不同晶型纳米MnO_2去除水中各形态砷的研究
摘要
本研究制备了不同晶型的纳米二氧化锰α-MnO2、β-MnO2和δ-MnO2,并对其吸附三价砷(As(Ⅲ))、五价砷(As(V))、一甲基砷(MMA)、二甲基砷(DMA)进行了研究。在对已有的除砷方法进行分析、研究的基础上,提出了以预氧化吸附技术为原理的除砷方法。研究以高锰酸钾、硫酸锰、过硫酸铵等为主要原料,制得新型吸附剂,用这种吸附剂可通过预氧化与吸附同时进行,将水中的各形态砷除去。实验对这种新型除砷吸附剂的除砷条件进行了探讨。采用静态吸附除砷实验,对除砷效果及影响因素进行了讨论。实验结果表明,纳米二氧化锰能有效地将含砷量为1.0mg/L的水降至我国饮水卫生标准0.01mg/L以下,吸附过程受pH、温度、砷初始浓度和时间的影响。与其他除砷吸附剂相比,纳米二氧化锰有良好的去除效果。吸附动力学研究表明：α-MnO2、β-MnO2和δ-Mn02对水中各形态砷的吸附符合Langmuir吸附等温方程。其中,α-MnO2对各形态砷的去除效果最好,可将含砷量高达2.0mg/L的水降至我国饮水卫生标准0.01mg/L以下。a-MnO2对As (Ⅲ)、As (Ⅴ)、MMA、DMA的最大吸附容量分别为103.09mg/g、106.38 mg/g、92.59 mg/g和95.24 mg/g。
实验研究表明,纳米二氧化锰除砷方法具有除砷效率高、原料易得、去除快速的优点,是一种很有发展前景的去除生活饮用水中的砷的方法。
This study prepared different types of nano-crystal manganese dioxidesα-MnO2、β-MnO2 andδ-MnO2, and the adsorption of Arsenite (As (Ⅲ)), Arsenate (As(Ⅴ)), Monomethylarsonous acid (MMA), Dimethylarsinic acid (DMA) byα-MnO2、β-MnO2 andδ-MnO2 was studied. Based on analysis of the existing methods of arsenic removal, this research presented an arsenic removal method classified as pre-oxidation and adsorption technology. The study prepared a new adsorbent with potassium permanganate, manganese sulfate, and ammonium persulfate as main raw materials, and this adsorbent can function as pre-oxidation and adsorption at the same time and remove various forms of arsenic from water. The experiments investigated the conditions of arsenic removal by this new arsenic removal adsorbent. The experiments of arsenic removal by static adsorption were conducted, and the effect and influence factors of the arsenic removal were discussed. The results showed that water of 1.0mg/L As can be effectively reduced to below 0.01mg/L by nano-manganese dioxide, which is the drinking water health standard in China. The adsorption process is affected by pH, temperature, initial arsenic concentration and time period. Compared with other arsenic removal adsorbents, the nano-crystal manganese dioxides achieve good removal effect. Adsorption kinetics study shows that:the absorption of various forms of arsenic byα-MnO2,β-MnO2 andδ-MnO2 is in accordance with Langmuir Adsorption Isotherm.α-MnO2 is the best in various forms of arsenic removal, andα-MnO2 can reduce water of 2.0mg/L As to below 0.01mg/L. The maximum adsorption capacity of As (Ⅲ), As (Ⅴ), MMA, DMA respectively are 103.09mg/g,106.38mg/g,92.59mg/g and 95.24mg/g.
The experimental studies have shown that nano-manganese dioxide method for arsenic removal has the advantages of high removal efficiency, easy-to-prepare reactants, and rapid removal process. Nano-manganese dioxide method for arsenic removal is a prospective removal method of arsenic in drinking water.
