本文關鍵詞：廊道推流式生物電化學系統(tǒng)還原偶氮染料效能和機制研究　出處：《哈爾濱工業(yè)大學》2017年博士論文　論文類型：學位論文

  更多相關文章： 偶氮染料 茜素黃R 還原脫色 生物電化學系統(tǒng) 陰極生物膜

【摘要】：偶氮染料是分子結(jié)構(gòu)中含有一個或多個偶氮鍵(-N=N-)的芳香類化合物,是目前工業(yè)中應用最多的合成染料,具有結(jié)構(gòu)穩(wěn)定、抗酸堿、抗微生物等特點,被大量使用,尤其是印染等產(chǎn)業(yè)。偶氮染料表現(xiàn)出極高的色度,在自然界中極難降解及代謝產(chǎn)物高毒性和致癌性的特點,含有偶氮染料的廢水對生態(tài)系統(tǒng)和人類健康造成嚴重威脅。中國印染產(chǎn)業(yè)規(guī)模巨大,產(chǎn)生的工業(yè)廢水中含有大量的偶氮染料,我國現(xiàn)在對于相關廢水的處理主要針對廢水的脫色脫毒來進行處理。傳統(tǒng)的物理和化學處理方法,成本高且容易產(chǎn)生有毒有害的中間產(chǎn)物。厭氧生物處理可以對偶氮染料進行有效脫色,然而厭氧生物處理所需時間過長,導致脫色效率較低,且廢水中缺乏可直接利用的電子供體,成為生物處理偶氮染料類廢水的制約性因素。生物電化學系統(tǒng)(Bioelectrochemical Systems,BESs),以微生物為催化劑在電極進行氧化/還原反應,結(jié)合了生物處理和電化學方法的優(yōu)點,已成為近年來發(fā)展迅速、很有前景的環(huán)境污染處理技術。本研究選取茜素黃R(Alizarin Yellow R,茜素黃R),一種最普遍應用的偶氮染料為模式污染物,針對傳統(tǒng)的雙極室生物電化學系統(tǒng)成本高、且難以工程放大,開發(fā)設計了一種廊道推流式連續(xù)流生物電化學反應器(Plug Flow Baffled-Bioelectrochmical Reactor,PFB-BER),圍繞高脫色效能和低電能耗,優(yōu)化了反應器的設計運行參數(shù);結(jié)合陰極生物膜微生物群落結(jié)構(gòu)組成,解析了連續(xù)流情況下PFB-BER的長期脫色效能和與好氧曝氣(Aeration Reactor)系統(tǒng)聯(lián)合(PFB-BER-AR)后的長期礦化效能。以反應器構(gòu)型改進為目的,建立了一種廊道推流式生物電化學反應器,在連續(xù)流條件下可以實現(xiàn)對茜素黃R的快速還原脫色,脫色效率較開路情況下提高了1.27倍(水力停留時間為24h時),對苯二胺和5-氨基水楊酸生成率分別為95%和50%。循環(huán)伏安曲線和交流阻抗分析表明,系統(tǒng)外加電壓控制在0.5V,使陰極電位控制在-0.9 V左右,可以保證茜素黃R的還原反應的發(fā)生,充分還原降解。反應器的總內(nèi)阻為121.1Ω,遠小于純電化學反應器的內(nèi)阻。隨著反應器水力停留時間的縮短,反應器的還原脫色效率降低。當水力停留時間從8 h縮短到4 h時,還原脫色效率從69.9%降低到44.9%。增加一組電極組可以明顯提高脫色效率,4 h的脫色效率由44.8%升高到83.1%。對比外加電壓能耗,發(fā)現(xiàn)在相對一致的還原脫色效率下,水力停留時間為4 h的兩組電極反應裝置,要比水力停留時間為12 h的一組電極反應裝置能耗低。適當增加電極組,可有效提高脫色效率并避免高的電壓能耗。在生物電化學反應器陰極系統(tǒng)中,茜素黃R可以被快速還原脫色(乙酸鈉:0.1818±0.0139/h;葡萄糖:0.4620±0.0567/h),其還原脫色效率較非生物陰極(0.0.1197±0.0004/h)分別提高了1.5倍(乙酸鈉)和3.9倍(葡萄糖)。其出水色度符合國家二級出水標準色度要求(40)。不同參數(shù)條件下,茜素黃R的還原脫色速率隨初始濃度的增加而降低,隨外加電壓的升高而升高;以葡萄糖為底物,茜素黃R的去除速率及產(chǎn)物的生成速率是以乙酸鈉為底物條件的3倍�；陧憫婺Ｐ蛿M合,得出茜素黃R初始濃度為130-135 mg/L和155 mg/L和外加電壓為0.66 V和0.58 V(分別以乙酸鈉和葡萄糖為基質(zhì))時,生物陰極的脫色效率最高,且單位能耗最低。生物陰極生物膜群落結(jié)構(gòu)分析表明,馴化后細菌群落結(jié)構(gòu)發(fā)生很大變化,以葡萄糖為底物時,Citrobacter、Enterococcus和Alkaliflexus等菌屬為主導菌屬,以乙酸鈉為底物時,Acintobacter和Achromobacter等為主導菌屬。底物不同導致群落結(jié)構(gòu)差異和不同的還原脫色效率,表明以葡萄糖作為電子供體時能馴化出有利于茜素黃R還原脫色的菌群,提高反應器的性能。廊道推流式生物電化學反應器在長期運行的情況下,可以持續(xù)穩(wěn)定地脫色茜素黃R。將此反應器與好氧曝氣裝置聯(lián)合,其還原產(chǎn)物(對苯二胺和5-氨基水楊酸)可進一步被氧化,實現(xiàn)茜素黃R的長期持續(xù)礦化。微生物群落結(jié)構(gòu)分析表明,長期運行情況下,電極類型和電極位置明顯影響了電極生物膜上菌群的豐度和菌屬類型。陽極生物膜以Ornatilinea菌屬為主導,陰極生物膜以Acinetobacter,Pseudomonas和Geobacter為主導,Geobacter菌屬在第二組電極組上的含量遠高于第一組電極組。推斷生物膜結(jié)構(gòu)的變化受水中污染物濃度影響較大。本研究證實生物電化學系統(tǒng)可作為還原脫色偶氮染料的有效手段,開發(fā)設計的廊道推流式反應器可作為一種新型工藝處理模式,為染料類廢水的脫色和徹底脫毒及系統(tǒng)工藝放大提供一種新的技術手段。
[Abstract]:Azo dyes are aromatic compounds containing one or more azobenzene bonds (-N=N-) in the molecular structure. They are the most widely used synthetic dyes in the industry. They are characterized by stable structure, acid and alkali resistance and microbial resistance. They are widely used, especially in printing and dyeing industries. Azo dyes show very high chromaticity. They are extremely difficult to degrade in nature and the characteristics of high toxicity and carcinogenicity of metabolites. Wastewater containing azo dyes poses a serious threat to ecosystem and human health. The scale of China's printing and dyeing industry is huge. Industrial wastewater contains a lot of azo dyes. Now, the treatment of related