不同滤料滤池启动期内对铁锰离子的去除机制
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摘要
采用两座小试生物滤池,考察了锰矿砂和石英砂滤料在启动期内对铁锰离子的去除特性,并结合材料表征手段解析了过滤去除机制.启动运行结果表明,在进水铁锰质量浓度为2～3 mg·L~(-1)和0. 3～0. 6 mg·L~(-1)时,石英砂滤池分别需要15 d和30 d完成铁锰的去除,而锰矿砂滤池在10 d内完成除铁过程,而出水锰质量浓度始终低于0. 1 mg·L~(-1),满足国标要求.锰矿砂表面天然铁锰氧化物的吸附催化作用是其去除效果优于石英砂的关键.一方面,当铁氧化物在石英砂滤池内形成后,其同样能继续吸附催化铁离子,两滤池对铁离子的最终转化产物为复合氧化物,2价与3价铁的比值在1∶1. 44～1∶1. 54之间.其次,在启动期内,锰矿砂滤池对锰离子的去除以吸附催化氧化完成,其产物为3价态锰,而后续在生物作用下趋于转化为4价;石英砂滤池对锰离子的去除以吸附主导,但吸附容量饱和后以生物作用为主.最终,锰离子转化产物为2价、3价和4价态的复合态氧化物.此外,锰氧化产物呈层状结构,铁氧化产物为颗粒形态,二者均能披覆在滤料表面,但后者更容易被反洗出滤层,而前者则倾向于披覆在锰矿砂表面或积累在石英砂滤层孔隙间.
Two lab-scale biofilters packed with manganese ore sand and quartz sand were constructed to reveal the behavior in removing iron and manganese during the start-up period. Meanwhile,the removal mechanism of the two sands was also investigated by means of EDS,XPS,and SEM. With the influent iron( 2-3 mg·L~(-1)) and manganese( 0. 3-0. 6 mg·L~(-1)),the start-up operational results indicated that the quartz sand biofilter needed 15 and 30 d to achieve the removal of iron and manganese,respectively. The manganese ore sand only required 10 d to remove iron,while the effluent manganese was always below of 0. 1 mg·L~(-1). The results confirmed that the natural iron and manganese oxides coated on the manganese ore sand surface could explain its better removal behavior as compared to quartz sand. However,the generated iron oxide could also act as the adsorbent and catalyst like natural iron oxide,only when iron removal occurred in the quartz sand biofilter. The final product of iron removal was a complex consisting of divalent and trivalent iron,with a specific value of 1 ∶ 1. 44-1 ∶ 1. 54. Moreover,during the start-up period,manganese ore sand transformed manganese from divalent to trivalent by the catalytic effect,while the latter tended to be converted to the quadrivalent state under the bioactivity. The quartz sand could adsorb manganese but easily became saturated,and then the removal was dominated by bioactivity. The product generated by the manganese removal process was also a complex with the three valences. Moreover,the two complexes could coat onto the surface of the sands,but most of the iron complex was easily washed out of the filtering layer. Conversely,the manganese complex tended to coat onto the manganese ore sand surface or accumulate between the pores of quartz sand.
Two lab-scale biofilters packed with manganese ore sand and quartz sand were constructed to reveal the behavior in removing iron and manganese during the start-up period. Meanwhile,the removal mechanism of the two sands was also investigated by means of EDS,XPS,and SEM. With the influent iron( 2-3 mg·L~(-1)) and manganese( 0. 3-0. 6 mg·L~(-1)),the start-up operational results indicated that the quartz sand biofilter needed 15 and 30 d to achieve the removal of iron and manganese,respectively. The manganese ore sand only required 10 d to remove iron,while the effluent manganese was always below of 0. 1 mg·L~(-1). The results confirmed that the natural iron and manganese oxides coated on the manganese ore sand surface could explain its better removal behavior as compared to quartz sand. However,the generated iron oxide could also act as the adsorbent and catalyst like natural iron oxide,only when iron removal occurred in the quartz sand biofilter. The final product of iron removal was a complex consisting of divalent and trivalent iron,with a specific value of 1 ∶ 1. 44-1 ∶ 1. 54. Moreover,during the start-up period,manganese ore sand transformed manganese from divalent to trivalent by the catalytic effect,while the latter tended to be converted to the quadrivalent state under the bioactivity. The quartz sand could adsorb manganese but easily became saturated,and then the removal was dominated by bioactivity. The product generated by the manganese removal process was also a complex with the three valences. Moreover,the two complexes could coat onto the surface of the sands,but most of the iron complex was easily washed out of the filtering layer. Conversely,the manganese complex tended to coat onto the manganese ore sand surface or accumulate between the pores of quartz sand.
