催化填料研制及其变速生物滤池处理城市污水性能研究
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摘要
生物滤池是废水处理生物膜法的重要工艺之一，其关键技术是微生物附着生长的填料，核心内容是运行性能。论文围绕研制具有刺激微生物生长及利于微生物附着的生物催化填料，以及以生物催化填料为载体的生产性缺氧变速生物滤池处理城市污水的性能进行了试验研究，得到以下结论：
(1)通过填料烧制正交试验及微生物挂膜对比试验，获得了生物催化填料的生产性最佳配比和烧制工艺，成功地研制出一种新型多孔生物催化填料，与普通陶粒和高炉渣相比，其表面粗糙度高、表面微孔有效孔容大、挂膜时间短且挂膜率高，因此更适合微生物附着和增殖，是一种理想的废水生物处理填料。
(2)对生物膜法微生物附着填料的物理特性评价指标进行了分析，指出填料表面孔结构分布是影响多孔填料表面微生物附着特性最主要的物理参数，提出以表面微孔有效孔容及其相应的微孔均值孔径和表面分数维值组成的指标体系表征填料的物理特性，为评价多孔填料的优劣提供了新思路。
(3)论文首次应用分形理论及分数维概念定量表征了多孔填料表面粗糙度，实现了多孔填料表面粗糙度的描述从定性发展为定量，从表观概述发展为微观分析。论文以本研究中采用的填料为例，计算出了其分数维值分别为：生物催化填料2.70～2.78，普通陶粒2.75，高炉渣2.53。
均值孔径是本论文以统计学理论为基础提出的一个描述多孔填料微孔结构分布的新参数，它有效克服了中值孔径和平均孔径难以突出孔径分布特征以及孔径曲线使用不便的不足。
(4)本研究对生物滤池结构进行改进，在国内外首创变速流动的滤池构造，较大幅度地延长了生物滤池的冲洗周期，在一定程度上减轻了滤池易堵塞的问题。在生产性规模装置上的运行试验表明：只要每2～4周排泥一次，则滤池填料层的冲洗周期为2～4个月。
(5)以生物催化填料为载体的生产性缺氧变速生物滤池在22～28℃条件下50d左右完成启动过程；在17～27℃条件下处理城市污水，水量为485～737m~3／d，滤池HRT为7.7～5.0h(填料层HRT为3.9～2.6h)时，出水COD小于120mg／L，SS小于30mg／L，部分BOD_5略大于30mg／L(概率约为40％)。滤池对P有一定的去除效果，但出水NH_3-N浓度略有升高。滤池运行期间pH值始终保持中性。滤池填料层HRT、填料层厚度、水温等对滤池性能有重要影响。论文推导了填料层有机物的降解动力学模型为：S_出=(S_1-S_n)／П(1+K_(2i)X_it_i)+S_n，并根据试验数据得出相应的K_2值和S_n值。
重庆大学博士学位论文
（6）对缺氧变速生物滤池微生物学特性的研究表明：滤池填料层内微生物主要
以生物膜形式存在，填料层内微生物量与相应的脱氢酶活性有良好的相关性。滤池
中有机物的降解主要遵循厌氧降解途径，厌氧降解过程各类微生物生理类群之间呈
现良好的代谢平衡：硫酸盐还原菌没有对产甲烷菌形成抑制。
本研究为以催化填料缺氧变速生物滤池为主体技术的城市污水处理新工艺的工
程应用提供了依据，具有较大的实用价值。
Biofilter is an important biofilm process for wastewater treatment, its critical technology being media attached with microbe and its core issue performance of biofilter. In addition to a concentrated study of a new microbe-catalyzed media which can not only stimulate microbial growth but also promote biomass attachment, this dissertation carries out a full-scale experiment of performance of anoxic variable rate biofilter with this microbe-catalyzed media in municipal wastewater treatment. The conclusion is as follows:
(1) Through orthogonal sintering experiments of media and contrasting experiments for biomass attachment, the optimal component proportion of the microbe-catalyzed media and the optimal sintering process are obtained by the studies on the productive exploitation. Compared with ceramic granule and blast furnace slag, microbe-catalyzed media has a coarser surface, a bigger available pore volume, a quicker and better biofilm growth, and is ideal for wastewater treatment.
