COD/SO_4~(2-)对硫酸盐有机废水厌氧处理颗粒污泥活性的影响
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摘要
为了考察COD/SO_4~(2-)值对硫酸盐有机废水厌氧处理颗粒污泥活性的影响,文章采用五隔室厌氧折流板反应器(ABR),通过逐步降低COD/SO_4~(2-)值,研究了运行过程中各隔室COD和SO_4~(2-)的去除、挥发性脂肪酸(VFA)和硫化物的分布规律以及颗粒污泥活性变化情况。结果表明:(1)在COD/SO_4~(2-)值由12.5降至4.0的过程中,COD的去除主要由第3隔室承担,SO_4~(2-)的去除由第1隔室后移并波及到第1、2、3隔室,COD和SO_4~(2-)总去除率在90%左右;VFA主要在第1、2隔室产生,在第3隔室急剧下降,而硫化物的产生由第1隔室后移至第2隔室;第3隔室颗粒污泥保持较高的比产甲烷活性(SMA)和辅酶F_(420)含量,其平均值分别为55.23 mL CH4/(gVSS·d)和10.45μmol/L,第3、4隔室的颗粒污泥的脱氢酶活性(DHA)随COD/SO_4~(2-)值变化波动较大,同时出现胞外聚合物(EPS)的积累。(2)当COD/SO_4~(2-)值降至3.0,COD的去除主要由第4隔室承担,总去除率降低至40%,SO_4~(2-)的去除则后移并波及到第1、2、3、4隔室,总去除率最终稳定在90%左右;第3隔室VFA去除不明显,出现VFA积累,硫化物的产生后移至第3隔室;第3隔室颗粒污泥的DHA、SMA、辅酶F_(420)含量均急剧下降,其数值分别为0.278μmol TTC/(g·min)、6.84 mL CH_4/(gVSS·d)和5.71μmol/L,第4、5隔室颗粒污泥的DHA和SMA总体升高,但辅酶F_(420)含量和EPS浓度均降低。
In order to investigate the effect of COD/SO_4~(2-) on the activity of anaerobic granular sludge in anaerobic treatment of organic wastewater containing sulfate,five compartment anaerobic baffled reactor(ABR) have been used.The ratio of COD/SO_4~(2-) has been gradually reduced by increasing the sulfate concentration.The removal of COD and SO_4~(2-) ,the distribution of volatile fatty acid(VFA) and sulfide,and the characteristics of granular sludge in each compartment have been studied.The results showed that:the ratio of COD/SO_4~(2-) decreased from 12.5 to 4.0,the Compartment 3 mainly takes on the removal of COD,the removal of SO_4~(2-) is moved back by Compartment 1 and spread to Compartments 1,2,and 3,the removal rates of COD and SO_4~(2-) were about 90%.The VFA was mainly produced in the Compartments 1 and 2,and then declined sharply in the Compartment 3,the production of sulfide shifted from the Compartment 1 to Compartment 2.Granular sludge maintained a high specific methanogenic activity(SMA) and coenzyme F_(420) in the Compartment 3,the average values were55.23 mL CH_4/(gVSS·d) and 10.45 μmol/L,respectively.The dehydrogenase activity(DHA) in Compartments 3 and 4 varied greatly with the change of COD/SO_4~(2-) .Extracellular polymeric substance(EPS) accumulated on the surface of granular sludge.When the ratio of COD/SO_4~(2-) decreased to 3.0,the COD was mainly removed in the Compartment 4,the removal rate of COD decreased sharply to 40%,the removal of SO_4~(2-) moves backward and spreads to Compartments 1,2,3,and 4,the removal rate of SO_4~(2-) stabilized at about 90% after a drastic reduction.VFA accumulated in the Compartment 3,sulfide production moved to the Compartment 3.The granular sludge DHA,SMA,and coenzyme F_(420) content decreased sharply in the Com-partment 3,the average values were 0.278 μmol TTC/(g·min),6.84 mL CH4/(gVSS·d) and 5.71 μmol/L,respectively.The granular sludge DHA and SMA increased in Compartments 4 and 5,but the content of coenzyme F420 and EPS concentrations decreased in Compartments 4 and 5.