wastewater is mainly aimed at the decolorization and detoxification of wastewater. Traditional physical and chemical treatment methods have high cost and easy to produce toxic and harmful intermediate products. Anaerobic biotreatment can effectively decolorization azo dyes. However, the time needed for anaerobic biotreatment is too long, resulting in low decolorization efficiency, and the lack of directly used electronic donors in waste water has become a restrictive factor for biological treatment of azo dye wastewater. Bioelectrochemical Systems (BESs) has been used as an oxidant / reductive electrode at the electrode, combined with the advantages of biological treatment and electrochemical methods. It has become a promising and promising environmental pollution treatment technology in recent years. This study selected the Alizarin Yellow R (Alizarin Yellow R, Alizarin Yellow R), one of the most common applications of azo dyes as model pollutant, the cost of double chamber bioelectrochemical system of traditional high, and difficult to scale-up, design a corridor push flow type continuous bio electrochemical reactor (Plug Flow Baffled-Bioelectrochmical Reactor, PFB-BER), around the high decolorization efficiency and low electric power consumption, design and operation parameters of the reactor were optimized; combined with the microbial community structure of the cathode biofilm composition, analysis of the long-term continuous decolorization efficiency in case of PFB-BER and aeration and aerobic (Aeration Reactor) system (PFB-BER-AR) combined with long-term efficacy after mineralization. In order to improve the reactor configuration for the purpose of establishing a corridor push flow bio electrochemical reactor under continuous flow can achieve rapid decolorization of Alizarin Yellow R, decolorization efficiency is increased by 1.27 times under the condition of open circuit (HRT 24h), two of benzene amine and 5- amino salicylic acid generation rates were 95% and 50%. Cyclic voltammetry and AC impedance analysis indicate that the external voltage of the system is controlled at 0.5V, so that the cathodic potential is controlled at about -0.9 V, which can guarantee the reduction reaction of Alizarin Yellow R, and fully degrade and degrade. The total internal resistance of the reactor is 121.1 Omega, which is far less than the internal resistance of the pure electrochemical reactor. With the shortening of the hydraulic retention time of the reactor, the reduction and decolorization efficiency of the reactor decreased. When the hydraulic retention time is shortened from 8 h to 4 h, the reduction decolorization efficiency is reduced from 69.9% to 44.9%. The decolorization efficiency of a group of electrodes increased significantly, and the decolorization efficiency of 4 h increased from 44.8% to 83.1%. Compared with the external voltage consumption, it was found that under the relatively uniform reduction and decolorization efficiency, the two group of electrode reaction devices with hydraulic retention time of 4 h had lower energy consumption than a set of electrode reaction devices with a hydraulic retention time of 12 h. The appropriate increase of the electrode group