实验研究表明,纳米二氧化锰除砷方法具有除砷效率高、原料易得、去除快速的优点,是一种很有发展前景的去除生活饮用水中的砷的方法。
This study prepared different types of nano-crystal manganese dioxidesα-MnO2、β-MnO2 andδ-MnO2, and the adsorption of Arsenite (As (Ⅲ)), Arsenate (As(Ⅴ)), Monomethylarsonous acid (MMA), Dimethylarsinic acid (DMA) byα-MnO2、β-MnO2 andδ-MnO2 was studied. Based on analysis of the existing methods of arsenic removal, this research presented an arsenic removal method classified as pre-oxidation and adsorption technology. The study prepared a new adsorbent with potassium permanganate, manganese sulfate, and ammonium persulfate as main raw materials, and this adsorbent can function as pre-oxidation and adsorption at the same time and remove various forms of arsenic from water. The experiments investigated the conditions of arsenic removal by this new arsenic removal adsorbent. The experiments of arsenic removal by static adsorption were conducted, and the effect and influence factors of the arsenic removal were discussed. The results showed that water of 1.0mg/L As can be effectively reduced to below 0.01mg/L by nano-manganese dioxide, which is the drinking water health standard in China. The adsorption process is affected by pH, temperature, initial arsenic concentration and time period. Compared with other arsenic removal adsorbents, the nano-crystal manganese dioxides achieve good removal effect. Adsorption kinetics study shows that:the absorption of various forms of arsenic byα-MnO2,β-MnO2 andδ-MnO2 is in accordance with Langmuir Adsorption Isotherm.α-MnO2 is the best in various forms of arsenic removal, andα-MnO2 can reduce water of 2.0mg/L As to below 0.01mg/L. The maximum adsorption capacity of As (Ⅲ), As (Ⅴ), MMA, DMA respectively are 103.09mg/g,106.38mg/g,92.59mg/g and 95.24mg/g.
The experimental studies have shown that nano-manganese dioxide method for arsenic removal has the advantages of high removal efficiency, easy-to-prepare reactants, and rapid removal process. Nano-manganese dioxide method for arsenic removal is a prospective removal method of arsenic in drinking water.
引文
[1]沈雁峰,孙殿军,赵新华,等.中国饮水型地方性砷中毒病区和高砷区水砷筛查报告[J].中国地方病学杂志,2005,24(2)：172-175.
[2]马文成,孙靖,刘晓化,等.饮水除砷方法的研究进展[J].中国地方病防治杂志,2004,19(5)：284.
[3]刘巧玲.饮用水除砷处理方法研究[J].建筑建材装饰,2009,10(58)：131-133.
[4]石荣,贾永锋,王承智.土壤矿物质吸附砷的研究进展[J].土壤通报,2007,38(3)：584-589.
[5]杨凡.关于膜技术在饮用水除砷处理中的研究与应用[J].科技资讯,2009,18：7-8.
[6]Goh KH, Lim TT, Dong Z. Enhanced arsenic removal by hydrothermally treated nanocrystalline Mg/Al layered double hydroxide with nitrate intercalation[J]. Environmental Science and Technology,2009,43(7): 2537-2543.
[7]Sabbatini P, Rossi F, Thern G, et al. Iron oxide adsorbers for arsenic removal: A low cost treatment for rural areas and mobile applications. Desalination,2009, 248(1-3):184-192.
[8]肖亚兵,钱抄华,黄进泉,等.纳米二氧化钛对砷(Ⅲ)砷(Ⅴ)吸附性能的研究[J].分析科学学报,2003,19(2)：172-174.
[9]喻德忠,邹菁,艾军.纳米二氧化锆对砷(Ⅲ)和砷(Ⅴ)的吸附性质研究[J].武汉化工学院学报,2004,26(3)：1-3.
[10]Park H, Kanel SR, Choi HC. Arsenic Removal by Nano-scale Zero Valent Iron and how it is Affected by Natural Organic Matter[J]. Environmental Applications of Nanoscale and Microscale Reactive Metal Particles,2009,1027(8):135-161.
[11]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,22(4)：743-747.
[12]Yang ZH, Zhang YC, Zhang WX, et al. Nanorods of manganese oxides: Synthesis, characterization and catalytic application[J]. Journal of Solid State Chemistry,2006,179(2006):679-684.
[13]Xi GC, Peng YY, Zhu YC, et al. Preparation of β-MnO2 nanorods through a y-MnOOH precursor route[J]. Material Research Bulletin,2004,39(2004): 1641-1648.