引文
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[13]李冬,曹瑞华,杨航,等.低温高铁锰氨氮地下水生物同池净化[J].环境科学,2017,38(12):5097-5105.Li D,Cao R H,Yang H,et al. Removal of high concentration of iron,manganese and ammonia nitrogen from low temperature groundwater using single bio-filter[J]. Environmental Science,2017,38(12):5097-5105.
[14] Li C Y,Wang S T,Du X P,et al. Immobilization of iron-and manganese-oxidizing bacteria with a biofilm-forming bacterium for the effective removal of iron and manganese from groundwater[J]. Bioresource Technology,2016,220:76-84.
[15] Li L P,Wei D B,Wei G H,et al. Product identification and the mechanisms involved in the transformation of cefazolin by birnessite(δ-MnO2)[J]. Chemical Engineering Journal,2017,320:116-123.
[16] Li Y,Wei D B,Du Y G. Oxidative transformation of levofloxacin byδ-MnO2:products,pathways and toxicity assessment[J].Chemosphere,2015,119:282-288.
[17]哈里德.几种锰氧化物纳米材料的合成、表征及其在颜料催化降解中的应用[D].武汉:华中科技大学,2011.Khalid A M A. Synthesis,characterization of several manganese oxides nanomaterials and their application in catalytic degradation of dyes[D]. Wuhan:Huazhong University of Science and Technology,2011.
[18] GB 5749-2006,生活饮用水卫生标准[S].
[19]蔡言安,李冬,曾辉平,等.生物滤池净化含铁锰高氨氮地下水试验研究[J].中国环境科学,2014,34(8):1993-1997.Cai Y A,Li D,Zeng H P,et al. Removal of iron,manganese and high ammonia from groundwater by biofilter[J]. China Environmental Science,2014,34(8):1993-1997.
[20] Remucal C K,Ginder-Vogel M. A critical review of the reactivity of manganese oxides with organic contaminants[J].Environmental Science:Processes&Impacts,2014,16(6):1247-1266.
[21] Tebo B M,Bargar J R,Clement B G,et al. Biogenic manganese oxides:properties and mechanisms of formation[J]. Annual Review of Earth and Planetary Sciences,2004,32:287-328.
[22]曾辉平,吕赛赛,杨航,等.铁锰泥除砷颗粒吸附剂对As(Ⅴ)的吸附去除[J].环境科学,2018,39(1):170-178.Zeng H P,LüS S,Yang H,et al. Arsenic(Ⅴ)removal by granular adsorbents made from backwashing residuals from biofilters for iron and manganese removal[J]. Environmental Science,2018,39(1):170-178.
[23]胡慧萍,王梦,丁治英,等. FT-IR、XPS和DFT研究水杨酸钠在针铁矿或赤铁矿上的吸附机理[J].物理化学学报,2016,32(8):2059-2068.Hu H P,Wang M,Ding Z Y,et al. FT-IR,XPS and DFT study of the adsorption mechanism of sodium salicylate onto goethite or hematite[J]. Acta Physico-Chimica Sinica,2016,32(8):2059-2068.
[24]李冬,曹瑞华,曾辉平,等.高铁锰氨氮地下水净化试验及氧化动力学[J].中国环境科学,2017,37(11):4140-4150.Li D,Cao R H,Zeng H P,et al. Analysis of the removal and oxidation kinetics of high-iron manganese and ammonia nitrogen from groundwater[J]. China Environmental Science,2017,37(11):4140-4150.
