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沼气循环厌氧膜生物反应器处理高盐废水的可行性研究

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I 摘要 随着我国工业化进程的加快,越来越多的工业生产领域将产生高盐废水,如何有 效地处理此类废水是一个难题,探究能耐受更高盐度的生物处理法是现在国内外研究 的重点。 高盐废水中最常见的是高氯盐废水和高硫酸盐废水,其主要的来源渠道为,海水 利用、印染、造纸、制药、海产品加工、奶制品加工、化工和农药等,在这些废水中, 其 Cl - 以及 SO 4 2- 的浓度可高达 9000mg/L。本课题采用自行研发的沼气循环厌氧膜生 物反应器(MCAnMBR)对这两类废水进行中试试验。试验前期先探索本反应器处理 高氯盐废水和高硫酸盐废水的可行性,随后探究本反应器对两类高盐废水的耐受值和 相应的工艺运行参数,并对稳定运行阶段的污泥粒径、微生物形态、厌氧产气量以及 厌氧产气组分进行测定。整个试验期间,通过记录跨膜压差了解膜污染过程。 MCAnMBR 处理高氯盐废水具有可行性,在温度为 22.6℃~26.5℃,进水 COD 浓 度 为 24650~34720mg/L , 进 水 NaCl 浓 度 为 16.72g/L , 容 积 负 荷 为 4.9~6.9kgCOD/(m 3 d),HRT 为 120h,MLSS 为 25g/L 时,未对反应器产生明显的抑 制作用,其出水 COD 浓度低于 2000mg/L,COD 总去除率达 94.25%~99.61%,反应 器内 VFA 小于 100mg/L。 MCAnMBR 经驯化可处理进水 NaCl 浓度为 19~20g/L 的高氯盐废水,反应器稳 定运行的工艺参数为,温度 20℃~26℃,进水 COD 浓度为 21648.9mg/L~23764.8mg/L, 进水 NaCl 浓度 19~20g/L,HRT 为 120h,有机负荷 4.5 kgCOD/(m 3 d),MLSS 为 27g/L。 反应器稳定运行阶段,系统对 COD 去除效果较好,COD 总去除率在 84.58%~90.44% 之 间 , 反 应 器 内 pH 为 7.61~7.85 , 碱 度 为 1251mg/L~1511mg/L , VFA 为 260.68mg/L~410.57mg/L,MLVSS/MLSS 为 0.6572。 MCAnMBR 处 理高 硫 酸盐 废 水 具有 可 行性 , 可处 理 进水 COD 浓 度 为 18000~21000mg/L、SO 4 2- 浓度为 9082~9600mg/L、COD/SO 4 2- 为 2 的高 Na 2 SO 4 废水。 反应器稳定运行的工艺参数为,温度为 23.3℃~25.4℃,HRT 为 120h,MLSS 为 17.24g/L,有机负荷为 3.68~4.36kgCOD/(m 3 d),反应器运行效果良好,出水 COD 浓 度为 650.83~976.56mg/L,COD 总去除率达 95.36%~97.9%,SO 4 2- 还原率为 49.76%, 反应器内VFA为300.181~706.63mg/L,碱度为2172.17~3379.21mg/L,pH为7.18~7.61, MLVSS/MLSS 为 0.6429。 在高氯盐的环境中,污泥粒径分布在 6~76μm 之间,在高硫酸盐的环境中,污泥 粒径在 4~34μm 之间。MCAnMBR 在处理高氯化钠模拟废水时,微生物絮体较为紧实, 周边可见大量杆状菌种,游离的球状菌种较少,而在处理高硫酸钠模拟废水时,微生苏州科技大学硕士学位报告 摘要 II 物絮体松散,以球状菌种为主,未见杆状菌种。总的来说,沼气循环+水利搅拌使反 应器内污泥更分散,传质速率更快,比其它类型的反应器相比具有一定的优势。 对跨膜压差进行检测,发现 MCAnMBR 比其它类型的 AnMBR 能连续运行更长 的时间,整个膜污染过程符合三阶段理论,第一阶段为跨膜压差的短期快速增长,第 二阶段为长期缓慢、稳定增长,第三阶段为短期急速增长。在整个试验过程中,膜贡 献率在 0~30%之间,平均为 5.9%,有效地强化了 MCAnMBR 的去除效能,使出水水 质更加稳定,膜分离率在 0~93%之间,平均为 35.41%,温度的变化可提高膜对污染 物的分离率,在 28℃时,能达到 90%的膜分离率。 关键词,沼气循环厌氧膜生物反应器;高氯盐废水;高硫酸盐废水;跨膜压差苏州科技大学硕士学位报告 Abstract i Abstract Nowadays, many production fields produce high salt organic wastewater with the development of industrialization in China. However, it’s very difficult to solve the problem about how to treat the high salt organic wastewater. Therefore, domestic and international experts in this field are devoting to explore the biological method which is high salinity tolerated. There are two kind of the most common wastewater of high salt wastewater: the high chlorine salt wastewater and the high sulfate wastewater, which are mainly from seawater desalination, printing and dyeing, paper making, pharmacy, seafood, dairy products processing, chemical, pesticide and so on. In this topic, the Methane Cycle Anaerobic Membrane Bioreactor(MCAnMBR)researched by ourselves is used to do the pilot-scale experiment on these two kinds of wastewater which contain a concentration of Cl - and SO 4 2- as high as 9000mg/L. Before the experiment, we will probe the feasibility of using the MCAnMBR to treat the wastewater, after that, tolerance values and process operation parameters of MCAnMBR will be explored. Meanwhile, the sludge particle size, microbial morphology, particle size of anaerobic gas production and anaerobic gas composition will be measured at the stage of stable operation. We realize the membrane fouling process through record the differential pressure across the membrane during the whole experiment. Using MCAnMBR to treat these two kind of wastewater is viable. There is no obviously inhibitory effect for the reactor, When the temperature between 22.6℃ and 26.5 ℃ , the influent concentration of COD between 24650mg/L and 34720mg/L, the influent concentration of NaCl reaches 16.72g/L, the volume loading from 4.9kgCOD/(m 3 d) to 6.9kgCOD/(m 3 d), the HRT up to 120h and the MLSS resches 25g/L. In the meantime, when the influent concentration of COD less than 2000mg/L and the total removal rate of COD between 94.25% and 99.61%, the VFA in the reactor will less than 100mg/L. The high chlorine salt influent contains a concentration of NaCl from 19g/L to 20g/L can be treated by the domestic MCAnMBR; The effects of stable operation process of the reactor are: temperature, from 20℃ to 26℃. The influent concentration of COD, between 1648.9mg/L and 23764.8mg/L; The influent concentration of NaCl, from 19g/L to 20g/L; The HRT, up to 20h; The organic loading rate(OLR), reaches 4.5 kgCOD/(m 3 d) and the MLSS, resches 27g/L. The removal effects of COD by MCAnMBR is excellent when the苏州科技大学硕士学位报告 Abstract ii reactor in a stable operation environment. In this environment, the total removal rate of COD between 84.58% and 90.44%, the pH of the reactor from 7.61 to 7.85, the alkalinity between 1251mg/L and 1511mg/L, the VFA from 260.68mg/L to 410.57mg/L and MLVSS/MLSS is 0.6572. Using MCAnMBR to treat the high sulfate wastewater is doable. The high Na 2 SO 4 inflow can be treated when it’s concentration