本文選題：氫自養(yǎng)反硝化 + UBER反應(yīng)器�。� 參考：《中國科學院煙臺海岸帶研究所》2017年博士論文

【摘要】：近年來,隨著工農(nóng)業(yè)的發(fā)展和人口的快速增長,水體中各類含氮化合物的含量急劇增加,其中絕大部分含氮化合物會在適宜的環(huán)境條件下轉(zhuǎn)化為相對穩(wěn)定的硝態(tài)氮。通常,由于高負荷含氮污廢水直接輸入等原因,地表水體中的碳氮比往往相對較低,同時由于自然水體相對較弱的自凈能力,使得硝態(tài)氮在地表水體中不斷累積,高濃度硝態(tài)氮已成為部分地區(qū)地表水最為突出的污染因子,其嚴重影響了地表水的資源價值,并危害人們的身體健康。因此,硝態(tài)氮的有效脫除已經(jīng)成為當前水污染防治領(lǐng)域所面臨的主要技術(shù)瓶頸之一。污染水體中去除硝酸氮的傳統(tǒng)方法主要包括物理、化學、生物及其復合技術(shù)方法等,但這些方法均存在運行成本高,產(chǎn)生二次污染等缺陷。氫自養(yǎng)反硝化技術(shù)被認為是一種經(jīng)濟有效的硝態(tài)氮脫除技術(shù),但傳統(tǒng)的氫自養(yǎng)反硝化反應(yīng)器存在電極與基質(zhì)接觸面較小、過水斷面水流不均勻、陰極利用率低等不足。目前,國內(nèi)外關(guān)于城市污水硝態(tài)氮脫除的研究進展迅速,但尚未發(fā)現(xiàn)專門用于地表水中硝態(tài)氮去除的成熟工藝。因此,識別硝態(tài)氮的來源及其形成過程,并據(jù)此研發(fā)針對地表水硝態(tài)氮去除的工藝對當前水處理領(lǐng)域的技術(shù)進步具有重要意義。本論文以膠東地區(qū)地表水體硝態(tài)氮高、碳氮比低及難以采用常規(guī)技術(shù)手段進行脫氮等水質(zhì)問題為導向,在充分調(diào)研的基礎(chǔ)上設(shè)計并優(yōu)化了升流式三維電極氫自養(yǎng)反硝化反應(yīng)器,實現(xiàn)了地表水硝態(tài)氮的高效去除,論文選題具有重要理論意義和實際應(yīng)用價值,取得的主要研究成果如下:論文通過對入庫流域輸入、土壤地表徑流及大氣沉降等不同來源氮通量與總量的實測核算,同時結(jié)合15N穩(wěn)定同位素示蹤技術(shù),對煙臺門樓水庫硝態(tài)氮的來源進行了準確識別和超標原因解析,同時發(fā)現(xiàn):(1)庫區(qū)水體氮素污染主要為硝態(tài)氮(占總氮比例90%),由于水體中DO值較高(3 mg/L),且碳氮比較低(1),反硝化脫氮作用較弱;(2)庫區(qū)水體總氮來源主要為上游河流輸入(沿岸畜禽養(yǎng)殖等污染排放)和周邊土壤地表徑流面源污染輸入(化肥流失等);(3)門樓水庫雖然對硝態(tài)氮去除有一定的自凈能力,但自凈脫氮率只有20%,因此需要適當?shù)娜斯娀幚�。本研究根�?jù)門樓水庫流域等膠東地區(qū)地表水的水質(zhì)特征,配置硝態(tài)氮濃度適宜的模擬水樣,并在現(xiàn)有氫自養(yǎng)反硝化反應(yīng)器的基礎(chǔ)上對其主要構(gòu)建和參數(shù)進行了改進和優(yōu)化:(1)將傳統(tǒng)的平流式電化學氫自養(yǎng)反硝化反應(yīng)器改為升流式電化學反應(yīng)器(UBER),從而增加其基質(zhì)的利用率;(2)在氫自養(yǎng)反硝化反應(yīng)器中添加碳粒,構(gòu)建三維電極并提高電極與基質(zhì)的接觸面積,提高反應(yīng)效率;(3)設(shè)置兩個串聯(lián)式UBER反應(yīng)器,保障水力停留時間并增加其出水穩(wěn)定性。系列實驗研究發(fā)現(xiàn),當電流強度為10 m A、水力停留時間(HRT)為6 h時,氫自養(yǎng)反硝化反應(yīng)器對硝態(tài)氮的去除率最高(~95%)。經(jīng)優(yōu)化設(shè)計的新型氫自養(yǎng)反硝化反應(yīng)器在較低溫度(15℃)時就可實現(xiàn)較高的脫氮率(~90%),這對北方地區(qū)越冬期間開展高效脫氮工作具有重要的指導意義。然而,研究結(jié)果表明,該體系若在高濃度氨氮存在的條件下,氫自養(yǎng)反硝化反應(yīng)器對硝態(tài)氮的去除效率會明顯下降。為了實現(xiàn)對污染水體中硝態(tài)氮和銨態(tài)氮的同步去除,本研究又對上述氫自養(yǎng)反硝化反應(yīng)器進行了進一步改進,在原UBER反應(yīng)器的底部設(shè)置硝化區(qū),將含有銨態(tài)氮和硝態(tài)氮的模擬廢水先經(jīng)過硝化區(qū)進行硝化后再進行氫自養(yǎng)反硝化,以實現(xiàn)同步硝化反硝化。研究結(jié)果表明:(1)改進的UBER系統(tǒng)能夠?qū)崿F(xiàn)同步硝化反硝化,且脫氮率較高(90%),其中耗氧區(qū)主要以異養(yǎng)反硝化為主,自養(yǎng)硝化區(qū)主要以氫自養(yǎng)反硝化為主;(2)生物膜溶解氧(DO)在異養(yǎng)硝化區(qū)和氫自養(yǎng)反硝化區(qū)的垂向分布分布表明,有氧和缺氧層在生物膜中共存,從而促進了高效脫氮。由于沿海地區(qū)地表水中通常含有一定量的硫酸鹽,而硫酸鹽還原過程可能會抑制硝酸鹽的反硝化作用,因此本研究又對脫氮體系中的硫氮耦合作用進行了深入研究。為了探明硫?qū)渥责B(yǎng)反硝化的影響機制,提高氫自養(yǎng)反硝化的脫氮效率,本研究主要通過調(diào)節(jié)進水S/N來觀察其對氫自養(yǎng)反硝化脫氮的影響。研究結(jié)果表明:(1)在較低的S/N(1:2)下硫酸鹽不會抑制氫自養(yǎng)反硝化反應(yīng)器的脫氮效率,可以實現(xiàn)NO_3~--N與SO_4~2--S的同步脫除,硝態(tài)氮的去除率及硫酸鹽的去除率均可達到80%左右;(2)隨著S/N升高(1:1),硫酸鹽還原產(chǎn)生的硫化物累積會對氫自養(yǎng)反硝化及硫酸鹽還原本身產(chǎn)生抑制作用,其臨界抑制濃度分別為10 mg/L和15 mg/L;(3)在較高的S/N下(2:1),較高的硫化物濃度和較低的pH均對氫自養(yǎng)反硝化產(chǎn)生抑制作用。因此,在對含一定濃度硫酸鹽水體進行脫氮時,S/N也對脫氮效率有顯著影響,較低的S/N有助于實現(xiàn)NO_3~--N與SO_4~(2-)-S的同步脫除。
[Abstract]:In recent years, with the development of industry and agriculture and the rapid growth of population, the content of various nitrogen compounds in the water body increases rapidly. Most of the nitrogen compounds will be converted to relatively stable nitrate nitrogen under suitable environment conditions. Usually, the carbon and nitrogen ratio in the surface water is compared to the direct input of high load nitrogen waste water. The higher concentration of nitrate nitrogen has become the most prominent pollution factor in surface water in some areas, which has seriously affected the resource value of surface water and endangers the health of people. Therefore, the effective removal of nitrate nitrogen has already been effectively removed. It has become one of the main technical bottlenecks