In order to investigate the effect of COD/SO_4~(2-) on the activity of anaerobic granular sludge in anaerobic treatment of organic wastewater containing sulfate,five compartment anaerobic baffled reactor(ABR) have been used.The ratio of COD/SO_4~(2-) has been gradually reduced by increasing the sulfate concentration.The removal of COD and SO_4~(2-) ,the distribution of volatile fatty acid(VFA) and sulfide,and the characteristics of granular sludge in each compartment have been studied.The results showed that:the ratio of COD/SO_4~(2-) decreased from 12.5 to 4.0,the Compartment 3 mainly takes on the removal of COD,the removal of SO_4~(2-) is moved back by Compartment 1 and spread to Compartments 1,2,and 3,the removal rates of COD and SO_4~(2-) were about 90%.The VFA was mainly produced in the Compartments 1 and 2,and then declined sharply in the Compartment 3,the production of sulfide shifted from the Compartment 1 to Compartment 2.Granular sludge maintained a high specific methanogenic activity(SMA) and coenzyme F_(420) in the Compartment 3,the average values were55.23 mL CH_4/(gVSS·d) and 10.45 μmol/L,respectively.The dehydrogenase activity(DHA) in Compartments 3 and 4 varied greatly with the change of COD/SO_4~(2-) .Extracellular polymeric substance(EPS) accumulated on the surface of granular sludge.When the ratio of COD/SO_4~(2-) decreased to 3.0,the COD was mainly removed in the Compartment 4,the removal rate of COD decreased sharply to 40%,the removal of SO_4~(2-) moves backward and spreads to Compartments 1,2,3,and 4,the removal rate of SO_4~(2-) stabilized at about 90% after a drastic reduction.VFA accumulated in the Compartment 3,sulfide production moved to the Compartment 3.The granular sludge DHA,SMA,and coenzyme F_(420) content decreased sharply in the Com-partment 3,the average values were 0.278 μmol TTC/(g·min),6.84 mL CH4/(gVSS·d) and 5.71 μmol/L,respectively.The granular sludge DHA and SMA increased in Compartments 4 and 5,but the content of coenzyme F420 and EPS concentrations decreased in Compartments 4 and 5.
引文
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[3]Isa Z,Grusenmeyers S,Verstraete W.Sulfate reduction relative to methan production in high-sulfate anaerobic digestion:technical aspects[J].Appl Environ Microbiol,1986,51(3):572-579.
[4]司胜敏,李滦宁,柴社立,等.厌氧生物法处理高浓度酸性硫酸盐废水研究[J].世界地质,2008,27(3):310-313.Si Shengmin,Li Luanning,Chai Sheli,et al.Research on treatment of high concentration sulfate acidic wastewater by an anaerobic bioreactor[J].Global Geology,2008,27(3):310-313.
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[6]Lopes SIC,Capela MI,Lens PNL.Sulfate reduction during the acidification of sucrose at p H 5 under thermophilic(55℃)conditions II:effect of sulfide and COD/SO42-ratio[J].Bioresour Technol,2010,101(12):4278-4284.
[7]周兴求,伍健东,阮君.SO42-对厌氧折流板反应器中颗粒污泥性能的影响[J].安全与环境学报,2008,8(3):74-77.Zhou Xingqiu,Wu Jiandong,Ruan Jun.The effect of SO42-on the performance of ABR anaerobic granular sludge[J].Journal of Safety and Environment,2008,8(3):74-77.
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[9]Li Jin,Wang Jun,Luan Zhaokun,et al.Biological sulfate removal from acrylic fiber manufacturing wastewater using a two-stage UASB reactor[J].Journal of Environmental Sciences,2012,24(2):343-350.
