本文選題：微生物電化學(xué)系統(tǒng) + 梯級(jí)降解��； 參考：《哈爾濱工業(yè)大學(xué)》2017年博士論文

【摘要】：微生物電化學(xué)系統(tǒng)(Microbial electrochemical systems,MESs)是利用產(chǎn)電菌的催化作用將有機(jī)物中的化學(xué)能直接轉(zhuǎn)化為電能的裝置。作為一種兼具廢水處理和能源回收的新型水處理技術(shù),MESs在電極材料修飾、反應(yīng)器構(gòu)型優(yōu)化及胞外電子傳遞機(jī)制等方面已取得較大突破。然而,在處理成分復(fù)雜的有機(jī)廢水時(shí),MESs表現(xiàn)出產(chǎn)電性能下降、運(yùn)行能耗高及碳氮同步去除效果差等問題,限制了其在實(shí)際廢水處理中的應(yīng)用。針對(duì)以上問題,本論文從提高M(jìn)ESs對(duì)復(fù)雜有機(jī)物的降解效能、降低脫氮系統(tǒng)運(yùn)行能耗兩方面展開研究,構(gòu)建了可實(shí)現(xiàn)廢水中碳氮同步去除及凈能量回收的微生物電化學(xué)系統(tǒng),并對(duì)有機(jī)物降解過程與微生物種群的協(xié)同作用關(guān)系及脫氮機(jī)制進(jìn)行深入探討,對(duì)于建立微生物電化學(xué)強(qiáng)化廢水處理技術(shù)具有重要意義。以提高M(jìn)ESs對(duì)復(fù)雜有機(jī)物的處理效能及產(chǎn)電性能為目的,將連續(xù)攪拌釜式反應(yīng)器(CSTR)與MESs耦合,構(gòu)建了連續(xù)攪拌微生物電化學(xué)系統(tǒng)(CSMES)。在四通路的電極組合方式下,當(dāng)進(jìn)水有機(jī)負(fù)荷為12 kg COD/m~3/d時(shí),系統(tǒng)內(nèi)四個(gè)電池的最大功率密度分別為583±9、562±7、533±10和572±6 mW/m2。其COD去除率、甲烷產(chǎn)率及能量回收率分別為87.1±1.1%、1.48±0.15 L/L/d和32.1%,均優(yōu)于平行運(yùn)行的對(duì)照反應(yīng)器CSTR。高通量測(cè)序結(jié)果表明,電流的存在使地桿菌屬(Geobacter,14.5%)這種典型的產(chǎn)電菌屬選擇性富集在CSMES的陽(yáng)極上,相對(duì)復(fù)雜的細(xì)菌群落結(jié)構(gòu)使其同時(shí)含有豐度較高的嗜乙酸產(chǎn)甲烷菌屬(52.1%)和嗜氫產(chǎn)甲烷菌屬(47.0%),而CSTR以單一的嗜乙酸產(chǎn)甲烷菌屬為主(79.1%)。底端全混流攪拌區(qū)(CMZ)的厭氧消化與頂端微生物電化學(xué)區(qū)(MEZ)的產(chǎn)電過程之間的協(xié)同作用強(qiáng)化了小分子揮發(fā)酸的去除,緩解了發(fā)酵產(chǎn)物對(duì)產(chǎn)甲烷菌的抑制作用,從而提高了CMZ中產(chǎn)甲烷菌的多樣性及活性,強(qiáng)化了CSMES的有機(jī)物去除效能并使其能量回收率高于CSTR。以啤酒廢水為處理對(duì)象,考察CSMES對(duì)復(fù)雜有機(jī)物的降解機(jī)制。CSMES底端的CMZ以發(fā)生水解酸化反應(yīng)為主,啤酒廢水中79.1±5.6%的可溶性蛋白質(zhì)和86.6±2.2%的可溶性糖類首先在該區(qū)被發(fā)酵菌屬(Clostridium和Bacteroides,19.7%和5.0%)降解為小分子物質(zhì),供產(chǎn)甲烷菌屬(Methanosaeta和Methanobacterium,40.3%和38.4%)利用。部分小分子物質(zhì)及未被降解的蛋白質(zhì)和糖類等沿著水力方向進(jìn)入頂端的MEZ進(jìn)一步被該區(qū)的產(chǎn)氫產(chǎn)乙酸菌屬(Syntrophobacter,20.8%)及產(chǎn)電菌屬(Geobacter,12.4%)利用進(jìn)行產(chǎn)電,提高出水水質(zhì)的同時(shí)以電能的形式回收了啤酒廢水中的能量。CSMES對(duì)可溶性蛋白質(zhì)和糖類等有機(jī)物的梯級(jí)降解過程是保證其處理復(fù)雜有機(jī)物時(shí)產(chǎn)電性能相對(duì)穩(wěn)定的基礎(chǔ),而以上四類菌群的空間分布結(jié)構(gòu)及協(xié)同作用是該梯級(jí)降解過程的生物學(xué)依據(jù)。以降低微生物電化學(xué)脫氮系統(tǒng)運(yùn)行能耗為目的,利用虹吸式排水原理,構(gòu)建了復(fù)氧式生物陰極微生物電化學(xué)系統(tǒng)(ABMES)。為了提高生物陰極材料在間歇式復(fù)氧過程中對(duì)氧氣的吸附能力,以PTFE對(duì)柱狀活性炭(CAC)表面的一側(cè)進(jìn)行疏水處理,制備疏水型柱狀活性炭生物陰極材料(PTFE-coated CAC)。將其應(yīng)用于ABMES中可獲得8.2±0.8 W/m~3的最大功率密度,較未經(jīng)處理的CAC生物陰極比,提高了39%。PTFE-coated CAC的疏水表面對(duì)空氣的高親和力強(qiáng)化了氧氣向陰極生物膜內(nèi)部的傳質(zhì)過程,使其空氣捕獲率(29.7±0.6 L/m~3)較CAC生物陰極比提高了54±3.8%,從而使其氧還原催化性能優(yōu)于CAC生物陰極。間歇式復(fù)氧狀態(tài)及飽和溶解氧狀態(tài)下的陰極內(nèi)阻分析結(jié)果表明,電極表面產(chǎn)電菌較高的氧還原催化活性對(duì)PTFE-coated CAC性能的提高也起到一定作用。ABMES通過在陰極室實(shí)現(xiàn)同步硝化反硝化作用完成脫氮過程。外阻、COD/N及陰極室進(jìn)水-排水頻率三個(gè)因素通過影響陰極氧還原反應(yīng)、硝化過程及反硝化過程對(duì)ABMES的產(chǎn)電性能及脫氮效能產(chǎn)生較大影響。在外阻為5Ω、陰極室進(jìn)水-排水頻率為8 cph的條件下,以ABMES處理一種低碳氮比的實(shí)際廢水——污泥消化液(COD/N=2.5),其最大功率密度及總氮去除率分別為8.9±0.2 W/m~3和53.2±3.8%。這種間歇式復(fù)氧方法所需能耗僅占系統(tǒng)產(chǎn)能的14.3%,避免了脫氮過程中使用高能耗的曝氣供氧方式。得失電子平衡分析結(jié)果表明,異養(yǎng)反硝化與電化學(xué)反硝化過程的共同作用是促使ABMES在低碳氮比條件下獲得較高總氮去除率的原因。以CSMES-ABMES組成的串聯(lián)系統(tǒng)處理含氨氮的有機(jī)廢水——養(yǎng)豬廢水,考察其同步脫氮除碳性能。以聚合氯化鋁對(duì)養(yǎng)豬廢水進(jìn)行混凝處理,混凝后上清液中COD和SS的濃度分別下降到6745±522 mg/L和2441±185 mg/L。以串聯(lián)系統(tǒng)處理經(jīng)混凝沉淀的養(yǎng)豬廢水,其中對(duì)COD和SS起主要去除作用的為CSMES,而ABMES負(fù)責(zé)氨氮及總氮的去除。串聯(lián)系統(tǒng)總的COD、SS、氨氮及總氮的去除率分別為97.7±4.5%、94.4±5.8%、85.1±3.3%及43.8±2.3%,并獲得了1.298 kWh/m~3的凈能量,在完成碳氮同步去除的同時(shí)實(shí)現(xiàn)污水能源化,理論上可以實(shí)現(xiàn)能量自持。
