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硫铁矿自养反硝化耦合厌氧氨氧化脱氮工艺与机制研究

Study on nitrogen removal process and mechanism by iron sulfide autotrophic denitrification coupled with Anammox

作者:王艳菲
  • 学号
    2017******
  • 学位
    博士
  • 电子邮箱
    wan******com
  • 答辩日期
    2022.12.06
  • 导师
    管运涛
  • 学科名
    环境科学与工程
  • 页码
    171
  • 保密级别
    公开
  • 培养单位
    005 环境学院
  • 中文关键词
    硫铁矿,耦合作用,厌氧氨氧化,有机碳,自养反硝化
  • 英文关键词
    Iron sulfide, Coupling interaction, Anammox, Organic carbon, Autotrophic denitrification

摘要

硫铁矿可作为经济有效的自养反硝化工艺电子供体用于去除污水中的硝酸盐,适用于低C/N污水处理且无需额外添加有机碳源。而对于实际污水中的氨氮,厌氧氨氧化(Anammox)工艺的发展使微氧或厌氧条件下氨氧化结合自养反硝化实现NH4+/NO3?同步去除具有可行性。本研究采用单硫铁矿(FeS)和黄铁矿(FeS2)作为电子供体构建硫铁矿自养反硝化耦合厌氧氨氧化同步脱氮反应系统实现NH4+/NO3?高效协同去除,探究其同步脱氮作用机制。 单硫铁矿自养反硝化耦合厌氧氨氧化同步脱氮反应器(Rfa)长期运行(298天)实现了NH4+/NO3?的同步高效去除。随着FeS投加浓度的增大,出水水质波动较大且NO2?积累明显。进而采用电子缓释材料黄铁矿作为反硝化电子供体,搭建了黄铁矿自养反硝化耦合厌氧氨氧化同步脱氮反应器(Rpa,265天),当水力停留时间为6 h时,长期稳定运行下NH4+和NO3?的平均去除率均达到90%以上,去除负荷分别为52.8和59.4 mg N/(L?d)。同时,NH4+去除集中在反应器底部且主要通过硫酸盐还原厌氧氨氧化(Sulfammox, 37%~60%)、三价铁还原厌氧氨氧化(Feammox, 26%~45%)、Anammox(6%~28%)、硝化作用(4%~8%)去除,而NO3?主要在反应器中上部通过自养反硝化去除。 针对实际污水中含有有机物的情景,通过添加有机碳源搭建了黄铁矿混养反硝化耦合厌氧氨氧化同步脱氮反应器(Rpm,190天)以探究有机碳源的影响。长期运行下系统NH4+、NO3?、COD的平均去除率可以达到81%、99%、83%。在混合进水模式(含NH4+与NO3?)下,有机碳源的存在促使进水中NO3?通过短程异养反硝化产生NO2?从而有助于进水中NH4+通过Anammox作用去除,提高反硝化速率的同时能够进一步降低出水SO42?和总Fe浓度,减少水环境生态风险。 深入解析微生物群落结构演替变化与互作关系,不同脱氮功能菌属在氮、硫、碳代谢中协同互作实现NH4+/NO3?的同步高效去除。底物浓度和进水模式变化是不同阶段微生物种群分布呈现明显差异的原因。通过宏基因分析不同反应系统内氮、硫、碳代谢通路,发现反应器底部相关功能菌属(Nitrospira、Nitrosomonas、Ca. Brocadia、Ca. Kuenenia)携带硝化、Anammox、硫酸盐还原过程的关键功能基因而具有氨氧化作用潜能,而Thiobacillus、Rhodanobacter、Azospira等功能菌属携带反硝化的关键基因,其分布在反应器不同高度,具有反硝化与硫氧化的代谢潜能。

Iron sulfide, an economical and effective electron donor, is suitable for the autotrophic denitrification process to remove nitrate in wastewater, especially for low C/N wastewater. For ammonia and nitrate pollutants in sewage, it’s feasible to simultaneous removal of NH4+/NO3? by combining autotrophic denitrification and Anammox (AutoDemmox) under microaerobic or anaerobic conditions. In this study, ferrous sulfide (FeS) and natural pyrite were used as the electron donor to construct iron sulfide reactors (Rfa and Rpa, respectively) for synergistic NH4+/NO3? removal. The effect of organic carbon on the removal of NH4+/NO3? in the pyrite simultaneous AutoDemmox system was further studied.In the FeS autotrophic denitrification and Anammox system (Rfa), the synergetic and efficient NH4+/NO3? removal was realized in the long-term operation (over 298 days). With the FeS dosage increased, the effluent quality fluctuated greatly, and more NO2? was accumulated. Therefore, natural pyrite, an alternative slow-releasing material, was then used in the pyrite autotrophic denitrification and Anammox biofilter reaction system (Rpa, over 265 days). The efficient removal of NH4+/NO3? was achieved during the long-term operation, and when HRT was 6 h, the average removal percentages of NH4+ and NO3? both were above 90%, and the removal loading rates were 52.8 and 59.4 mg N/(L?d), respectively. For dynamics of pollutant parameters along the up-flow direction of the reactor and the microbial activity, Sulfammox (37%~60%), Feammox (26%~45%), Anammox (6%~28%) and nitrification (4%~8%) were the main processes responsible for ammonia removal, while autotrophic denitrification along the middle-upper part of the reactor was the main reason for NO3? removal.Furthermore, the effect of organic carbon on the pyrite mixtrophic denitrification and Anammox system (Rpm, over 190 days) performance was investigated for efficient synchronous NH4+, NO3? , COD removal rates of 81%、99%、83% in a long-term operation period. It was founed that, with the mixed influent mode (inluding NH4+, NO3?), the addition of organic carbon promoted the simultaneous removal of NH4+/NO3?. The NO2? generated by partial denitrification of NO3? in influent enhanced the removal of NH4+ in influent by Anammox, thereby improving the denitrifying rate, and reducing the concentration of SO42? and Total-Fe in effluent with less ecological risk for water environment.Finaly, the succession of microbial community structure and microbial interactions were analyzed to provide theoretical guidance for system operation. By 16S rRNA, it was found that the variation of substrate concentration and influent pattern caused significant differences in the microbial community distribution in each system. Metagenomic approach was also used to analyze the nitrogen, sulfur, carbon metabolic pathways. It showed that the functional bacteria (Nitrospira, Nitrosomonas, Candidutus Brocadia and Candidatus Kuenenia) at the bottom of the reactor carried key functional genes of nitrification, Anammox and sulfate reduction, and had the potential for nitrification, Anammox, Sulfammox/Feammox, and the key functional genes of complete denitrification and sulfur oxidation were carried by Thiobacillus, Rhodanobacter, Azospira, etc., which were distributed at different sections of the reactor. The simultaneous and efficient removal of NH4+/NO3? was realized by different functional microorganisms through different nitrogen, sulfur, carbon metabolism pathways.