in the field of water pollution prevention and control. The traditional methods of removing nitrate in polluted water mainly include physical, chemical, biological and composite techniques, but these methods have high operating costs and two pollution defects. Hydrogen autotrophic denitrification is considered as a kind of economy. The effective nitrate removal technology is effective, but the traditional hydrogen autotrophic denitrification reactor has smaller contact surface between the electrode and substrate, the water flow in the cross section is not uniform, and the utilization rate of the cathode is low. At present, the research progress on the removal of nitrate nitrogen in urban sewage is rapid, but the mature workers who have been used for the removal of nitrate nitrogen in the surface water have not been found yet. Therefore, it is of great significance to identify the source of nitrate nitrogen and its formation process, and to develop the technology for the removal of nitrate nitrogen in the surface water is of great significance to the technological progress in the field of water treatment. This paper is guided by the high nitrate nitrogen, low carbon and nitrogen ratio and the difficulty of nitrogen removal by conventional technology in the surface water of Jiaodong. On the basis of full investigation, the upflow three-dimensional electrode hydrogen autotrophic denitrification reactor was designed and optimized, which realized the efficient removal of nitrate nitrogen in the surface water. The thesis has important theoretical significance and practical application value. The main achievements of this thesis are as follows: the paper through the input of the sink basin, soil surface runoff and atmospheric settlement, etc. According to the measured calculation of nitrogen flux and total amount of different sources, and combined with 15N stable isotope tracing technique, the source of nitrate nitrogen in Yantai Mun Lou reservoir was accurately identified and the reasons for exceeding the standard were analyzed. At the same time, it was found that (1) nitrogen pollution in the water body of the reservoir area was mainly nitrate nitrogen (90% of total nitrogen), because of the higher value of DO (3 mg/L), and the ratio of carbon and nitrogen to the water body. Lower (1), denitrification and nitrogen removal is weak; (2) the main source of total nitrogen in the reservoir area is the input of the upstream river (coastal livestock and poultry breeding and other pollution emission) and the input of surface runoff source pollution in the surrounding soil (chemical fertilizer loss and so on). (3) although the reservoir has a certain self purification ability to remove nitrate nitrogen, the self purification rate of nitrogen removal is only 20%. Therefore, it needs to be suitable. According to the characteristics of the water quality of the surface water in Jiaodong area, such as the valley of the men's reservoir, the present study arranged the suitable simulated water samples with nitric nitrogen concentration, and on the basis of the existing hydrogen autotrophic denitrification reactor, the main construction and parameters were improved and optimized. (1) the conventional advection electrochemical hydrogen autotrophic denitrification reaction was carried out. To increase the utilization rate of the matrix, the stress is changed to the upflow electrochemical reactor (UBER). (2) adding carbon particles to the hydrogen autotrophic denitrification reactor, building a three-dimensional electrode and improving the contact area between the