meet the following criteria: The concentration of COD between 18000mg/L and 21000mg/L; The concentration of SO 4 2- from 9082mg/L and 9600mg/L and the COD/SO 4 2- meet 2. The effects of stable operation process of the reactor are: Temperature, from 23.3℃ to 25.4℃; The HRT, up to 120h; The MLSS, reaches 17.24g/L; The OLR, between 3.68kgCOD/(m 3 d) and 4.36kgCOD/(m 3 d);The operation result of the reactor is good; The effluent concentration of COD, between 650.83mg/L and 976.56mg/L; The total removal rate of COD meet 95.36%~97.9%; The reduction percentage of SO 4 2- up to 49.76%; The VFA in the reactor, from 300.181mg/L to 706.63mg/L; The alkalinity, between 2172.17mg/L and 3379.21mg/L, The pH from 7.18 to 7.61 and MLVSS/MLSS is 0.6429. In an environment of high chlorine salt, the diameter of the sludge is between 6 and 76 microns and in an environment of high sulfate, the diameter of the sludge is between 4 and 34 microns. When the high sodium chloride simulated wastewater treated by MCAnMBR, the microbial flocs surrounded by a large number of bacillus and less free micrococcus will be relatively tight. On the contrary, when the high sodium sulfate simulated wastewater treated by MCAnMBR, the microbial flocs mainly surrounded by micrococcus and no bacillus will be relatively loose. In general, the reactor combine methane cycle and water stir together, will has more advantages than other reactors, the sludge in it will be looser and transmit more quickly. The detection of transmembrane pressure(TPM) improves that MCAnMBR can run longer time than other kind AnMBR. The whole membrane fouling process can be divided into three phases. First, the rapid growth of the TPM in the short term. Second, slow and steady growth for the long term. Lastly, rapid growth for the short term. During the whole experiment, the membrane contribution is between 0% and 30%, the average percentage is 5.9%, this phenomenon can improve the sewage treatment capacity of MCAnMBR effectively and can improve the stability of the effluent quality.The membrane separation rate is between 0% and 93%, the average percentage is 35.41%. Temperature rise is helpful for membrane separation of pollutants, when the temperature up to 28℃, the membrane separation rate will reaches 90%.苏州科技大学硕士学位报告 Abstract iii Keywords: Methane gas circulation anaerobic membrane bioreactor; High chlorine salt waste water; The high sulfate wastewater; Transmembrane pressure苏州科技大学硕士学位报告 目录 目录 摘要...............................................................................................................................................................I Abstract..........................................................................................................................................................i 目录...............................................................................................................................................................i 第一章 绪论................................................................................................................................................3 1.1 选题背景........................................................................................................................................3 1.2 厌氧膜生物反应器.......................................................................................................................4 1.2.1 厌氧膜生物反应器的发展简史........................................................................................4 1.2.2 厌氧膜生物反应器的在废水处理中的应用....................................................................5 1.3 高浓度氯化钠废水抑制机理讨论及相关研究动态...................................................................5 1.4 高浓度硫酸钠废水抑制机理讨论及相关研究动态...................................................................9 1.4.1 菌种竞争抑制机理.............................................................................................................9 1.4.2 H 2 S 抑制机理讨论及相关研究动态............................................................................... 11 1.5 膜污染.........................................................................................................................................13 1.6 课题的研究目的和主要研究内容.............................................................................................15 1.6.1 研究目的...........................................................................................................................15 1.6.2 主要研究内容..................................................................................................................15 第二章 试验装置及方法..........................................................................................................................17 2.1 试验装置.....................................................................................................................................17 2.2 