硫酸盐型厌氧氨氧化的启动特性与影响因素研究
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摘要
随着工业的不断发展,在化工、食品、制药、制革、造纸等领域的生产过程中排放出大量含高浓度硫酸根( SO_4~(2-))和氨氮(NH_4~+-N)的废水,对环境和人们的生命财产安全造成危害。这些废水处理难度大,传统的生物除硫和生物脱氮工艺遇到了很多问题。目前人们对同歩除硫脱氮的研究主要有无机条件下硫自养反硝化和有机条件下的S、N、C同步去除。硫酸盐型厌氧氨氧化是在传统厌氧氨氧化基础上发现的新的同步除硫脱氮途径,硫酸盐型厌氧氨氧化的发现为低C/N比、高SO_4~(2-)的可生化性差废水的处理开辟了新道路。
本试验以原有的硫自养反硝化反应器为基础、硫自养反硝化污泥为菌源,历时95天成功启动厌氧氨氧化反应。NH_4~+-N去除量:NO_2~--N去除量为1:1.33,NH_4~+-N和NO_2~--N去除率均达99.9%,反应器总氮容积负荷为0.165kg·(m3·d)-1。反应器内的污泥主要为灰白色、褐色颗粒污泥,颗粒污泥局部呈红色。在厌氧氨氧化活性稳定期,反应器内可能存在自养反硝化反应,反应器出水NO3--N浓度逐渐降低。进水、出水pH值基本保持一致,没有理论上的出水pH值上升现象。
成功启动厌氧氨氧化后,通过提高厌氧氨氧化的基质浓度,以提高反应器内生物量;然后逐步用SO_4~(2-)代替NO_2~-使SO_4~(2-)成为厌氧氨氧化的电子受体,历时158d硫酸盐型厌氧氨氧化成功启动。NH_4~+-N与SO_4~(2-)的去除量分别为76.2 mg·L~(-1)和68mg·L~(-1)。在传统厌氧氨氧化运行效果良好的缺氧条件下,硫酸盐型厌氧氨氧化启动的效果不理想,这与硫酸盐型厌氧氨氧化的标准吉布斯自由能变化小有关。硫酸盐型厌氧氨氧化反应器中存在硫自养反硝化与厌氧氨氧化协同作用,反应器出水中有NO_2~-积累,pH值出水低于进水。
本实验是利用厌氧氨氧化进行同步脱氮除硫,因此选取了几个影响厌氧氨氧化菌活性的营养因素和环境因素,研究这些因素对脱氮除硫效率的影响。研究发现:(1)硫酸盐型厌氧氨氧化的顺利进行易受NO_2~-的影响,NO_2~-的投加使NH_4~+-N和NO_2~- -N的去除效率迅速达到100%,NO_2~-会对硫酸盐型厌氧氨氧化产生竞争性抑制,使SO_4~(2-)的去除效率降低;(2)Fe~(3+)促进了NH_4~+-N的去除,且会使反应器氧化还原电位升高,氧化还原电位升高导致硫酸盐型厌氧氨氧化受到抑制;(3)有机物对厌氧氨氧化有抑制作用,使NH_4~+-N的去除效率降低,高浓度有机条件下,异养型硫酸盐还原菌导致了SO_4~(2-)的去除。
With the development of industry, factories of chemical, food, pharmaceutical, leather paper and other fields discharge lots of wastewater with high concentration of SO_4~(2-) and NH_4~+. The safty of environment and human were threatened by the wastewater. Traditional treatment methods of wastewater were incompetent on this kind of pollution. There are many researches on the autotrophic denitrification and the simultaneously remove of S, N, C. Anammox is one of the most efficient pathways to remove NH_4~+. Anammox with sulfate as electron acceptor is a new pathway which can remove SO_4~(2-) and NH_4~+at the same time. The discovery of this pathway open a new way for the treatment of wastewater with high concentration of SO_4~(2-) and NH_4~+.
A special reactor was used in this experiment. The reactor was running autotrophic denitrification previously. The sludge in this reactor was used as bacteria source to enrich anammox bacteria. Anammox process was started up successfully after 95d. The removal ratios of NH_4~+-N and NO_2~--N was more than 99.9%. The volume load of the reactor was 0.165 kg·(m3·d)-1. The colors of most of sludge were gray, black and red. In the stable period of anammox process, the concentration of NO3--N delined, maybe denitrification process occurred at the same time. The pH value of influent was consistent with the effluent`s, which was different from the anammox theory.
In order to enrich as much as bacteria, high concentration of nutrition was supplied. Then, NO_2~--N was replaced by SO_4~(2-) gradually to setup a new anammox pathway, and SO_4~(2-) finally became the electron acceptor of anammox process after 158d. The removal of NH_4~+-N and SO_4~(2-) were76.2 mg·L~(-1) and 68mg·L~(-1)respectively. Under this condition where traditional anammox process worked well, anammox with sulfate as electron acceptor performed badly. Maybe this can be attributed to the small standard Gibbs free energy change. Denitrification process occurred at the same time. The NO_2~- was detected in effluent, and the pH value of effluent was bigger than the influent`s.