electrode and the matrix, and improving the reaction efficiency. (3) setting up two series UBER reactors to ensure the hydraulic retention time and increase the stability of the effluent. The experimental study found that when the current intensity is 10 m A and the hydraulic retention time (HRT) is 6 h, the hydrogen autotrophic denitrification reactor has the highest removal rate of nitrate nitrogen (~95%). The high denitrification rate (~90%) can be achieved at a lower temperature (15 degrees C) after the optimized design of a new type of hydrogen autotrophic denitrification reactor (15 degrees C), which will carry out high efficiency during the overwintering period in the northern region. The work of denitrification has important guiding significance. However, the results show that the efficiency of the removal of nitrate nitrogen in the autotrophic denitrification reactor of the hydrogen autotrophic denitrification reactor will be obviously reduced under the presence of high concentration ammonia nitrogen. In order to realize the removal of nitrate nitrogen and ammonium nitrogen in the polluted water, the autotrophic denitrification reaction of the above-mentioned hydrogen is also studied. The device was further improved, and the nitrification area was set at the bottom of the original UBER reactor. The simulated wastewater containing ammonium nitrogen and nitrate nitrogen was first nitrification and then nitrification and denitrification was carried out to achieve simultaneous nitrification and denitrification. The results showed that: (1) the improved UBER system can achieve simultaneous nitrification and denitrification and the rate of denitrification is higher. High (90%), mainly heterotrophic denitrification, and autotrophic denitrification mainly in the autotrophic nitrification area; (2) the distribution of dissolved oxygen (DO) in the heterotrophic nitrification and autotrophic denitrification areas shows that oxygen and anoxic layers are stored in the biofilm, thus promoting high efficiency denitrification. It is usually contained in a certain amount of sulphate, and the process of sulfate reduction may inhibit the denitrification of nitrate. Therefore, this study further studies the interaction of sulfur and nitrogen in the denitrification system. In order to explore the mechanism of the effect of sulfur on the autotrophic denitrification of hydrogen, the efficiency of the denitrification of hydrogen autotrophic denitrification is improved. This study is mainly through the regulation of this study. The effect of influent S/N on the denitrification of hydrogen autotrophic denitrification was observed. The results showed that (1) the removal efficiency of the hydrogen autotrophic denitrification reactor was not inhibited under the lower S/N (1:2), and the simultaneous removal of NO_3~--N and SO_4~2--S could be achieved. The removal rate of nitrate nitrogen and the removal rate of sulfate could reach about 80%; (2) with S/N liters High (1:1), sulphate accumulation produced by sulfate reduction could inhibit hydrogen autotrophic denitrification and sulfate reduction by 10 mg/L and 15 mg/L, respectively, (3) under higher S/N (2:1), higher sulphide concentration and lower pH for hydrogen autotrophic denitrification. S/N also has a significant effect on nitrogen removal efficiency when nitrogen removal is carried out in sulfate water. Lower S/N is helpful for simultaneous removal of NO_3~--N and SO_4~ (2-) -S.
【學位授予單位】：中國科學院煙臺海岸帶研究所
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X52

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