厌氧折流板反应器中硫酸盐还原菌颗粒污泥处理含铜废水的研究
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摘要
随着经济的发展,各种废水的产生量大幅度上升,由此带来的环境污染问题日益严峻。以硫酸盐还原菌(Sulfate Reducing Bacteria ,简称SRB)为代表的厌氧微生物处理技术具有对污染物降解完全、处理成本低和不产生二次污染的特点,是一项极具发展潜力的污水处理技术。厌氧折流板反应器(Anaerobic Battled Reactor ,简称ABR)具有其独特的优势,设计简单、成本较低,截留污泥能力强,稳定性高,是一种高效的厌氧反应器。本文在分析了ABR反应器的研究与应用现状、硫酸盐还原菌处理重金属废水研究进展的基础上,较系统地对利用ABR反应器培养、驯化SRB颗粒污泥及处理含铜废水的性能进行了研究。
利用实验室自制的ABR反应器,采用人工葡萄糖配水进行实验,分析了ABR反应器启动过程的运行特性及SRB颗粒污泥的特性,结果表明:35℃恒温条件下,在ABR反应器中直接接种厌氧颗粒污泥, 57天可完成启动,最高容积负荷可达4.9kgCOD/(m3·d),COD与SO42-去除率都稳定在91%以上;启动完成后,反应器中1#、2#格室颗粒污泥的VSS/TSS值比接种污泥的值大,颗粒污泥具有较高的生物活性和良好的沉淀性。
接着,通过静态试验研究了在不同pH值、SO42-质量浓度、Cu2+质量浓度条件下系统比产甲烷活性的变化规律以及SRB颗粒污泥去除有机物、还原硫酸盐、去除Cu2+等的效果。结果表明:(1)当pH=6~8时,SRB颗粒污泥活性最高,SO42-的去除率最高达91.8%,COD去除率为83.2%~90.5%,SRB颗粒污泥对Cu2+的去除效率也达到最佳,去除率>91.6%。(2)当SO42-质量浓度为2000mg/L,COD与SO42-质量浓度的比值ω(COD)/ω(SO42-)=2时,SRB颗粒污泥的活性最高,此时系统比产甲烷活性为406.2mL/(g·d),SO42-和Cu2+去除率分别达到93.4%、97.1%,且Cu2+去除率与SO42-还原率呈正相关关系。(3)当Cu2+质量浓度为10 mg/L时,系统产甲烷量达到最大值,为58.3mL/h,COD去除率高达90.5 %,但SO42-最大去除率(91.9%)却出现在Cu2+浓度为8mg/L时;当溶液的Cu2+浓度低于35mg/L时,SRB颗粒污泥对Cu2+的去除效率基本稳定在98%以上。
最后,研究了ABR反应器处理含铜废水的运行特性,结果表明:(1)在整个进水硫酸盐浓度调节阶段(即SO42-质量浓度由2000mg/L逐步降低到500mg/L,再逐步提到到2000mg/L),水中溶解性硫化物(DS)质量浓度在51~246mg/L的范围内波动,没有达到毒害厌氧微生物的浓度,而Cu2+去除率也始终保持在95.1%以上,SO42-去除率维持在83.1%～92.7%之间。(2)当水力停留时间(HRT)由初始状态的20h缩短至7h,COD容积负荷由4.8kgCOD/(m3·d)增加到13.7kgCOD/(m3·d),COD去除率、SO42-去除率、Cu2+的去除率、DS质量浓度均呈阶梯状下降。(3)随着进水Cu2+浓度的增加,厌氧系统对Cu2+的去除效率基本稳定在90%以上,出水SO42-浓度在266 ~562 mg/L之间;当Cu2+浓度增加到10mg/L时,COD去除率低至69%;ABR反应器1#格室内单位质量SRB颗粒污泥中总铜的量也随着运行时间不断增加,且SRB颗粒污泥中的重金属铜主要以有机质硫化态的形式存在。
通过扫描电镜观察到,接种污泥表面高低不平,有些区域光滑,有些区域粗糙,颗粒污泥中的微生物形态较为单一,以杆菌为主,也有少量的球菌;启动结束后的颗粒污泥表面较为光滑,颗粒表面有较多孔穴,污泥中微生物含量更丰富,形态更多样,微生物分布比接种污泥更密集。但通入模拟含铜废水后,颗粒污泥的粒径也不断增大,表面高低不平,颗粒污泥的结构也越来越蓬松,在较强的水力冲击下,容易解体而被冲出反应器。
The environmental pollution become worse and worse when more and more wastewater is produced rapidly with the economic development. The treatment technology with anaerobic microorganism which is on the representation of SRB has a lot of advantages, such as reducing the pollutant completely, lower cost and none of the second pollution and it becomes the hotest wastewater treatment at present. According to the structural characteristic of ABR, it has a lot of advantages, such as simple structure, lower price, strong ability of retaining sludge, and high stability and so on, and it has became one of the hot topic of anaerobic reactor study nowadays. On the bases of analyses of principle and applications of ABR and present researches on the heavy metals treatment by SRB, the operation characteristic and performance of treating copper wastewater with SRB granular sludge which was domesticated in ABR were studied systematically in the paper.