[10]Lu X,Zhen G,Ni J,et al.Effect of influent COD/SO42-ratios on biodegradation behaviors of starch wastewater in an upflow anaerobic sludge blanket(UASB)reactor[J].Bioresource Technology,2016,214:175-183.
[11]中国环境保护总局.水和废水监测分析方法[M].第四版.北京:中国环境科学出版社,2002.China National Environmental Protection Administration.Water and Wastewater Monitoring and Analysis Methods[M].Fourth Edition.Beijing:China Environmental Science Press,2002.
[12]贺延龄.废水的厌氧生物处理[M].北京:中国轻工业出版社,1998:514-521.He Yanling.Anaerobic Biological Treatment of Wastewater[M].Beijing:China Light Industry Press,1998:514-521.
[13]魏民,郑国臣,李建政,等.表征水体中生物活性及脱氢酶检测方法研究[J].东北水利水电,2012,8:43-46.Wei Min,Zheng Guochen,Li Jianzheng,et al.Study on bioactivity and dehydrogenase detection methods in water bodies[J].Journal of Northeast Water Resources and Hydropower,2012,8:43-46.
[14]赵连梅,迟勇志,张春青.TTC-脱氢酶测定中标准曲线的影响因素研究[J].实验室科学,2009,4:72-74.Zhao Lianmei,Chi Yongzhi,Zhang Chunqing.Study on the factors affecting the standard curve in the determination of TTC-dehydrogenase[J].Laboratory Science,2009,4:72-74.
[15]马放.污染控制微生物学实验[M].哈尔滨:哈尔滨工业大学出版社,2002:119-122.Ma Fang.Microbiology Experiment of Pollution Control[M].Harbin:Harbin Institute of Technology Press,2002:119-122.
[16]赵阳,李秀芬,堵国成,等.钴及其配合物对产甲烷关键酶的影响[J].水资源保护,2008,24(3):82-91.Zhao Yang,Li Xiufen,Du Guocheng,et al.Effects of cobalt and its complexes on key enzymes for methanogenesis[J].Water Resources Protection,2008,24(3):82-91.
[17]赵阳,李秀芬,堵国成,等.钴的配合物对甲烷发酵和产甲烷过程中关键酶的影响[J].食品与生物技术学报,2007,26(5):71-74.Zhao Yang,Li Xiufen,Du Guocheng,et al.Effects of cobalt complexes on key enzymes in methane fermentation and methanogenesis[J].Journal of Food Science and Biotechnology,2007,26(5):71-74.
[18]Gaudy A F.Colorimetric determination of protein and carbohydrate[J].Ind Water Wastes,1962,7:17-22.
[19]Frolund B,Palmgren R,Keiding K,et al.Extraction of extracellular polymers from activated sludge using a cation exchange resin[J].Water Res,1996,30:1749-1758.
[20]Ren Nanqi,Li Jianzheng,Li Baikun,et al.Biohydrogen production from molasses by anaerobic fermentation with a pilot-scale bioreactor system[J].International Journal of Hydrogen Energy,2006,31:2147-2157.
[21]李建政,王颐,郑国臣,等.表征发酵产氢活性污泥效能的碘硝基四氮唑紫-比脱氢酶活性及其检测[J].科技导报,2009,27(15):104-108.Li Jianzheng,Wang Yi,Zheng Guochen,et al.Activity and detection of iodonitrotetrazolium violet-specific dehydrogenase activity for characterizing fermentative hydrogen production activated sludge[J].Science&Technology Review,2009,27(15):104-108.
[22]徐金兰,王志盈,杨永哲,等.ABR的启动与颗粒污泥形成特征[J].环境科学学报,2003,23(5):575-581.Xu Jinlan,Wang Zhiying,Yang Yongzhe,et al.Start-up of anaerobic baffled reactor(ABR)and the feature of granular sludge forming[J].Acta Scientiae Circumstantiae,2003,23(5):575-581.