[25] Cheng Y,Huang T L,Sun Y K,et al. Catalytic oxidation removal of ammonium from groundwater by manganese oxides filter:performance and mechanisms[J]. Chemical Engineering Journal,2017,322:82-89.
[26] Sahabi D M,Takeda M,Suzuki I,et al. Removal of Mn2+from water by “aged” biofilter media:the role of catalytic oxides layers[J]. Journal of Bioscience and Bioengineering,2009,107(2):151-157.
[27] Guo Y M,Huang T L,Wen G,et al. The simultaneous removal of ammonium and manganese from groundwater by ironmanganese co-oxide filter film:the role of chemical catalytic oxidation for ammonium removal[J]. Chemical Engineering Journal,2017,308:322-329.
[2]白筱莉,黄廷林,张瑞峰,等.铁锰复合氧化膜同步去除地表水中氨氮和锰[J].中国环境科学,2017,37(12):4534-4540.Bai X L,Huang T L,Zhang R F,et al. The simultaneous removal of ammonium and manganese from surface water by ironmanganese co-oxides film[J]. China Environmental Science,2017,37(12):4534-4540.
[3]孙楠,谌燕丽,张颖,等.碳化稻壳-铁锰氧化菌耦合净化严寒村镇高铁锰地下水效能与机制[J].环境科学,2017,38(3):1028-1037.Sun N,Chen Y L,Zhang Y,et al. Efficiency and mechanism of purifying high iron-manganese from ground water in the cold villages and towns based on the coupling of rice husk and ironmanganese oxidizing bacteria[J]. Environmental Science,2017,38(3):1028-1037.
[4]卓瑞双,黄廷林,张瑞峰,等.磷酸盐对铁锰复合氧化膜去除地表水中氨氮的影响[J].环境科学,2018,39(1):137-144.Zhuo R S,Huang T L,Zhang R F,et al. Effect of phosphate on the ammonium removal performance of iron-manganese co-oxide film in surface water treatment[J]. Environmental Science,2018,39(1):137-144.
[5] Vries D,Bertelkamp C,Schoonenberg Kegel F,et al. Iron and manganese removal:recent advances in modelling treatment efficiency by rapid sand filtration[J]. Water Research,2017,109:35-45.
[6] Abu Hasan H,Sheikh Abdullah S R,Kamarudin S K,et al.Simultaneous NH+4-N and Mn2+removal from drinking water using a biological aerated filter system:effects of different aeration rates[J]. Separation and Purification Technology,2013,118:547-556.
[7] Tekerlekopoulou A G,Pavlou S,Vayenas D V. Removal of ammonium, iron and manganese from potable water in biofiltration units:a review[J]. Journal of Chemical Technology and Biotechnology,2013,88(5):751-773.
[8] Cai Y A,Li D,Liang Y W,et al. Effective start-up biofiltration method for Fe, Mn, and ammonia removal and bacterial community analysis[J]. Bioresource Technology,2015,176:149-155.
[9]菅之舆,常洋洋,王立新,等.化学预氧化耦合生物锰氧化对水中有机物的去除[J].环境科学,2018,39(3):1188-1194.Jian Z Y,Chang Y Y,Wang L X,et al. Removal of organic matter from water by chemical preoxidation coupled with biogenic manganese oxidation[J]. Environmental Science,2018,39(3):1188-1194.
[10] Patil D S,Chavan S M,Oubagaranadin J U K. A review of technologies for manganese removal from wastewaters[J]. Journal of Environmental Chemical Engineering,2016,4(1):468-487.
[11]蔡言安,李冬,梁雨雯,等.净化低温微污染含铁锰地下水的工艺运行调试[J].中国给水排水,2014,30(13):1-5.Cai Y A,Li D,Liang Y W,et al. Removal of iron,manganese and ammonia from low temperature groundwater[J]. China Water&Wastewater,2014,30(13):1-5.
[12] Cai Y A,Li D,Liang Y W,et al. Operational parameters required for the start-up process of a biofilter to remove Fe,Mn,and NH3-N from low-temperature groundwater[J]. Desalination and Water Treatment,2016,57(8):3588-3596.