(2) Based on analysis of the indexes evaluating physical properties of microbe attached media used for biofilm process, it is pointed out that the surface micro-pore distribution is the main physical index to describe the physical properties of porous media surface, and the index system composed of available pore volume and corresponding expected value of pore diameter and coarse degree of the media surface is given at the same time. This is a new approach to evaluating porous media.
(3) For the first time surface coarse degree of porous media is defined quantitatively through fractal theory and fractional dimension. As a result, means of studying surface coarse degree of porous media is advanced from qualitative description to quantitative computation, and from apparent summary to deep micro-analysis. The fractional dimension value is calculated of micro-catalyzed media, ceramic granule and blast furnace slag as 2.70~2.78, 2.75 and 2.53 respectively in the study.
Expected value of pore diameter as put forward in this dissertation is a new parameter based on statistics theory, which, unlike the concepts of median pore diameter and mean diameter, can effectively characterize the diameter distribution features without the inconveniences of the pore diameter curve.
(4) Variable rate structure of biofilter is created for the first time, which greatly lessens the bio-filter's need for washing and relieve clogging of biofilter. Results of full-scale device experiments show that: if sludge is discharged once time every 2~4
weeks, washing duration of media layer would be 2-4 months.
(5) It takes about 50d for full-scale anoxic variable rate biofilter with microbe-catalyzed media to finish start-up at 22~28C. When influent flow varies between 485~737m3/d and HRT of biofilter between 7.7~5.0h (HRT of media layer between 3.9~2.6h), effluent COD is below 120 mg/L, SS is below 30 mg/L, and some of effluent BODs is slightly above 30 mg/L (the probability is about 40%) at normal temperature of 17~27C. Influent P is removed to some degree, while effluent NHa-N increases a little. During the operation the pH is kept around 7.0. HRT, depth of media layer and water temperature have great influence on the biofilter performance. The dynamic model of the organic substances degradation in media layer is induced as
follows: S = (S1 - Sn) / n(1 + K2iXiti) + Sn, and according to experiment data involved
K.2 and Sn were given.
(6) Microbes in media layer mostly exist as biofilm, and there is high correlation between the attached biomass and the relevant TTC dehydrogenase activity. The degradation of organic matter mainly accords with anaerobic approach, and the different species of microbes maintain a balanced metabolism. Sulfate reduction bacteria do not suppress methane production bacteria.
The study shows great value of application as it provides support for the utilization of anoxic variable rate biofilter with microbe-catalyzed media in municipal wastewater treatment.
(1)通过填料烧制正交试验及微生物挂膜对比试验，获得了生物催化填料的生产性最佳配比和烧制工艺，成功地研制出一种新型多孔生物催化填料，与普通陶粒和高炉渣相比，其表面粗糙度高、表面微孔有效孔容大、挂膜时间短且挂膜率高，因此更适合微生物附着和增殖，是一种理想的废水生物处理填料。
(2)对生物膜法微生物附着填料的物理特性评价指标进行了分析，指出填料表面孔结构分布是影响多孔填料表面微生物附着特性最主要的物理参数，提出以表面微孔有效孔容及其相应的微孔均值孔径和表面分数维值组成的指标体系表征填料的物理特性，为评价多孔填料的优劣提供了新思路。
(3)论文首次应用分形理论及分数维概念定量表征了多孔填料表面粗糙度，实现了多孔填料表面粗糙度的描述从定性发展为定量，从表观概述发展为微观分析。论文以本研究中采用的填料为例，计算出了其分数维值分别为：生物催化填料2.70～2.78，普通陶粒2.75，高炉渣2.53。
均值孔径是本论文以统计学理论为基础提出的一个描述多孔填料微孔结构分布的新参数，它有效克服了中值孔径和平均孔径难以突出孔径分布特征以及孔径曲线使用不便的不足。
(4)本研究对生物滤池结构进行改进，在国内外首创变速流动的滤池构造，较大幅度地延长了生物滤池的冲洗周期，在一定程度上减轻了滤池易堵塞的问题。在生产性规模装置上的运行试验表明：只要每2～4周排泥一次，则滤池填料层的冲洗周期为2～4个月。
(5)以生物催化填料为载体的生产性缺氧变速生物滤池在22～28℃条件下50d左右完成启动过程；在17～27℃条件下处理城市污水，水量为485～737m~3／d，滤池HRT为7.7～5.0h(填料层HRT为3.9～2.6h)时，出水COD小于120mg／L，SS小于30mg／L，部分BOD_5略大于30mg／L(概率约为40％)。滤池对P有一定的去除效果，但出水NH_3-N浓度略有升高。滤池运行期间pH值始终保持中性。滤池填料层HRT、填料层厚度、水温等对滤池性能有重要影响。论文推导了填料层有机物的降解动力学模型为：S_出=(S_1-S_n)／П(1+K_(2i)X_it_i)+S_n，并根据试验数据得出相应的K_2值和S_n值。
重庆大学博士学位论文
（6）对缺氧变速生物滤池微生物学特性的研究表明：滤池填料层内微生物主要
以生物膜形式存在，填料层内微生物量与相应的脱氢酶活性有良好的相关性。滤池
中有机物的降解主要遵循厌氧降解途径，厌氧降解过程各类微生物生理类群之间呈
现良好的代谢平衡：硫酸盐还原菌没有对产甲烷菌形成抑制。
本研究为以催化填料缺氧变速生物滤池为主体技术的城市污水处理新工艺的工
