水解酸化—两级厌氧工艺处理甲醇废水的试验研究
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摘要
随着厌氧工艺的处理效果不断提高、运行稳定性增加、抗冲击负荷能力增强、控制方式更趋于自动化,其适用范围也不断扩大,尤其是在高浓度有机废水处理领域的优势越来越明显。但与此同时,现有厌氧工艺存在的一些弊端也逐渐显露出来,如在处理水质变化剧烈的高浓度有机废水时,单相厌氧反应器易出现“酸化”现象,进而降低反应器的处理效能,甚至导致系统出现运行异常。本课题以自主研发的外循环厌氧反应器为处理单体;以两相厌氧原理和SMPA理论为基础,研发水解酸化-两级厌氧工艺,对其处理效能和运行稳定性进行深入研究;对影响工艺运行的生态因子进行探讨,并通过控制主要生态因子来实现反应器运行的优化;以实验室研究结果为指导,建立处理高浓度甲醇废水的中试工程,在实践中不断优化设计和运行参数,为该类废水的处理提供良好的技术支持。
实验室研究阶段,采用在水解酸化反应器中接种厌氧颗粒污泥和控制启动容积负荷、负荷提高幅度、pH值等生态因子,对反应器乙醇型发酵的形成情况进行考察,结果表明反应器在34d内完成快速启动,并形成稳定的乙醇型发酵。乙醇+乙酸质量浓度之和占液相末端产物总量的75.9%以上。
在两级厌氧反应器中接种厌氧颗粒污泥,并对其处理效能进行研究。试验结果表明,1#反应器在VLR=46.78kgCOD/m3·d、HRT=5.62h条件下,COD去除率达到93.2%;2#反应器COD去除率达到85.2%,两级厌氧反应器总去除率高达98.9%。同时,两级厌氧反应器表现出了良好的VFA去除能力,出水VFA保持在10mg/L以下。
试验对水解酸化反应器内所接中的厌氧颗粒污泥的物理特性及微生物群落组成的变化情况进行研究。同时,对酸化颗粒污泥的形成途径进行初步阐述。试验结果证明通过控制启动容积负荷及其提高方式和较低的pH值条件可实现由厌氧颗粒污泥向酸化颗粒污泥的转型。酸化颗粒污泥表观呈土黄色、淡黄色、乳白色和青灰色,颗粒污泥的粒径大小适中,沉降性能良好,有利于水解酸化反应器内保持足够的微生物量。
对工艺中各反应器颗粒污泥上的微生物相进行观察发现,水解酸化反应器酸化颗粒污泥中以短杆菌和芽孢菌为主;1#反应器颗粒污泥中以巴氏甲烷八叠球菌为优势菌属;2#反应器颗粒污泥中以索氏甲烷丝菌为优势菌,其他种属的产甲烷菌也有出现,但数量较少。
对影响工艺稳定运行的主要生态因子如温度、水力停留时间、pH值、容积负荷等进行研究,确定工艺高效稳定运行的最佳参数范围。同时初步建立水解酸化-两级厌氧工艺中各反应器的动力学模型,并分别推导出其动力学参数。
以实验室研究结果为指导,建立水解酸化-两级厌氧工艺处理高浓度甲醇废水的中试工程,全面考察工艺的启动情况和处理效能。结果表明,以颗粒污泥作为两级厌氧反应器的接种污泥,在50d内完成快速启动。水解酸化反应器的发酵类型为混合型发酵,液相末端产物的顺序为:乙酸>丙酸>丁酸>戊酸;出水VFA最高值为14.6mmol/L,较低的水解出水VFA浓度与甲醇废水的水质特点和厌氧分级处理有关。
两级厌氧反应器的有机物去除能力随容积负荷的提高而增加,启动结束时,ECA反应器COD去除率可稳定在85%左右;ECB反应器COD去除率可稳定在80%左右,两级厌氧反应器总的COD去除率可达到95.3～98.1%。当水解酸化-两级厌氧工艺的进水COD在7000～11000mg/L时,出水COD浓度可降低到300mg/L以下。
水质骤然升高所导致的冲击负荷并没有对水解酸化-两级厌氧工艺的稳定运行造成大的影响,系统出水COD始终低于450mg/L,出水水质较为稳定,工艺表现出了良好的抗冲击负荷的能力。
With the development of treatment effect, running stability, ability of resisting shock loading and automatic control mode, the application scope of anaerobic process expands continuously and shows obviously advantage in high-strength industrial wastewater treatment. However, there are some defects of single phase anaerobic reactor when treating high-strength organic wastewater with rapid changes of water quality, such as“acidification”risk. In this study, Hydrolytic Acidification & Two-Stage Anaerobic process (HATS) was developed which based on Two-phase anaerobic and SMPA theory and used External Circulation anaerobic reactor as treating unit.
Early work was finished in laboratory with purpose of ehancing the process treating efficiency, running stability such as the optimizing the ecological factors. Based on these results, the pilot-test project of high-strength methanol wastewater was established. The design and operation parameter was optimized steadily which provided technological support to methanol wastewater treatment.