试验用水.....................................................................................................................................20 2.3 监测项目及方法.........................................................................................................................21 2.4 计算方法.....................................................................................................................................21 第三章 MCAnMBR 处理高 NaCl 模拟废水的研究..............................................................................22 3.1 MCAnMBR 的启动概况.............................................................................................................22 3.2 MCAnMBR 对高浓度氯离子的耐受试验.................................................................................22 3.2.1 快速提高进水 NaCl 浓度阶段(试验温度,22.6℃~26.5℃)....................................22 3.2.2 排泥点与抑制点(试验温度,18.1℃~22.6℃)..........................................................24 3.2.3 耐盐值探究阶段(试验温度,14.9℃~18.1℃)..........................................................25 3.2.4 VFA、碱度以及碱度/VFA..............................................................................................26 3.2.5 MLSS、MLVSS/MLSS 以及污泥平均产率的变化...................................................... 27 3.2.6 产甲烷丰度与 COD 总去除率以及温度的关系............................................................28 3.3 高浓度氯离子环境下的启动以及有机冲击负荷耐受试验.................................................... 29 3.3.1 COD 去除效果的变化..................................................................................................... 29 3.3.2 VFA、碱度、pH 以及碱度/VFA 的变化.......................................................................31 3.3.3 气体产量和气体产率的变化..........................................................................................32 3.3.4 MLSS、MLVSS/MLSS 以及平均污泥浓度的变化...................................................... 33 3.4 本章小结.....................................................................................................................................34 第四章 MCAnMBR 处理高 Na 2 SO 4 模拟废水的研究.........................................................................35 4.1 试验装置的改进.........................................................................................................................35 4.2 反应器调试阶段..........................................................................................................................35 4.3 污泥接种与驯化.........................................................................................................................38 4.4 反应器处理高硫酸盐废水阶段.................................................................................................39 1苏州科技大学硕士学位报告 目录 4.4.1 硫酸根浓度对 COD 去除效果的影响...........................................................................39 4.4.2 硫酸根浓度对 VFA、碱度以及 pH 的影响...................................................................41 4.4.3 硫酸盐浓度对 SO 4 2- 去除效果的影响.............................................................................42 4.4.4 COD/SO 4 2- 对 COD 去除率及 SO 4 2- 还原率的影响........................................................44 4.4.5 菌种竞争抑制机理讨论...................................................................................................45 4.4.6 H 2 S 抑制机理....................................................................................................................47 4.4.7 反应器内污泥的变化.......................................................................................................47 4.5 本章小结......................................................................................................................................48 第五章 MCAnMBR 的污泥特性...........................................................................................................50 5.1 污泥粒径.....................................................................................................................................50 5.2 微生物形态.................................................................................................................................53 第六章 膜组件的贡献分析以及通量变化..............................................................................................55 6.1 膜组件贡献分析.........................................................................................................................55 6.2 跨膜压差变化以及膜污染进程分析.........................................................................................56 6.3 本章小结.....................................................................................................................................59 第七章 结论和建议..................................................................................................................................61 7.1 结论.............................................................................................................................................61 7.2 建议.............................................................................................................................................62