[Abstract]:Microbial electrochemical systems (MESs) is a device for direct conversion of chemical energy in organic matter into electrical energy by using the catalysis of electric bacteria. As a new water treatment technology with both waste water treatment and energy recovery, MESs is used in the modification of electrode materials, optimization of reactor configuration and the mechanism of exo electron transfer. However, in the treatment of complex organic wastewater, MESs shows a decline in electrical properties, high energy consumption and poor carbon nitrogen removal efficiency, which restricts its application in the treatment of waste water. In this paper, the degradation efficiency of complex organic compounds and reduction of nitrogen removal from the higher MESs are proposed in this paper. The two aspects of the energy consumption of the system are studied, and a microbiological electrochemical system can be constructed to realize the simultaneous removal of carbon and nitrogen in the wastewater and the net energy recovery. The relationship between the organic degradation process and the microbial population and the mechanism of nitrogen removal are discussed. It is important for the establishment of microbiological electrochemical enhanced wastewater treatment technology. In order to improve the efficiency and power production performance of MESs for complex organic matter, the continuous agitating reactor (CSTR) and MESs are coupled to build a continuous stirring microorganism electrochemical system (CSMES). The maximum power of four batteries in the system when the influent organic load is 12 kg COD/m~3/d in the four channel electrode combination mode. The COD removal rate was 583 + 7533 + 10 and 572 + 6 mW/m2. respectively. The methane yield and energy recovery were 87.1 + 1.1%, 1.48 + 0.15 L/L/d and 32.1%, respectively, which were superior to the parallel operating control reactor CSTR. high throughput sequencing results. On the anode of CSMES, the relatively complex bacterial community structure makes it contain more eosinophilic methanogenic bacteria (52.1%) and methanogenic bacteria (47%), while CSTR is dominated by a single eosinophilic methanogenic genus (79.1%). The anaerobic digestion of the bottom end total mixed flow area (CMZ) and the production of the apical microorganism electrochemistry school area (MEZ) The synergistic effect between the electrical processes enhanced the removal of the volatile acid of small molecules, alleviated the inhibitory effect of the fermentation products on methanogenic bacteria, thus enhanced the diversity and activity of methanogens in CMZ, enhanced the removal efficiency of CSMES organic matter and made its energy recovery rate higher than that of CSTR., and investigated the complexity of CSMES to the complex. The degradation mechanism of organic matter at the bottom of.CSMES was mainly hydrolyzed and acidified, and 79.1 + 5.6% of soluble protein and 86.6 + 2.2% soluble sugar in beer wastewater were first degraded to small molecular substances (Clostridium, Bacteroides, 19.7% and 5%) in this area for methanogenic bacteria (Methanosaeta and Methanobacterium). 40.3% and 38.4%) MEZ is used to produce hydrogen producing acetic acid (Syntrophobacter, 20.8%) and producing electric bacteria (Geobacter, 12.4%) by using the partial small molecule material and the non degraded protein and sugar and so on. The effluent water quality is improved and the beer wastewater is recovered in the form of electric energy. The cascade degradation process of energy.CSMES to soluble proteins and carbohydrates is the basis for ensuring the relatively stable electrical performance of the complex organic matter, while the spatial distribution structure and synergy of the four types of bacteria are the