[23]蒋永荣,胡明成,李学军,等.ABR处理硫酸盐有机废水的相分离特性研究[J].环境科学,2010,31(7):1544-1553.Jiang Yongrong,Hu Mingcheng,Li Xuejun,et al.Study on phase separation characteristics of ABR treated sulfate organic wastewater[J].Environmental Science,2010,31(7):1544-1553.
[24]唐一,胡纪萃.辅酶F420作为厌氧污泥活性指标的研究[J].中国沼气,1990,8(1):11-15.Tang Yi,Hu Jicui.Study on coenzyme F420as an index of anaerobic sludge activity[J].China Biogas,1990,8(1):11-15.
[25]Lu X Q,Zhen G Y,Estrada A L,et al.Operation performance and granule characterization of upflow anaerobic sludge blanket(UASB)reactor treating wastewater with starch as the sole carbon source[J].Bioresource Technology,2015,180:264-273.
[26]Liu Y Q,Liu Y,Tay J H.The effects of extracellular polymeric substances on the formation and stability of biogranules[J].Applied Microbiology Biotechnology,2004,65:143-148.
[27]Luonogo L A,Zhang X Q.Toxicity of carbon nanotubes to the activated sludge process[J].Journal of Hazardous Materials,2010,178(1):356-362.
[28]She Z L,Zheng X L,Yang B R,et al.Granule development and performance in sucrose fed anaerobic baffled reactors[J].J Biochnol,2006,122(2):198-208.
[29]Zhu G F,Li J Z,Wu P,et al.The performance and phase separated characteristics of an anaerobic baffled reactor treating soybean protein processing wastewater[J].Bioresource Technol,2008,99(17):8027-8033.
[30]O'Flaherty V,Lens P,Leahy B,et al.Long-term competition between sulfate reducing and methane producing bacteria during full-scale anaerobic treatment of citric acid production wastewater[J].Wat Res,1998,32(3):815-825.
[31]Mcartney D M.Competition between methanogens and shlphate reduce:effect of COD/SO42-ratio and acclimation[J].Water Environ Res,1993,65:1124-1131.
[32]王志强,张建民,张继.COD/SO42-对SRB处理含硫酸盐废水效果的影响[J].西安工程大学学报,2010,24(2):185-188.Wang Zhiqiang,Zhang Jianmin,Zhang Ji.Effect of COD/SO42-on the effect of SRB treatment of sulfate-containing wastewater[J].Journal of Xi'an Engineering University,2010,24(2):185-188.
[33]Hitton B L,Oleszkiemicz J A.Sulphate-induced inhibition of anaerobic digestion[J].Environ Eng,1988,114(6):1377-1391.
[2]Samir K K,Huang J C.ORP-based oxygenation for sulfide control in anaerobic treatment of high-sulfate wastewater[J].Water Res,2003,37(10):2053-2062.
[3]Isa Z,Grusenmeyers S,Verstraete W.Sulfate reduction relative to methan production in high-sulfate anaerobic digestion:technical aspects[J].Appl Environ Microbiol,1986,51(3):572-579.
[4]司胜敏,李滦宁,柴社立,等.厌氧生物法处理高浓度酸性硫酸盐废水研究[J].世界地质,2008,27(3):310-313.Si Shengmin,Li Luanning,Chai Sheli,et al.Research on treatment of high concentration sulfate acidic wastewater by an anaerobic bioreactor[J].Global Geology,2008,27(3):310-313.
[5]李清雪,范超,李龙和,等.ABR处理高浓度硫酸盐有机废水的性能[J].中国给水排水,2007,23(15):47-50.Li Qingxue,Fan Chao,Li Longhe,et al.Performance of ABR in treating high concentration sulfate organic wastewater[J].China Water&Wastewater,2007,23(15):47-50.