The running characteristics during the set-up of ABR and performance changes of granule sludge were analyzed using laboratory-made anaerobic baffled reactor. The experiment results showed that, when the reactor started at a constant temperature of 35℃with inoculated anaerobic granular sludge and simulated synthetic wastewater as substrate,the whole start-up period was 57 days, and the maximum volume loading rate was up to 4.9kgCOD/(m3·d), and the removal rate of COD and SO42- stabled above 91%. And after the set-up, the VSS/TSS of granule sludge in the first and second compartments more than that of inoculated sludge and the granule sludge could still attain high biological activity and fine settlement property.
Later, the effect of various pH, SO42- and Cu2+ concentration on the performance of sulfate reducing bacteria granular sludge treating COD, SO42- and Cu2+ were investigated by intermittent experiments in this paper. The results indicated that, (1) The SRB granular sludge would be likely to enter into the best operative state when pH was equal to 6~8. Besides, the maximum SO42- removal rate was 91.8%, the removal rate of COD was 83.2% to 90.5% and the maximum Cu2+ removal rate was over 91.6%. (2) The SRB granular sludge would be likely to enter into the best operative state whenω(COD)/ω(SO42-) was equal to 2 with the mass concentration of SO42- being 2000mg/L. Besides, specific methanogenic activity was 406.2mL/(g·d), the maximum SO42- removal rate was 93.4% and the maximum Cu2+ removal rate reached 97.1%, at the same time the removal rate of COD was positive correlation with the SO42- removal rate. (3) When the mass concentration of Cu2+ was equal to 10mg/L, the maximum content of methane produce was 58.3mL/h and the maximum COD removal rate was 90.5%. But the maximum SO42- removal rate (91.9%) presented at Cu2+=10mg/L. The removal rate of Cu2+ became stabled over 98% while mass concentration of Cu2+ was lower than 35mg/L.
At last, the operation characteristic and performance of treating copper wastewater with SRB granular sludge by ABR were studied. The results indicated that, (1) At the moment of changing the SO42- concentration (the SO42- concentration fell from 2000mg/L to 500mg/L, then increased from 500mg/L to 2000 mg/L ), the DS concentration ranged from 51mg/L to 246mg/L which is lower than the deadly concentration. Besides the Cu2+ removal rate was over 95.1% and the SO42- removal rate ranged from 83.1% to 92.7%. (2) When HRT was shorten from 20h to 7h with the COD volume load increased from 4.8 kgCOD/(m3·d) to 13.7 kgCOD/(m3·d), the removal rate of COD, SO42- and Cu2+ as well as DS concentration decreased steadily. (3) The removal rate of Cu2+ became stabled over 90% and the effluence SO42- concentration was from 266mg/L to 562mg/L with the increasing Cu2+ concentration in influence. The COD removal rate was lower to 69% while Cu2+ concentration increased to 10mg/L. The tatal copper content of SRB granular sludge in the first compartment increased day by day and the copper of SRB granular sludge was mainly in organic sulfate fraction.