In order to improve the performance of the new anammox with sulfate as electron acceptor, some factors related to anammox bacteria were choes to explor their influence on the new pathway. The removal of SO_4~(2-)was disturbed by NO_2~- largely; however the removal of NH_4~+-N was enhanced, so did the influence of Fe~(3+). High concentration organic inhibited the anammox process and the removal of NH_4~+-N declined; however the removal of SO_4~(2-) was enhanced.
本试验以原有的硫自养反硝化反应器为基础、硫自养反硝化污泥为菌源,历时95天成功启动厌氧氨氧化反应。NH_4~+-N去除量:NO_2~--N去除量为1:1.33,NH_4~+-N和NO_2~--N去除率均达99.9%,反应器总氮容积负荷为0.165kg·(m3·d)-1。反应器内的污泥主要为灰白色、褐色颗粒污泥,颗粒污泥局部呈红色。在厌氧氨氧化活性稳定期,反应器内可能存在自养反硝化反应,反应器出水NO3--N浓度逐渐降低。进水、出水pH值基本保持一致,没有理论上的出水pH值上升现象。
成功启动厌氧氨氧化后,通过提高厌氧氨氧化的基质浓度,以提高反应器内生物量;然后逐步用SO_4~(2-)代替NO_2~-使SO_4~(2-)成为厌氧氨氧化的电子受体,历时158d硫酸盐型厌氧氨氧化成功启动。NH_4~+-N与SO_4~(2-)的去除量分别为76.2 mg·L~(-1)和68mg·L~(-1)。在传统厌氧氨氧化运行效果良好的缺氧条件下,硫酸盐型厌氧氨氧化启动的效果不理想,这与硫酸盐型厌氧氨氧化的标准吉布斯自由能变化小有关。硫酸盐型厌氧氨氧化反应器中存在硫自养反硝化与厌氧氨氧化协同作用,反应器出水中有NO_2~-积累,pH值出水低于进水。
本实验是利用厌氧氨氧化进行同步脱氮除硫,因此选取了几个影响厌氧氨氧化菌活性的营养因素和环境因素,研究这些因素对脱氮除硫效率的影响。研究发现:(1)硫酸盐型厌氧氨氧化的顺利进行易受NO_2~-的影响,NO_2~-的投加使NH_4~+-N和NO_2~- -N的去除效率迅速达到100%,NO_2~-会对硫酸盐型厌氧氨氧化产生竞争性抑制,使SO_4~(2-)的去除效率降低;(2)Fe~(3+)促进了NH_4~+-N的去除,且会使反应器氧化还原电位升高,氧化还原电位升高导致硫酸盐型厌氧氨氧化受到抑制;(3)有机物对厌氧氨氧化有抑制作用,使NH_4~+-N的去除效率降低,高浓度有机条件下,异养型硫酸盐还原菌导致了SO_4~(2-)的去除。
With the development of industry, factories of chemical, food, pharmaceutical, leather paper and other fields discharge lots of wastewater with high concentration of SO_4~(2-) and NH_4~+. The safty of environment and human were threatened by the wastewater. Traditional treatment methods of wastewater were incompetent on this kind of pollution. There are many researches on the autotrophic denitrification and the simultaneously remove of S, N, C. Anammox is one of the most efficient pathways to remove NH_4~+. Anammox with sulfate as electron acceptor is a new pathway which can remove SO_4~(2-) and NH_4~+at the same time. The discovery of this pathway open a new way for the treatment of wastewater with high concentration of SO_4~(2-) and NH_4~+.
A special reactor was used in this experiment. The reactor was running autotrophic denitrification previously. The sludge in this reactor was used as bacteria source to enrich anammox bacteria. Anammox process was started up successfully after 95d. The removal ratios of NH_4~+-N and NO_2~--N was more than 99.9%. The volume load of the reactor was 0.165 kg·(m3·d)-1. The colors of most of sludge were gray, black and red. In the stable period of anammox process, the concentration of NO3--N delined, maybe denitrification process occurred at the same time. The pH value of influent was consistent with the effluent`s, which was different from the anammox theory.
In order to enrich as much as bacteria, high concentration of nutrition was supplied. Then, NO_2~--N was replaced by SO_4~(2-) gradually to setup a new anammox pathway, and SO_4~(2-) finally became the electron acceptor of anammox process after 158d. The removal of NH_4~+-N and SO_4~(2-) were76.2 mg·L~(-1) and 68mg·L~(-1)respectively. Under this condition where traditional anammox process worked well, anammox with sulfate as electron acceptor performed badly. Maybe this can be attributed to the small standard Gibbs free energy change. Denitrification process occurred at the same time. The NO_2~- was detected in effluent, and the pH value of effluent was bigger than the influent`s.
In order to improve the performance of the new anammox with sulfate as electron acceptor, some factors related to anammox bacteria were choes to explor their influence on the new pathway. The removal of SO_4~(2-)was disturbed by NO_2~- largely; however the removal of NH_4~+-N was enhanced, so did the influence of Fe~(3+). High concentration organic inhibited the anammox process and the removal of NH_4~+-N declined; however the removal of SO_4~(2-) was enhanced.
引文
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