can effectively improve the decolorization efficiency and avoid high voltage energy consumption. In the bio electrochemical reactor cathode system, Alizarin Yellow R can be rapid decolorization (acetate: 0.1818 + 0.0139/h; glucose: 0.4620 + 0.0567/h), the decolorization efficiency is non bio cathode (0.0.1197 + 0.0004/h) were increased 1.5 times and 3.9 times (acetate) (glucose). Its water color accords with the national standard of two grade effluent standard (40). Under different parameters, the reduction decolorization rate of Alizarin Yellow R decreased with the increase of initial concentration, and increased with the increase of applied voltage. On the basis of glucose, the removal rate of Alizarin Yellow R and product formation rate were 3 times higher than that of sodium acetate. Based on the fitting of the response surface model, it is concluded that the initial concentration of Alizarin Yellow R is 130-135 mg/L and 155 mg/L, and the applied voltage is 0.66 V and 0.58 V, respectively. When the sodium acetate and glucose are used as matrix respectively, the decolorization efficiency of the biological cathode is the highest and the unit energy consumption is the lowest. Analysis shows that the bio cathode biofilm community structure, domesticated bacterial community structure changed, with glucose as substrate, Citrobacter, Enterococcus and Alkaliflexus belongs to the genus of dominant species, with sodium acetate as substrate, Acintobacter and Achromobacter led to sp.. Different substrates lead to differences in community structure and different reductive decolorization efficiency. It indicates that when glucose is used as electron donor, bacteria can help to reduce the decolorization of Alizarin Yellow R, and improve the performance of the reactor. The Alizarin Yellow R can be continuously decolored in the long-term operation of the porch push-flow bioreactor. When the reactor is combined with aerobic aeration device, its reducing products (benzene two amine and 5- amino salicylic acid) can be further oxidized to achieve long-term continuous mineralization of Alizarin Yellow R. The analysis of microbial community structure showed that the type of electrode and the position of electrode significantly affected the abundance of bacteria and the type of bacteria on the electrode biofilm in the long run. The anodic biofilms were dominated by Ornatilinea bacteria, and the cathodic biofilms were dominated by Acinetobacter, Pseudomonas and Geobacter. The content of Geobacter bacteria on the second sets of electrode groups was much higher than that of the first set of electrode groups. It is inferred that the changes in the structure of the biofilm are greatly influenced by the concentration of pollutants in the water. This study demonstrated that bio electrochemical system can be used as effective means of decolorization of azo dyes, development and design of the corridor plug flow reactor can be used as a new treatment mode, for the decolorization of dye wastewater and thorough process of removing poison and system provides a new technical means to enlarge.
【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X703

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