發(fā)布時(shí)間：2018-08-21 08:10

【摘要】：有機(jī)砷被作為飼料添加劑被廣泛地應(yīng)用于畜牧業(yè)中。近年來(lái),有機(jī)砷的污染問(wèn)題越來(lái)越受到人們的重視,尤其是有機(jī)砷經(jīng)過(guò)自然降解轉(zhuǎn)化,會(huì)生成劇毒的無(wú)機(jī)砷,對(duì)環(huán)境和人類(lèi)帶來(lái)潛在的威脅。阿散酸和洛克沙胂是其中兩種最為主要的有機(jī)砷飼料添加劑,關(guān)于它們的研究還是比較有限的。本文研究了水溶液中有機(jī)砷在化學(xué)氧化過(guò)程中的動(dòng)力學(xué)、熱力學(xué)以及降解機(jī)理。論文的主要內(nèi)容如下：高錳酸鉀氧化降解阿散酸過(guò)程符合修正動(dòng)力學(xué)模型。研究了酸堿度、腐植酸以及離子強(qiáng)度對(duì)降解過(guò)程的影響,酸性條件下,阿散酸的降解速率較大,腐植酸的存在會(huì)促進(jìn)阿散酸的降解,離子強(qiáng)度對(duì)整個(gè)降解過(guò)程沒(méi)有影響。從熱力學(xué)的角度分析了降解過(guò)程,采用GC-MS推測(cè)了降解途徑,阿散酸在高錳酸鉀的氧化作用下,幾乎沒(méi)有礦化,砷完全被脫下,生成五價(jià)砷和苯胺。次氯酸鈉氧化降解阿散酸過(guò)程采用一般動(dòng)力學(xué)擬合,對(duì)阿散酸的反應(yīng)級(jí)數(shù)為0.5,對(duì)次氯酸鈉的反應(yīng)級(jí)數(shù)為1.8,整個(gè)反應(yīng)是一個(gè)級(jí)數(shù)為2.3的反應(yīng)過(guò)程。研究了酸堿度、腐植酸以及2種常見(jiàn)離子對(duì)降解過(guò)程的影響,酸性條件下,阿散酸的降解速率較大,腐植酸的存在會(huì)抑制阿散酸的降解,銨根離子抑制了降解過(guò)程,碳酸氫根離子對(duì)降解過(guò)程有一定的促進(jìn)作用。在真實(shí)水體中次氯酸鈉降解阿散酸的效果不甚理想。通過(guò)砷形態(tài)和GC-MS測(cè)定了中間產(chǎn)物,砷被氯取代,生成的三價(jià)砷迅速被氧化成為五價(jià)砷,同時(shí)生成三氯苯胺。次氯酸鈉氧化降解洛克沙胂過(guò)程符合偽一級(jí)動(dòng)力學(xué),對(duì)洛克沙胂的反應(yīng)級(jí)數(shù)為1,對(duì)次氯酸鈉的反應(yīng)級(jí)數(shù)為1,整個(gè)反應(yīng)是一個(gè)二級(jí)反應(yīng)。研究了酸堿度、腐植酸以及2種常見(jiàn)離子對(duì)降解過(guò)程的影響,酸性條件下,洛克沙胂的降解速率較大,腐植酸的存在會(huì)促進(jìn)洛克沙胂的降解,銨根離子抑制了降解過(guò)程,碳酸氫根離子對(duì)降解過(guò)程有一定的促進(jìn)作用。在真實(shí)水體中次氯酸鈉降解洛克沙胂的效果比較理想。通過(guò)砷形態(tài)和LC-MS測(cè)定了中間產(chǎn)物,砷被氯取代,生成的三價(jià)砷迅速被氧化成為五價(jià)砷,同時(shí)生成三氯硝基苯胺。
[Abstract]:Organic arsenic is widely used in animal husbandry as feed additive. In recent years, more and more attention has been paid to the pollution of organic arsenic, especially organic arsenic, which can produce highly toxic inorganic arsenic after natural degradation and transformation, which brings potential threat to the environment and human beings. Arsanilic acid and roxarsone are two of the most important organic arsenic feed additives. The kinetics, thermodynamics and degradation mechanism of organic arsenic in aqueous solution during chemical oxidation were studied. The main contents of this paper are as follows: the oxidation and degradation of arsonic acid by potassium permanganate accords with the modified kinetic model. The effects of acidity, humic acid and ionic strength on the degradation process were studied. Under acidic conditions, the degradation rate of arsonic acid was higher. The presence of humic acid could promote the degradation of arsonic acid, but the ionic strength had no effect on the whole degradation process. The degradation process was analyzed from the viewpoint of thermodynamics. The degradation pathway was inferred by GC-MS. Under the oxidation of potassium permanganate, there was almost no mineralization, and arsenic was completely removed to form pentavalent arsenic and aniline. The process of oxidative degradation of arsonic acid by sodium hypochlorite was fitted by general kinetics. The order of reaction was 0.5 for sodium hypochlorite and 1.8 for sodium hypochlorite. The whole reaction was a process of order 2.3. The effects of pH, humic acid and two common ions on the degradation process were studied. Under acidic conditions, the degradation rate of arsonic acid was higher. The presence of humic acid inhibited the degradation of arsonic acid, and the degradation process was inhibited by ammonium ion. Bicarbonate ions can promote the degradation process to some extent. The effect of sodium hypochlorite on the degradation of arsonic acid in real water is not satisfactory. The intermediate product was determined by arsenic morphology and GC-MS. Arsenic was replaced by chlorine and the resulting trivalent arsenic was quickly oxidized to pentavalent arsenic and trichloroaniline was formed at the same time. The oxidation degradation of roxarsone by sodium hypochlorite accords with pseudo-first-order kinetics. The order of reaction for roxarsone and sodium hypochlorite is 1, and the whole reaction is a second-order reaction. The effects of pH, humic acid and two common ions on the degradation of roxarsone were studied. The degradation rate of roxarsone was higher under acidic conditions. The presence of humic acid promoted the degradation of roxarsone, and the degradation process was inhibited by ammonium ion. Bicarbonate ions can promote the degradation process to some extent. The degradation of roxarsone by sodium hypochlorite in real water is ideal. The intermediate product was determined by arsenic speciation and LC-MS. Arsenic was replaced by chlorine and the resulting trivalent arsenic was quickly oxidized to pentavalent arsenic and trichloronitroaniline was formed at the same time.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：X131.2

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