[14]Hill LI, Verbaere A, Guyomard D. MnO2(α-,β-,γ-) compounds prepared by hydrothermal-electrochemical synthesis:characterization, morphology, and lithium insertion behavior[J]. Journal of Power Sources,119-121 (2003): 226-231.
[15]张月,王金霞,高艳阳.纳米Mn02的低热固相合成[J].化学工程师,2005,117(6)：20-21.
[16]李英品,周晓荃,周慧静等.纳米结构MnO2的水热合成、晶型及形貌变化[J].高等学校化学学报,2007,28(7)：1223-1226.
[17]张启卫,钟建生,黄行康等.δ-MnO2的制备与性能[J].应用化学,2005,22(8)：908-910.
[18]张萃,李亚峰,田西满.活性炭吸附处理含砷废水的研究[J].工业安全与环保,2009,35(12)：6-8.
[19]梁慧峰,马子川,张杰,等.新生态Mn02对水中As(V)的吸附作用研究[J].安全与环境学报,2005,5(1)：50-53.
[20]梁慧峰,马子川,张杰,等.新生态二氧化锰对水中三价砷去除作用的研究[J].环境污染与防治,2005,27(3)：168-172.
[21]杨远盛.阴离子粘土合成及吸附砷(V)的研究[D].合肥工业大学环境工程专业硕士学位论文,2005.
[22]刘懿颉,甘义群,王焰新,等.铁矿渣去除水中砷实验研究[J].环境科学与技术,2009,33(3)：166-170.
[23]张岚,岳银玲,李淑敏.铁屑对饮水中砷的去除效果评价[J].卫生研究,2008,37(3)：347-348.
[1]沈雁峰,孙殿军,赵新华,等.中国饮水型地方性砷中毒病区和高砷区水砷筛查报告[J].中国地方病学杂志,2005,24(2)：172-175.
[2]马文成,孙靖,刘晓化,等.饮水除砷方法的研究进展[J].中国地方病防治杂志,2004,19(5)：284.
[3]刘巧玲.饮用水除砷处理方法研究[J].建筑建材装饰,2009,10(58)：131-133.
[4]Jain A, Sharma VK, Mbuya OS. Removal of arsenite by Fe(Ⅵ), Fe(Ⅵ)/Fe(Ⅲ), and Fe(Ⅵ)/Al(Ⅲ) salts:Effect of pH and anions[J]. Journal of Hazardous Materials,2009,169(1-3):339-344.
[5]Baskan MB, Pala A. Determination of arsenic removal efficiency by ferric ions using response surface methodology [J]. Journal of Hazardous Materials,2009, 166(2-3):796-801.
[6]Song S, Lopez-Valdivieso A, Hernandez-Campos DJ, et al. Arsenic removal from high-arsenic water by enhaced coagulation with ferric ions and coarse calcite [J]. Water Research,2006,40:364-372.
[7]汪洪洋,吴涛.活性氧化铝吸附在水体砷污染应急处置中的应用[J].环境科技,2009,22(5)：28-31.
[8]Mohan D, Pittman CU. Arsenic removal from water/wastewater using adsorbents-A critical review. Journal of Hazardous Materials,2007,142(1-2): 1-53.
[9]陈云嫩.废麦糟生物吸附剂深度净化水体中砷、镉的研究[D].中南大学冶金环境工程专业硕士论文,2009.
[10]石荣,贾永锋,王承智.土壤矿物质吸附砷的研究进展[J].土壤通报,2007,38(3)：584-589.
[11]Biterna M, Antonoglou L, Lazou E, et al. Arsenite removal from waters by zero valent iron:Batch and column tests [J]. Chemosphere,2010,78(1):7-12.
[12]Goh KH, Lim TT, Dong Z. Enhanced arsenic removal by hydrothermally treated nanocrystalline Mg/Al layered double hydroxide with nitrate intercalation [J]. Environmental Science and Technology,2009,43(7): 2537-2543.
[13]Sabbatini P, Rossi F, Thern G, et al. Iron oxide adsorbers for arsenic removal: A low cost treatment for rural areas and mobile applications. Desalination, 2009,248(1-3):184-192.
