【摘要】：基于活化氧氣的高級(jí)氧化技術(shù)作為一種簡單、綠色、低成本的處理技術(shù),在水處理領(lǐng)域中已引起廣泛的關(guān)注,高級(jí)氧化技術(shù)中產(chǎn)生的活性自由基是作用于水中污染物氧化和降解的關(guān)鍵物種,因此,在溫和條件下,活化氧氣產(chǎn)生高活性自由基簡單、高效、低成本體系的構(gòu)建具有較強(qiáng)的科學(xué)意義和實(shí)際應(yīng)用價(jià)值。本研究構(gòu)建了基于鄰氨基酚、對(duì)氨基酚和對(duì)苯二酚類還原性有機(jī)污染物的“還原性物質(zhì)/Co2+-HCO3-”催化活化氧氣產(chǎn)生高活性自由基的體系,分別從催化活化氧氣體系的構(gòu)建、底物的氧化降解特性、產(chǎn)生活性物種的類型、機(jī)制以及體系的效能研究等方面進(jìn)行了系統(tǒng)詳細(xì)的探討,得出一些創(chuàng)新性結(jié)論。①本研究成功構(gòu)建了基于鄰氨基酚(OAP)、對(duì)氨基酚(PAP)和對(duì)苯二酚(H2Q)的“還原性物質(zhì)/Co2+-HCO3-”催化活化氧氣氧化產(chǎn)生高活性自由基的體系,該體系表現(xiàn)出了較好的催化氧化活性,還原性物質(zhì)自身對(duì)于活性自由基的產(chǎn)生起著非常重要的作用,進(jìn)一步對(duì)構(gòu)建體系的效能研究表明,所構(gòu)建的PAP-Co2+-HCO3-和H2Q-Co2+-HCO3-體系在氧化自身還原性物質(zhì)的同時(shí)對(duì)于含染料廢水的處理也表現(xiàn)出一定活性,在廢水處理過程中能達(dá)到以廢治廢的目的。②OAP-Co2+-HCO3-體系中,OAP能被有效地氧化為2-氨基吩惡嗪-3-酮(APZ),體系中Co2+、HCO3-和O2對(duì)OAP的氧化過程缺一不可;O2與形成的Co II(HCO3-)(OAP)配合物相互作用,生成O2?-(單電子還原產(chǎn)物)和O22-(雙電子還原產(chǎn)物),O22-經(jīng)過歧化作用和質(zhì)子化作用生成中間產(chǎn)物H2O2;電子順磁共振技術(shù)和自由基抑制技術(shù)研究表明體系中生成的H2O2分解成的非游離型羥基自由基?OH是作用于OAP氧化的活性物種。③PAP-HCO3-和PAP-Co2+-HCO3-體系均能活化氧氣作用于PAP的氧化,Co2+的加入能夠促進(jìn)在PAP-Co2+-HCO3-體系產(chǎn)生非游離型羥基自由基,該非游離型羥基自由基是作用于PAP氧化的主要活性物種,它的產(chǎn)生來自于兩個(gè)步驟:i)O2的還原產(chǎn)物O2-?介導(dǎo)的H2O2的生成,ii)生成的H2O2與Co2+-HCO3-配合物通過Fenton反應(yīng)生成非游離型羥基自由基,與此同時(shí),在PAP氧化過程中產(chǎn)生的高活性?OH自由基能進(jìn)一步作用于偶氮染料AOII的脫色降解。④H2Q-HCO3-和H2Q-Co2+-HCO3-體系均能活化氧氣作用于H2Q的氧化,在HCO3-溶液中,H2Q的氧化過程為,首先失去一個(gè)電子轉(zhuǎn)化為半醌自由基BQ?-,繼而再失去一個(gè)電子轉(zhuǎn)化為對(duì)苯醌,在此過程中O2被還原成H2O2,在Co2+的作用下H2O2分解成羥基自由基,并證明體系中產(chǎn)生羥基自由基是作用于H2Q的主要活性物種,另外體系中的產(chǎn)生HCO4-也部分作用于H2Q的氧。H2Q-Co2+-HCO3-體系能作用于AOII的降解,體系中產(chǎn)生的羥基自由基能有效攻擊AOII分子結(jié)構(gòu)上的兩個(gè)C-N鍵,AOII分子結(jié)構(gòu)中的N元素以N2的形式釋放出去,體系中檢測到的AOII的降解產(chǎn)物主要為對(duì)苯磺酸鈉和1,2-萘醌及其進(jìn)一步氧化產(chǎn)物。
[Abstract]:As a simple, green and low cost treatment technology, advanced oxidation technology based on activated oxygen has attracted extensive attention in the field of water treatment. The active free radicals produced in advanced oxidation technology are the key species acting on the oxidation and degradation of pollutants in water. Therefore, under mild conditions, activated oxygen produces high active free radicals. The construction of low cost system has strong scientific significance and practical application value. In this study, a "reductive substance / Co2-HCO3-" catalyzed activated oxygen to produce highly active free radicals based on o-aminophenol, p-aminophenol and hydrocatechol reductive organic pollutants was constructed. The construction of catalytic activated oxygen system, the oxidative degradation characteristics of substrate, the type of active species produced, the mechanism and the efficiency of the system were discussed in detail. Some innovative conclusions are drawn. 