[6]Lopes SIC,Capela MI,Lens PNL.Sulfate reduction during the acidification of sucrose at p H 5 under thermophilic(55℃)conditions II:effect of sulfide and COD/SO42-ratio[J].Bioresour Technol,2010,101(12):4278-4284.
[7]周兴求,伍健东,阮君.SO42-对厌氧折流板反应器中颗粒污泥性能的影响[J].安全与环境学报,2008,8(3):74-77.Zhou Xingqiu,Wu Jiandong,Ruan Jun.The effect of SO42-on the performance of ABR anaerobic granular sludge[J].Journal of Safety and Environment,2008,8(3):74-77.
[8]容翠娟,邓秀梅,蒋永荣,等.COD/SO42-值对硫酸盐有机废水处理效率的影响[J].环境科学与技术,2011,34(4):148-151.Rong Cuijuan,Deng Xiumei,Jiang Yongrong,et al.Effect of COD/SO42-on treatment of organic wastewater containing sulfate[J].Environmental Science&Technology,2011,34(4):148-151.
[9]Li Jin,Wang Jun,Luan Zhaokun,et al.Biological sulfate removal from acrylic fiber manufacturing wastewater using a two-stage UASB reactor[J].Journal of Environmental Sciences,2012,24(2):343-350.
[10]Lu X,Zhen G,Ni J,et al.Effect of influent COD/SO42-ratios on biodegradation behaviors of starch wastewater in an upflow anaerobic sludge blanket(UASB)reactor[J].Bioresource Technology,2016,214:175-183.
[11]中国环境保护总局.水和废水监测分析方法[M].第四版.北京:中国环境科学出版社,2002.China National Environmental Protection Administration.Water and Wastewater Monitoring and Analysis Methods[M].Fourth Edition.Beijing:China Environmental Science Press,2002.
[12]贺延龄.废水的厌氧生物处理[M].北京:中国轻工业出版社,1998:514-521.He Yanling.Anaerobic Biological Treatment of Wastewater[M].Beijing:China Light Industry Press,1998:514-521.
[13]魏民,郑国臣,李建政,等.表征水体中生物活性及脱氢酶检测方法研究[J].东北水利水电,2012,8:43-46.Wei Min,Zheng Guochen,Li Jianzheng,et al.Study on bioactivity and dehydrogenase detection methods in water bodies[J].Journal of Northeast Water Resources and Hydropower,2012,8:43-46.
[14]赵连梅,迟勇志,张春青.TTC-脱氢酶测定中标准曲线的影响因素研究[J].实验室科学,2009,4:72-74.Zhao Lianmei,Chi Yongzhi,Zhang Chunqing.Study on the factors affecting the standard curve in the determination of TTC-dehydrogenase[J].Laboratory Science,2009,4:72-74.
[15]马放.污染控制微生物学实验[M].哈尔滨:哈尔滨工业大学出版社,2002:119-122.Ma Fang.Microbiology Experiment of Pollution Control[M].Harbin:Harbin Institute of Technology Press,2002:119-122.
[16]赵阳,李秀芬,堵国成,等.钴及其配合物对产甲烷关键酶的影响[J].水资源保护,2008,24(3):82-91.Zhao Yang,Li Xiufen,Du Guocheng,et al.Effects of cobalt and its complexes on key enzymes for methanogenesis[J].Water Resources Protection,2008,24(3):82-91.
[17]赵阳,李秀芬,堵国成,等.钴的配合物对甲烷发酵和产甲烷过程中关键酶的影响[J].食品与生物技术学报,2007,26(5):71-74.Zhao Yang,Li Xiufen,Du Guocheng,et al.Effects of cobalt complexes on key enzymes in methane fermentation and methanogenesis[J].Journal of Food Science and Biotechnology,2007,26(5):71-74.
[18]Gaudy A F.Colorimetric determination of protein and carbohydrate[J].Ind Water Wastes,1962,7:17-22.