[14]Anirudhan TS, Unnithan MR. Arsenic (V) removal from aqueous solutions using an anion exchanger derived from coconut coir pith and its recovery [J]. Chemosphere,2007,66:60-66.
[15]Zhang XZ, Jiang K, Tian ZB, et al. Removal of arsenic in water by an ion-exchange fiber with amino groups [J]. Journal of Applied Polymer Science, 2008,110(6):3934-3940.
[16]宫慧芝,高双,罗姚佳,等.环境中条件致病菌对无机砷毒性降解作用[J].中国公共卫生,2008,24(4)：454.
[17]Balasubramanian N, Kojima T, Basha A, et al. Removal of arsenic from aqueous solution using electrocoagulation [J]. Journal of Hazardous Materials, 2009,167(1-3):966-969.
[18]Zongo I, Maiga AH, Wethe J, et al. Electrocoagulation for the treatment of textile wastewaters with Al or Fe electrodes:Compared variations of COD levels, turbidity and absorbance [J]. Journal of Hazardous Materials,2009, 169(1-3):70-76.
[19]杨凡.关于膜技术在饮用水除砷处理中的研究与应用[J].科技资讯,2009,18：7-8.
[20]Wang XW, Liu WJ, Li DS, et al. Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane:effects of arsenic concentration, pH, and co-existing ions[J]. Frontiers of Environmental Science & Engineering in China,2009,3(4):428-433.
[21]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,22(4)：743-747.
[22]Park H, Kanel SR, Choi HC. Arsenic Removal by Nano-scale Zero Valent Iron and how it is Affected by Natural Organic Matter [J]. Environmental Applications of Nanoscale and Microscale Reactive Metal Particles,2009, 1027(8):135-161.
[2]马文成,孙靖,刘晓化,等.饮水除砷方法的研究进展[J].中国地方病防治杂志,2004,19(5)：284.
[3]刘巧玲.饮用水除砷处理方法研究[J].建筑建材装饰,2009,10(58)：131-133.
[4]石荣,贾永锋,王承智.土壤矿物质吸附砷的研究进展[J].土壤通报,2007,38(3)：584-589.
[5]杨凡.关于膜技术在饮用水除砷处理中的研究与应用[J].科技资讯,2009,18：7-8.
[6]Goh KH, Lim TT, Dong Z. Enhanced arsenic removal by hydrothermally treated nanocrystalline Mg/Al layered double hydroxide with nitrate intercalation[J]. Environmental Science and Technology,2009,43(7): 2537-2543.
[7]Sabbatini P, Rossi F, Thern G, et al. Iron oxide adsorbers for arsenic removal: A low cost treatment for rural areas and mobile applications. Desalination,2009, 248(1-3):184-192.
[8]肖亚兵,钱抄华,黄进泉,等.纳米二氧化钛对砷(Ⅲ)砷(Ⅴ)吸附性能的研究[J].分析科学学报,2003,19(2)：172-174.
[9]喻德忠,邹菁,艾军.纳米二氧化锆对砷(Ⅲ)和砷(Ⅴ)的吸附性质研究[J].武汉化工学院学报,2004,26(3)：1-3.
[10]Park H, Kanel SR, Choi HC. Arsenic Removal by Nano-scale Zero Valent Iron and how it is Affected by Natural Organic Matter[J]. Environmental Applications of Nanoscale and Microscale Reactive Metal Particles,2009,1027(8):135-161.
[11]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,22(4)：743-747.
[12]Yang ZH, Zhang YC, Zhang WX, et al. Nanorods of manganese oxides: Synthesis, characterization and catalytic application[J]. Journal of Solid State Chemistry,2006,179(2006):679-684.
[13]Xi GC, Peng YY, Zhu YC, et al. Preparation of β-MnO2 nanorods through a y-MnOOH precursor route[J]. Material Research Bulletin,2004,39(2004): 1641-1648.
[14]Hill LI, Verbaere A, Guyomard D. MnO2(α-,β-,γ-) compounds prepared by hydrothermal-electrochemical synthesis:characterization, morphology, and lithium insertion behavior[J]. Journal of Power Sources,119-121 (2003): 226-231.