In laboratory studies, the ethanol-type fermentation formation of hydrolytic acidification reactor was studied with seeded with anaerobic granular sludge, controlling volume loading rate, loading rate raising range, pH, etc. Test showed that reactor was quick start-up in 34d and formed the ethanol-type fermentation with controlling volume loading rate, loading rate raising type, pH, etc. The mass concentration of ethanol + acetic acid was 75.9 percent of liquid terminal products.
The treatment efficiency of Two-Stage ananerobic reactor was studied with seeded with anaerobic granular sludge. Test showed that 1# reactor COD removal rate reached to 93.2% under VLR=46.78kgCOD/m3·d, HRT=5.62h. 2# reactor COD removal rate reached to 85.2%. The total COD removal rate reached to 98.9%. The Two-stage anaerobic system also presented well VFA removing ability with effluent VFA below 10mg/L.
The physical properties and microbial community composition of anaerobic granule sludge seeded in hydrolytic acidification reactor was studied. And the forming way of acidizing granule sludge was also primarily explained in this paper. In hydrolytic acidification reactor, the anaerobic granular sludge transformed to acidizing granule sludge with controlling proper volume loading rate, loading rate raising type, low pH. The color of granular sludge turned from black to yellowish brown, faint yellow, cream white or caesious with preferable particle size and well settling performance which was helpful to hydrolytic acidification reactor retaining enough microbial biomass.
The dominant microflora of hydrolytic acidification reactor was Brevibacterium and Spore bacteria. The dominant microflora of 1# reactor was Methanosarcina barkeri. Methanothrix soehngenii was the dominant microflora of 2# reactor. Other Methanogens also appeared, but less.
The ecological factors which had effects on HATS treating efficiency was studied in this paper, such as temperature, pH values, VLR, HRT, etc. And the Optimal parameter set was determined. The kinetic model of each reactor in HATS was established and the kinetic parameter was deduced.
Based on experitmental results, the pilot-test project of high-strength methanol wastewater was established and the start- up and treatment efficiency of HATS was studied. Test showed that toke granule sludge as the inoculation sludge of Two-Stage reactor, HATS accomplished the quick start-up within 50 days. The fermentation type of hydrolytic acidification reactor was mixed-fermentation. The sequence of liquid terminal products was acetic acid > propanoic acid > butanoic acid > pentoic acid. Maximum effluent VFA of hydrolytic acidification reactor was 14.6mmol/L. The low VFA concentration was related to the water quality characteristics of methanol wastewater and anaerobic stage treatment.
COD removal ability of Two-stage anaerobic system increased with the enhancement of VLR. At the end of start-up period, COD removal rate of ECA reactor was about 85% and that of ECB reactor was about 80%. The total COD removal rate of Two-stage anaerobic system could arrive to 95.3～98.1%. When the influent COD of HATS was between 7000～11000mg/L, effluent COD was lower than 300mg/L.
Shock loading caused by strong fluctuation of water quality did not influence the stable running of HATS. Effluent COD was always below 450mg/L, and effluent water quality was stable. The HATS presented well ability of resisting shock loading.
实验室研究阶段,采用在水解酸化反应器中接种厌氧颗粒污泥和控制启动容积负荷、负荷提高幅度、pH值等生态因子,对反应器乙醇型发酵的形成情况进行考察,结果表明反应器在34d内完成快速启动,并形成稳定的乙醇型发酵。乙醇+乙酸质量浓度之和占液相末端产物总量的75.9%以上。
在两级厌氧反应器中接种厌氧颗粒污泥,并对其处理效能进行研究。试验结果表明,1#反应器在VLR=46.78kgCOD/m3·d、HRT=5.62h条件下,COD去除率达到93.2%;2#反应器COD去除率达到85.2%,两级厌氧反应器总去除率高达98.9%。同时,两级厌氧反应器表现出了良好的VFA去除能力,出水VFA保持在10mg/L以下。
试验对水解酸化反应器内所接中的厌氧颗粒污泥的物理特性及微生物群落组成的变化情况进行研究。同时,对酸化颗粒污泥的形成途径进行初步阐述。试验结果证明通过控制启动容积负荷及其提高方式和较低的pH值条件可实现由厌氧颗粒污泥向酸化颗粒污泥的转型。酸化颗粒污泥表观呈土黄色、淡黄色、乳白色和青灰色,颗粒污泥的粒径大小适中,沉降性能良好,有利于水解酸化反应器内保持足够的微生物量。
对工艺中各反应器颗粒污泥上的微生物相进行观察发现,水解酸化反应器酸化颗粒污泥中以短杆菌和芽孢菌为主;1#反应器颗粒污泥中以巴氏甲烷八叠球菌为优势菌属;2#反应器颗粒污泥中以索氏甲烷丝菌为优势菌,其他种属的产甲烷菌也有出现,但数量较少。
对影响工艺稳定运行的主要生态因子如温度、水力停留时间、pH值、容积负荷等进行研究,确定工艺高效稳定运行的最佳参数范围。同时初步建立水解酸化-两级厌氧工艺中各反应器的动力学模型,并分别推导出其动力学参数。
以实验室研究结果为指导,建立水解酸化-两级厌氧工艺处理高浓度甲醇废水的中试工程,全面考察工艺的启动情况和处理效能。结果表明,以颗粒污泥作为两级厌氧反应器的接种污泥,在50d内完成快速启动。水解酸化反应器的发酵类型为混合型发酵,液相末端产物的顺序为:乙酸>丙酸>丁酸>戊酸;出水VFA最高值为14.6mmol/L,较低的水解出水VFA浓度与甲醇废水的水质特点和厌氧分级处理有关。
两级厌氧反应器的有机物去除能力随容积负荷的提高而增加,启动结束时,ECA反应器COD去除率可稳定在85%左右;ECB反应器COD去除率可稳定在80%左右,两级厌氧反应器总的COD去除率可达到95.3～98.1%。当水解酸化-两级厌氧工艺的进水COD在7000～11000mg/L时,出水COD浓度可降低到300mg/L以下。
水质骤然升高所导致的冲击负荷并没有对水解酸化-两级厌氧工艺的稳定运行造成大的影响,系统出水COD始终低于450mg/L,出水水质较为稳定,工艺表现出了良好的抗冲击负荷的能力。