biological basis for the cascade degradation process to reduce the operating energy of the microbial electrochemical denitrogenation system. In order to improve the adsorption capacity of oxygen in the process of intermittent reoxygenation, ABMES was constructed with the principle of siphon drainage. In order to improve the adsorption capacity of the cathode material to oxygen during the intermittent reoxygenation process, a hydrophobic columnar activated carbon (P) cathode material (P) was prepared by water treatment on one side of the surface of the columnar activated carbon (CAC). TFE-coated CAC). The maximum power density of 8.2 + 0.8 W/m~3 can be obtained by using it in ABMES. Compared with the untreated CAC Biological Cathode ratio, the high affinity of the hydrophobic surface of 39%.PTFE-coated CAC enhances the mass transfer process of oxygen to the cathode biofilm, and the air capture rate (29.7 + 0.6 L/m~3) is more than the CAC cathode. The ratio of oxygen reduction catalyzed by 54 + 3.8% was improved, and the catalytic performance of oxygen reduction was better than that of the CAC cathode. The results of the intermittent reoxygenation state and the cathodic resistance analysis in the saturated dissolved oxygen state showed that the higher oxygen reduction catalytic activity on the electrode surface also played a role in improving the performance of the PTFE-coated CAC through the cathode chamber. The nitrification and denitrification process has completed the process of denitrification. The three factors of external resistance, COD/N and the frequency of influent drainage of the cathode chamber affect the cathodic oxygen reduction reaction, nitrification process and denitrification process have a great influence on the electric property and denitrification efficiency of ABMES. Under the condition of the external resistance is 5 Omega, the influent water frequency of the cathode chamber is 8 CPH, it is treated with ABMES. The actual wastewater of low carbon and nitrogen ratio, COD/N=2.5, has the maximum power density and total nitrogen removal rate of 8.9 + 0.2 W/m~3 and 53.2 + 3.8%.. The energy consumption of the intermittent reoxygenation method is only 14.3% of the capacity of the system. It avoids the high energy consumption oxygen supply mode in the process of denitrification. The common effect of heterotrophic denitrification and electrochemical denitrification is the reason for ABMES to obtain higher total nitrogen removal rate under the low carbon and nitrogen ratio. The series system composed of CSMES-ABMES is used to treat organic wastewater containing ammonia nitrogen - pig wastewater and investigate its synchronous denitrification and decarbonization energy. The concentration of COD and SS in the supernatant after coagulation was reduced to 6745 + 522 mg/L and 2441 + 185 mg/L. respectively to treat the pig wastewater with coagulation sedimentation in series system. The main removal effect of COD and SS was CSMES, and ABMES was responsible for the removal of ammonia nitrogen and total nitrogen. The total COD, SS, ammonia nitrogen and total nitrogen removal rate of the series system was 97.7, respectively. It is + 4.5%, 94.4 + 5.8%, 85.1 + 3.3% and 43.8 + 2.3%, and the net energy of 1.298 kWh/m~3 is obtained. At the same time, the sewage energy is realized at the same time of carbon and nitrogen removal. The energy self holding can be realized in theory.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703
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本文編號(hào)：1987269