[19]Frolund B,Palmgren R,Keiding K,et al.Extraction of extracellular polymers from activated sludge using a cation exchange resin[J].Water Res,1996,30:1749-1758.
[20]Ren Nanqi,Li Jianzheng,Li Baikun,et al.Biohydrogen production from molasses by anaerobic fermentation with a pilot-scale bioreactor system[J].International Journal of Hydrogen Energy,2006,31:2147-2157.
[21]李建政,王颐,郑国臣,等.表征发酵产氢活性污泥效能的碘硝基四氮唑紫-比脱氢酶活性及其检测[J].科技导报,2009,27(15):104-108.Li Jianzheng,Wang Yi,Zheng Guochen,et al.Activity and detection of iodonitrotetrazolium violet-specific dehydrogenase activity for characterizing fermentative hydrogen production activated sludge[J].Science&Technology Review,2009,27(15):104-108.
[22]徐金兰,王志盈,杨永哲,等.ABR的启动与颗粒污泥形成特征[J].环境科学学报,2003,23(5):575-581.Xu Jinlan,Wang Zhiying,Yang Yongzhe,et al.Start-up of anaerobic baffled reactor(ABR)and the feature of granular sludge forming[J].Acta Scientiae Circumstantiae,2003,23(5):575-581.
[23]蒋永荣,胡明成,李学军,等.ABR处理硫酸盐有机废水的相分离特性研究[J].环境科学,2010,31(7):1544-1553.Jiang Yongrong,Hu Mingcheng,Li Xuejun,et al.Study on phase separation characteristics of ABR treated sulfate organic wastewater[J].Environmental Science,2010,31(7):1544-1553.
[24]唐一,胡纪萃.辅酶F420作为厌氧污泥活性指标的研究[J].中国沼气,1990,8(1):11-15.Tang Yi,Hu Jicui.Study on coenzyme F420as an index of anaerobic sludge activity[J].China Biogas,1990,8(1):11-15.
[25]Lu X Q,Zhen G Y,Estrada A L,et al.Operation performance and granule characterization of upflow anaerobic sludge blanket(UASB)reactor treating wastewater with starch as the sole carbon source[J].Bioresource Technology,2015,180:264-273.
[26]Liu Y Q,Liu Y,Tay J H.The effects of extracellular polymeric substances on the formation and stability of biogranules[J].Applied Microbiology Biotechnology,2004,65:143-148.
[27]Luonogo L A,Zhang X Q.Toxicity of carbon nanotubes to the activated sludge process[J].Journal of Hazardous Materials,2010,178(1):356-362.
[28]She Z L,Zheng X L,Yang B R,et al.Granule development and performance in sucrose fed anaerobic baffled reactors[J].J Biochnol,2006,122(2):198-208.
[29]Zhu G F,Li J Z,Wu P,et al.The performance and phase separated characteristics of an anaerobic baffled reactor treating soybean protein processing wastewater[J].Bioresource Technol,2008,99(17):8027-8033.
[30]O'Flaherty V,Lens P,Leahy B,et al.Long-term competition between sulfate reducing and methane producing bacteria during full-scale anaerobic treatment of citric acid production wastewater[J].Wat Res,1998,32(3):815-825.
[31]Mcartney D M.Competition between methanogens and shlphate reduce:effect of COD/SO42-ratio and acclimation[J].Water Environ Res,1993,65:1124-1131.
[32]王志强,张建民,张继.COD/SO42-对SRB处理含硫酸盐废水效果的影响[J].西安工程大学学报,2010,24(2):185-188.Wang Zhiqiang,Zhang Jianmin,Zhang Ji.Effect of COD/SO42-on the effect of SRB treatment of sulfate-containing wastewater[J].Journal of Xi'an Engineering University,2010,24(2):185-188.
[33]Hitton B L,Oleszkiemicz J A.Sulphate-induced inhibition of anaerobic digestion[J].Environ Eng,1988,114(6):1377-1391.