With the development of treatment effect, running stability, ability of resisting shock loading and automatic control mode, the application scope of anaerobic process expands continuously and shows obviously advantage in high-strength industrial wastewater treatment. However, there are some defects of single phase anaerobic reactor when treating high-strength organic wastewater with rapid changes of water quality, such as“acidification”risk. In this study, Hydrolytic Acidification & Two-Stage Anaerobic process (HATS) was developed which based on Two-phase anaerobic and SMPA theory and used External Circulation anaerobic reactor as treating unit.
Early work was finished in laboratory with purpose of ehancing the process treating efficiency, running stability such as the optimizing the ecological factors. Based on these results, the pilot-test project of high-strength methanol wastewater was established. The design and operation parameter was optimized steadily which provided technological support to methanol wastewater treatment.
In laboratory studies, the ethanol-type fermentation formation of hydrolytic acidification reactor was studied with seeded with anaerobic granular sludge, controlling volume loading rate, loading rate raising range, pH, etc. Test showed that reactor was quick start-up in 34d and formed the ethanol-type fermentation with controlling volume loading rate, loading rate raising type, pH, etc. The mass concentration of ethanol + acetic acid was 75.9 percent of liquid terminal products.
The treatment efficiency of Two-Stage ananerobic reactor was studied with seeded with anaerobic granular sludge. Test showed that 1# reactor COD removal rate reached to 93.2% under VLR=46.78kgCOD/m3·d, HRT=5.62h. 2# reactor COD removal rate reached to 85.2%. The total COD removal rate reached to 98.9%. The Two-stage anaerobic system also presented well VFA removing ability with effluent VFA below 10mg/L.
The physical properties and microbial community composition of anaerobic granule sludge seeded in hydrolytic acidification reactor was studied. And the forming way of acidizing granule sludge was also primarily explained in this paper. In hydrolytic acidification reactor, the anaerobic granular sludge transformed to acidizing granule sludge with controlling proper volume loading rate, loading rate raising type, low pH. The color of granular sludge turned from black to yellowish brown, faint yellow, cream white or caesious with preferable particle size and well settling performance which was helpful to hydrolytic acidification reactor retaining enough microbial biomass.
The dominant microflora of hydrolytic acidification reactor was Brevibacterium and Spore bacteria. The dominant microflora of 1# reactor was Methanosarcina barkeri. Methanothrix soehngenii was the dominant microflora of 2# reactor. Other Methanogens also appeared, but less.
The ecological factors which had effects on HATS treating efficiency was studied in this paper, such as temperature, pH values, VLR, HRT, etc. And the Optimal parameter set was determined. The kinetic model of each reactor in HATS was established and the kinetic parameter was deduced.
Based on experitmental results, the pilot-test project of high-strength methanol wastewater was established and the start- up and treatment efficiency of HATS was studied. Test showed that toke granule sludge as the inoculation sludge of Two-Stage reactor, HATS accomplished the quick start-up within 50 days. The fermentation type of hydrolytic acidification reactor was mixed-fermentation. The sequence of liquid terminal products was acetic acid > propanoic acid > butanoic acid > pentoic acid. Maximum effluent VFA of hydrolytic acidification reactor was 14.6mmol/L. The low VFA concentration was related to the water quality characteristics of methanol wastewater and anaerobic stage treatment.
COD removal ability of Two-stage anaerobic system increased with the enhancement of VLR. At the end of start-up period, COD removal rate of ECA reactor was about 85% and that of ECB reactor was about 80%. The total COD removal rate of Two-stage anaerobic system could arrive to 95.3～98.1%. When the influent COD of HATS was between 7000～11000mg/L, effluent COD was lower than 300mg/L.
Shock loading caused by strong fluctuation of water quality did not influence the stable running of HATS. Effluent COD was always below 450mg/L, and effluent water quality was stable. The HATS presented well ability of resisting shock loading.
引文
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