程应用提供了依据，具有较大的实用价值。
Biofilter is an important biofilm process for wastewater treatment, its critical technology being media attached with microbe and its core issue performance of biofilter. In addition to a concentrated study of a new microbe-catalyzed media which can not only stimulate microbial growth but also promote biomass attachment, this dissertation carries out a full-scale experiment of performance of anoxic variable rate biofilter with this microbe-catalyzed media in municipal wastewater treatment. The conclusion is as follows:
(1) Through orthogonal sintering experiments of media and contrasting experiments for biomass attachment, the optimal component proportion of the microbe-catalyzed media and the optimal sintering process are obtained by the studies on the productive exploitation. Compared with ceramic granule and blast furnace slag, microbe-catalyzed media has a coarser surface, a bigger available pore volume, a quicker and better biofilm growth, and is ideal for wastewater treatment.
(2) Based on analysis of the indexes evaluating physical properties of microbe attached media used for biofilm process, it is pointed out that the surface micro-pore distribution is the main physical index to describe the physical properties of porous media surface, and the index system composed of available pore volume and corresponding expected value of pore diameter and coarse degree of the media surface is given at the same time. This is a new approach to evaluating porous media.
(3) For the first time surface coarse degree of porous media is defined quantitatively through fractal theory and fractional dimension. As a result, means of studying surface coarse degree of porous media is advanced from qualitative description to quantitative computation, and from apparent summary to deep micro-analysis. The fractional dimension value is calculated of micro-catalyzed media, ceramic granule and blast furnace slag as 2.70~2.78, 2.75 and 2.53 respectively in the study.
Expected value of pore diameter as put forward in this dissertation is a new parameter based on statistics theory, which, unlike the concepts of median pore diameter and mean diameter, can effectively characterize the diameter distribution features without the inconveniences of the pore diameter curve.
(4) Variable rate structure of biofilter is created for the first time, which greatly lessens the bio-filter's need for washing and relieve clogging of biofilter. Results of full-scale device experiments show that: if sludge is discharged once time every 2~4
weeks, washing duration of media layer would be 2-4 months.
(5) It takes about 50d for full-scale anoxic variable rate biofilter with microbe-catalyzed media to finish start-up at 22~28C. When influent flow varies between 485~737m3/d and HRT of biofilter between 7.7~5.0h (HRT of media layer between 3.9~2.6h), effluent COD is below 120 mg/L, SS is below 30 mg/L, and some of effluent BODs is slightly above 30 mg/L (the probability is about 40%) at normal temperature of 17~27C. Influent P is removed to some degree, while effluent NHa-N increases a little. During the operation the pH is kept around 7.0. HRT, depth of media layer and water temperature have great influence on the biofilter performance. The dynamic model of the organic substances degradation in media layer is induced as
follows: S = (S1 - Sn) / n(1 + K2iXiti) + Sn, and according to experiment data involved
K.2 and Sn were given.
(6) Microbes in media layer mostly exist as biofilm, and there is high correlation between the attached biomass and the relevant TTC dehydrogenase activity. The degradation of organic matter mainly accords with anaerobic approach, and the different species of microbes maintain a balanced metabolism. Sulfate reduction bacteria do not suppress methane production bacteria.
The study shows great value of application as it provides support for the utilization of anoxic variable rate biofilter with microbe-catalyzed media in municipal wastewater treatment.
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