1 in this study, a system based on o-aminophenol (OAP), p-aminophenol (PAP) and hydrocatechol (H2Q) was successfully constructed, which catalyzed the oxidation of activated oxygen to produce highly active free radicals. The system showed good catalytic oxidation activity, and the reductive substances themselves played a very important role in the production of active free radicals. The further study on the efficiency of the construction system shows that the constructed PAP-Co2-HCO3- and H2Q-Co2-HCO3- systems not only oxidize their own reductive substances, but also show certain activity for the treatment of dye-containing wastewater, and can achieve the purpose of treating waste with waste in the process of wastewater treatment. In 2OAP-Co2-HCO3- system, OAP can be effectively oxidized to Co2 in 2-aminophene oxazin-3-one (APZ), system. The oxidation process of OAP by HCO3- and O2 is indispensable. O _ 2 interacts with the formed Co II (HCO3-) (OAP) complex to form O _ 2 (single electron reduction product) and O22-(double electron reduction product). O _ 22-forms intermediate H _ 2O _ 2 through disambiguation and protonation. Electron parammagnetic resonance technique and free radical inhibition technique show that the non-free hydroxyl radical formed by H2O2 in the system? OH is an active species acting on the oxidation of OAP. 3PAP-HCO3- and PAP-Co2-HCO3- systems can activate oxygen to act on the oxidation of PAP, and the addition of Co2 can promote the production of non-free hydroxyl radicals in PAP-Co2-HCO3- system. The non-free hydroxyl radical is the main active species acting on PAP oxidation, and its production comes from the reduction product O2 of: i) O2 in two steps. The H2O2 formed by, ii) mediated by H2O2 reacts with Co2-HCO3- to form non-free hydroxyl radical by Fenton reaction. At the same time, the high activity OH radical produced during PAP oxidation can further act on the decolorization and degradation of azo dye AOII. 4H2Q-HCO3- and H2Q-Co2-HCO3- systems can activate oxygen to oxidize H2Q. In HCO3- solution, the oxidation process of H2Q is. In this process, O2 is reduced to H2O2, and H2O2 is decomposed into hydroxyl radical under the action of Co2. It is proved that the hydroxyl radical in the system is the main active species acting on H2Q, and the production of HCO4- in the system can also partly act on the oxygen of H2Q. The H2Q-Co2-HCO3- system can act on the degradation of AOII, and it is proved that the hydroxyl radical produced in the system is the main active species acting on H2Q. in addition, the generation of hydroxyl radical in the system can also partly act on the oxygen of H2Q. H2Q-Co2-HCO3- system can act on the degradation of AOII. The hydroxyl radical produced in the system can effectively attack two C-N bonds on the molecular structure of AOII. The N element in the molecular structure of AOII is released in the form of N2. The degradation products of AOII detected in the system are mainly sodium p-benzenesulfonate and 1, 2-Naphthoquinones and their further oxidation products.
【學(xué)位授予單位】：武漢紡織大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X703.1

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本文編號(hào)：2499973