The SEM showed that the inoculated granular sludge surface was rugged and species of microorganisms in it was single such as bacillus and coccus. On the other hand, the surface of domesticated SRB granular sludge was slippery, lacunaris and diversiform. There were various microorganisms in the domesticated SRB granular sludge and they were dense. The granular sludge grew up day by day with treating the copper wastewater. The surface of the granular sludge was so shaggy that it was disaggregated by the current in the ABR.
利用实验室自制的ABR反应器,采用人工葡萄糖配水进行实验,分析了ABR反应器启动过程的运行特性及SRB颗粒污泥的特性,结果表明:35℃恒温条件下,在ABR反应器中直接接种厌氧颗粒污泥, 57天可完成启动,最高容积负荷可达4.9kgCOD/(m3·d),COD与SO42-去除率都稳定在91%以上;启动完成后,反应器中1#、2#格室颗粒污泥的VSS/TSS值比接种污泥的值大,颗粒污泥具有较高的生物活性和良好的沉淀性。
接着,通过静态试验研究了在不同pH值、SO42-质量浓度、Cu2+质量浓度条件下系统比产甲烷活性的变化规律以及SRB颗粒污泥去除有机物、还原硫酸盐、去除Cu2+等的效果。结果表明:(1)当pH=6~8时,SRB颗粒污泥活性最高,SO42-的去除率最高达91.8%,COD去除率为83.2%~90.5%,SRB颗粒污泥对Cu2+的去除效率也达到最佳,去除率>91.6%。(2)当SO42-质量浓度为2000mg/L,COD与SO42-质量浓度的比值ω(COD)/ω(SO42-)=2时,SRB颗粒污泥的活性最高,此时系统比产甲烷活性为406.2mL/(g·d),SO42-和Cu2+去除率分别达到93.4%、97.1%,且Cu2+去除率与SO42-还原率呈正相关关系。(3)当Cu2+质量浓度为10 mg/L时,系统产甲烷量达到最大值,为58.3mL/h,COD去除率高达90.5 %,但SO42-最大去除率(91.9%)却出现在Cu2+浓度为8mg/L时;当溶液的Cu2+浓度低于35mg/L时,SRB颗粒污泥对Cu2+的去除效率基本稳定在98%以上。
最后,研究了ABR反应器处理含铜废水的运行特性,结果表明:(1)在整个进水硫酸盐浓度调节阶段(即SO42-质量浓度由2000mg/L逐步降低到500mg/L,再逐步提到到2000mg/L),水中溶解性硫化物(DS)质量浓度在51~246mg/L的范围内波动,没有达到毒害厌氧微生物的浓度,而Cu2+去除率也始终保持在95.1%以上,SO42-去除率维持在83.1%～92.7%之间。(2)当水力停留时间(HRT)由初始状态的20h缩短至7h,COD容积负荷由4.8kgCOD/(m3·d)增加到13.7kgCOD/(m3·d),COD去除率、SO42-去除率、Cu2+的去除率、DS质量浓度均呈阶梯状下降。(3)随着进水Cu2+浓度的增加,厌氧系统对Cu2+的去除效率基本稳定在90%以上,出水SO42-浓度在266 ~562 mg/L之间;当Cu2+浓度增加到10mg/L时,COD去除率低至69%;ABR反应器1#格室内单位质量SRB颗粒污泥中总铜的量也随着运行时间不断增加,且SRB颗粒污泥中的重金属铜主要以有机质硫化态的形式存在。
通过扫描电镜观察到,接种污泥表面高低不平,有些区域光滑,有些区域粗糙,颗粒污泥中的微生物形态较为单一,以杆菌为主,也有少量的球菌;启动结束后的颗粒污泥表面较为光滑,颗粒表面有较多孔穴,污泥中微生物含量更丰富,形态更多样,微生物分布比接种污泥更密集。但通入模拟含铜废水后,颗粒污泥的粒径也不断增大,表面高低不平,颗粒污泥的结构也越来越蓬松,在较强的水力冲击下,容易解体而被冲出反应器。
The environmental pollution become worse and worse when more and more wastewater is produced rapidly with the economic development. The treatment technology with anaerobic microorganism which is on the representation of SRB has a lot of advantages, such as reducing the pollutant completely, lower cost and none of the second pollution and it becomes the hotest wastewater treatment at present. According to the structural characteristic of ABR, it has a lot of advantages, such as simple structure, lower price, strong ability of retaining sludge, and high stability and so on, and it has became one of the hot topic of anaerobic reactor study nowadays. On the bases of analyses of principle and applications of ABR and present researches on the heavy metals treatment by SRB, the operation characteristic and performance of treating copper wastewater with SRB granular sludge which was domesticated in ABR were studied systematically in the paper.
