥物左氧氟沙星、和有機氯農藥林丹作為研究對象。選取具有強氧化性的OH自由基作為引發(fā)劑,重點研究它們在OH自由基存在條件下的降解機理,為環(huán)境降解和廢棄物處理提供了計算依據。全文采用了量子化學高精度密度泛函的方法(Density Functional Theory, DFT),在MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p)水平下重點計算了這三種物質由OH引發(fā)的降解路徑,給出了熱力學數(shù)據和動力學常數(shù),得到一些重要結論：1.三氯生在氣相條件下的OH降解機理和動力學研究。作為一種廣譜殺菌劑,三氯生被大量用于生產和生活中,排放到環(huán)境中可對環(huán)境產生危害和污染。為了研究其在環(huán)境中的降解轉化過程,量子化學計算的方法被用來計算其反應過程,并使用變分過渡態(tài)理論計算了其動力學數(shù)據。計算了OH引發(fā)的加成和抽提兩條反應路徑,并且研究了其進一步分解成酚類、醛類和其他易降解物質的反應。研究了三氯生在環(huán)境中轉化成為二VA英、呋喃、和多氯聯(lián)苯的降解機理和反應路徑,表明三氯生在環(huán)境中可以轉化成為毒性更大的持久性有機污染物,給環(huán)境帶來潛在污染。在298.15 K時,加成反應和抽提反應的反應比例分別是kadd/ktotal=0.955和kabs/ktotal=0.045。說明加成反應是三氯生由OH引發(fā)的降解的主要反應,同時三氯生的抽提反應可在環(huán)境中進一步反應,轉化成為二VA英。2.林丹在大氣中的光催化反應機理研究研究了OH自由基引發(fā)的林丹在大氣中光降解反應的機理。使用密度泛函(DFT)理論計算提出了林丹在大氣中的鏈式反應機理。給出了每一降解步驟的勢壘和反應熱數(shù)據。同時用量子化學計算方法證明林丹脫C1無法直接從鏈式結構直接脫去HCl得到,給出了合理的脫C脫Cl機理,明確了林丹在大氣中降解礦化的路徑。3.左氧氟沙星在水中由OH引發(fā)的降解反應機理研究高級氧化方法可應用于左氧氟沙星的降解。利用OH自由基的高氧化活性可有效的去除水中的抗生素。研究OH自由基降解左氧氟沙星有助于給高級氧化處理技術提供更詳盡的理論數(shù)據支持。文章分別研究了OH自由基對左氧氟沙星的加成和抽提降解。計算了反應熱和反應勢壘,找出能量最優(yōu)降解路徑并給出了動力學數(shù)據。
[Abstract]:The use of organic chemicals in the production and life of human beings is huge. These chemicals play an antibacterial role in bactericidal activities and play an important role in the health of human beings and crops. But at the same time, it is also released into the environment, which is continuously detected in the atmosphere, water and soil. These substances can be further transported, transformed and enriched in the environment. It is harmful to ecological security and human health. At present, drug pollution in the environment is difficult to degrade, and there are various forms in the environment. Personal care products (PPPs) and pesticides with POPs properties as novel organic pollutants have been widely concerned. In this paper, personal care products additive triclosan was selected. The antibiotic levofloxacin and organochlorine pesticide Lin Dan were selected as initiators to study their degradation mechanism in the presence of OH radical. It provides the basis for environmental degradation and waste disposal. The method of quantum chemical high precision density functional is used in this paper, which is called Density Functional Theory. DFT, in the MPWB1K/6-311, 3dffl / / MPWB1K / 6-31Gd / / MPWB1K / / MPWB1K / 6-31Gd. The degradation paths initiated by OH were calculated and the thermodynamic data and kinetic constants were given. Some important conclusions were drawn: 1.The degradation mechanism and kinetics of triclosan in gaseous phase. As a broad-spectrum bactericide, triclosan is widely used in production and life. In order to study the degradation and transformation process in the environment, quantum chemical calculation method is used to calculate the reaction process. The kinetic data were calculated by using the variational transition state theory, the addition and extraction pathways initiated by OH were calculated, and the further decomposition to phenols was studied. Reaction of aldehydes with other biodegradable substances. The degradation mechanism and reaction pathway of trichlorobenzene into diVA furan and polychlorinated biphenyls in the environment were studied. It shows that trichlorogenic can be converted into more toxic persistent organic pollutants in the environment and bring potential pollution to the environment. At 298.15 K. The ratio of addition reaction to extraction reaction is kadd/ktotal=0.955 and Kabs / ktotal0.045, respectively. It shows that the addition reaction is induced by OH. The main reaction to the solution. At the same time, the extraction reaction of triclosan can be further reacted in the environment. Studies on the photocatalytic reaction mechanism of Lin Dan in the atmosphere; the photodegradation mechanism of Lin Dan initiated by OH radical in the atmosphere. The mechanism of Lin Dan's chain reaction in the atmosphere is proposed by theoretical calculation. The potential barrier and reaction heat data of each degradation step are given. It is proved by quantum chemical calculation that Lin Dan can't remove C1 directly from chain structure. To HCl. A reasonable mechanism of dechlorination is given. The path of degradation and mineralization of lindane in the atmosphere .3.The degradation mechanism of levofloxacin in water induced by OH; the advanced oxidation method can be applied to the degradation of levofloxacin. The study on the degradation of levofloxacin by OH free radical is helpful to provide more detailed theoretical data for advanced oxidation treatment technology. This paper studies the effect of OH free radical on levofloxacin in water. Addition and extraction degradation of Fluorfloxacin. Reaction heat and reaction barrier were calculated. The optimal energy degradation path is found and the kinetic data are given.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：X50

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