[13]李冬,曹瑞华,杨航,等.低温高铁锰氨氮地下水生物同池净化[J].环境科学,2017,38(12):5097-5105.Li D,Cao R H,Yang H,et al. Removal of high concentration of iron,manganese and ammonia nitrogen from low temperature groundwater using single bio-filter[J]. Environmental Science,2017,38(12):5097-5105.
[14] Li C Y,Wang S T,Du X P,et al. Immobilization of iron-and manganese-oxidizing bacteria with a biofilm-forming bacterium for the effective removal of iron and manganese from groundwater[J]. Bioresource Technology,2016,220:76-84.
[15] Li L P,Wei D B,Wei G H,et al. Product identification and the mechanisms involved in the transformation of cefazolin by birnessite(δ-MnO2)[J]. Chemical Engineering Journal,2017,320:116-123.
[16] Li Y,Wei D B,Du Y G. Oxidative transformation of levofloxacin byδ-MnO2:products,pathways and toxicity assessment[J].Chemosphere,2015,119:282-288.
[17]哈里德.几种锰氧化物纳米材料的合成、表征及其在颜料催化降解中的应用[D].武汉:华中科技大学,2011.Khalid A M A. Synthesis,characterization of several manganese oxides nanomaterials and their application in catalytic degradation of dyes[D]. Wuhan:Huazhong University of Science and Technology,2011.
[18] GB 5749-2006,生活饮用水卫生标准[S].
[19]蔡言安,李冬,曾辉平,等.生物滤池净化含铁锰高氨氮地下水试验研究[J].中国环境科学,2014,34(8):1993-1997.Cai Y A,Li D,Zeng H P,et al. Removal of iron,manganese and high ammonia from groundwater by biofilter[J]. China Environmental Science,2014,34(8):1993-1997.
[20] Remucal C K,Ginder-Vogel M. A critical review of the reactivity of manganese oxides with organic contaminants[J].Environmental Science:Processes&Impacts,2014,16(6):1247-1266.
[21] Tebo B M,Bargar J R,Clement B G,et al. Biogenic manganese oxides:properties and mechanisms of formation[J]. Annual Review of Earth and Planetary Sciences,2004,32:287-328.
[22]曾辉平,吕赛赛,杨航,等.铁锰泥除砷颗粒吸附剂对As(Ⅴ)的吸附去除[J].环境科学,2018,39(1):170-178.Zeng H P,LüS S,Yang H,et al. Arsenic(Ⅴ)removal by granular adsorbents made from backwashing residuals from biofilters for iron and manganese removal[J]. Environmental Science,2018,39(1):170-178.
[23]胡慧萍,王梦,丁治英,等. FT-IR、XPS和DFT研究水杨酸钠在针铁矿或赤铁矿上的吸附机理[J].物理化学学报,2016,32(8):2059-2068.Hu H P,Wang M,Ding Z Y,et al. FT-IR,XPS and DFT study of the adsorption mechanism of sodium salicylate onto goethite or hematite[J]. Acta Physico-Chimica Sinica,2016,32(8):2059-2068.
[24]李冬,曹瑞华,曾辉平,等.高铁锰氨氮地下水净化试验及氧化动力学[J].中国环境科学,2017,37(11):4140-4150.Li D,Cao R H,Zeng H P,et al. Analysis of the removal and oxidation kinetics of high-iron manganese and ammonia nitrogen from groundwater[J]. China Environmental Science,2017,37(11):4140-4150.
[25] Cheng Y,Huang T L,Sun Y K,et al. Catalytic oxidation removal of ammonium from groundwater by manganese oxides filter:performance and mechanisms[J]. Chemical Engineering Journal,2017,322:82-89.
[26] Sahabi D M,Takeda M,Suzuki I,et al. Removal of Mn2+from water by “aged” biofilter media:the role of catalytic oxides layers[J]. Journal of Bioscience and Bioengineering,2009,107(2):151-157.
[27] Guo Y M,Huang T L,Wen G,et al. The simultaneous removal of ammonium and manganese from groundwater by ironmanganese co-oxide filter film:the role of chemical catalytic oxidation for ammonium removal[J]. Chemical Engineering Journal,2017,308:322-329.