The running characteristics during the set-up of ABR and performance changes of granule sludge were analyzed using laboratory-made anaerobic baffled reactor. The experiment results showed that, when the reactor started at a constant temperature of 35℃with inoculated anaerobic granular sludge and simulated synthetic wastewater as substrate,the whole start-up period was 57 days, and the maximum volume loading rate was up to 4.9kgCOD/(m3·d), and the removal rate of COD and SO42- stabled above 91%. And after the set-up, the VSS/TSS of granule sludge in the first and second compartments more than that of inoculated sludge and the granule sludge could still attain high biological activity and fine settlement property.
Later, the effect of various pH, SO42- and Cu2+ concentration on the performance of sulfate reducing bacteria granular sludge treating COD, SO42- and Cu2+ were investigated by intermittent experiments in this paper. The results indicated that, (1) The SRB granular sludge would be likely to enter into the best operative state when pH was equal to 6~8. Besides, the maximum SO42- removal rate was 91.8%, the removal rate of COD was 83.2% to 90.5% and the maximum Cu2+ removal rate was over 91.6%. (2) The SRB granular sludge would be likely to enter into the best operative state whenω(COD)/ω(SO42-) was equal to 2 with the mass concentration of SO42- being 2000mg/L. Besides, specific methanogenic activity was 406.2mL/(g·d), the maximum SO42- removal rate was 93.4% and the maximum Cu2+ removal rate reached 97.1%, at the same time the removal rate of COD was positive correlation with the SO42- removal rate. (3) When the mass concentration of Cu2+ was equal to 10mg/L, the maximum content of methane produce was 58.3mL/h and the maximum COD removal rate was 90.5%. But the maximum SO42- removal rate (91.9%) presented at Cu2+=10mg/L. The removal rate of Cu2+ became stabled over 98% while mass concentration of Cu2+ was lower than 35mg/L.
At last, the operation characteristic and performance of treating copper wastewater with SRB granular sludge by ABR were studied. The results indicated that, (1) At the moment of changing the SO42- concentration (the SO42- concentration fell from 2000mg/L to 500mg/L, then increased from 500mg/L to 2000 mg/L ), the DS concentration ranged from 51mg/L to 246mg/L which is lower than the deadly concentration. Besides the Cu2+ removal rate was over 95.1% and the SO42- removal rate ranged from 83.1% to 92.7%. (2) When HRT was shorten from 20h to 7h with the COD volume load increased from 4.8 kgCOD/(m3·d) to 13.7 kgCOD/(m3·d), the removal rate of COD, SO42- and Cu2+ as well as DS concentration decreased steadily. (3) The removal rate of Cu2+ became stabled over 90% and the effluence SO42- concentration was from 266mg/L to 562mg/L with the increasing Cu2+ concentration in influence. The COD removal rate was lower to 69% while Cu2+ concentration increased to 10mg/L. The tatal copper content of SRB granular sludge in the first compartment increased day by day and the copper of SRB granular sludge was mainly in organic sulfate fraction.
The SEM showed that the inoculated granular sludge surface was rugged and species of microorganisms in it was single such as bacillus and coccus. On the other hand, the surface of domesticated SRB granular sludge was slippery, lacunaris and diversiform. There were various microorganisms in the domesticated SRB granular sludge and they were dense. The granular sludge grew up day by day with treating the copper wastewater. The surface of the granular sludge was so shaggy that it was disaggregated by the current in the ABR.
引文
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