[15]张月,王金霞,高艳阳.纳米Mn02的低热固相合成[J].化学工程师,2005,117(6)：20-21.
[16]李英品,周晓荃,周慧静等.纳米结构MnO2的水热合成、晶型及形貌变化[J].高等学校化学学报,2007,28(7)：1223-1226.
[17]张启卫,钟建生,黄行康等.δ-MnO2的制备与性能[J].应用化学,2005,22(8)：908-910.
[18]张萃,李亚峰,田西满.活性炭吸附处理含砷废水的研究[J].工业安全与环保,2009,35(12)：6-8.
[19]梁慧峰,马子川,张杰,等.新生态Mn02对水中As(V)的吸附作用研究[J].安全与环境学报,2005,5(1)：50-53.
[20]梁慧峰,马子川,张杰,等.新生态二氧化锰对水中三价砷去除作用的研究[J].环境污染与防治,2005,27(3)：168-172.
[21]杨远盛.阴离子粘土合成及吸附砷(V)的研究[D].合肥工业大学环境工程专业硕士学位论文,2005.
[22]刘懿颉,甘义群,王焰新,等.铁矿渣去除水中砷实验研究[J].环境科学与技术,2009,33(3)：166-170.
[23]张岚,岳银玲,李淑敏.铁屑对饮水中砷的去除效果评价[J].卫生研究,2008,37(3)：347-348.
[1]沈雁峰,孙殿军,赵新华,等.中国饮水型地方性砷中毒病区和高砷区水砷筛查报告[J].中国地方病学杂志,2005,24(2)：172-175.
[2]马文成,孙靖,刘晓化,等.饮水除砷方法的研究进展[J].中国地方病防治杂志,2004,19(5)：284.
[3]刘巧玲.饮用水除砷处理方法研究[J].建筑建材装饰,2009,10(58)：131-133.
[4]Jain A, Sharma VK, Mbuya OS. Removal of arsenite by Fe(Ⅵ), Fe(Ⅵ)/Fe(Ⅲ), and Fe(Ⅵ)/Al(Ⅲ) salts:Effect of pH and anions[J]. Journal of Hazardous Materials,2009,169(1-3):339-344.
[5]Baskan MB, Pala A. Determination of arsenic removal efficiency by ferric ions using response surface methodology [J]. Journal of Hazardous Materials,2009, 166(2-3):796-801.
[6]Song S, Lopez-Valdivieso A, Hernandez-Campos DJ, et al. Arsenic removal from high-arsenic water by enhaced coagulation with ferric ions and coarse calcite [J]. Water Research,2006,40:364-372.
[7]汪洪洋,吴涛.活性氧化铝吸附在水体砷污染应急处置中的应用[J].环境科技,2009,22(5)：28-31.
[8]Mohan D, Pittman CU. Arsenic removal from water/wastewater using adsorbents-A critical review. Journal of Hazardous Materials,2007,142(1-2): 1-53.
[9]陈云嫩.废麦糟生物吸附剂深度净化水体中砷、镉的研究[D].中南大学冶金环境工程专业硕士论文,2009.
[10]石荣,贾永锋,王承智.土壤矿物质吸附砷的研究进展[J].土壤通报,2007,38(3)：584-589.
[11]Biterna M, Antonoglou L, Lazou E, et al. Arsenite removal from waters by zero valent iron:Batch and column tests [J]. Chemosphere,2010,78(1):7-12.
[12]Goh KH, Lim TT, Dong Z. Enhanced arsenic removal by hydrothermally treated nanocrystalline Mg/Al layered double hydroxide with nitrate intercalation [J]. Environmental Science and Technology,2009,43(7): 2537-2543.
[13]Sabbatini P, Rossi F, Thern G, et al. Iron oxide adsorbers for arsenic removal: A low cost treatment for rural areas and mobile applications. Desalination, 2009,248(1-3):184-192.
[14]Anirudhan TS, Unnithan MR. Arsenic (V) removal from aqueous solutions using an anion exchanger derived from coconut coir pith and its recovery [J]. Chemosphere,2007,66:60-66.
[15]Zhang XZ, Jiang K, Tian ZB, et al. Removal of arsenic in water by an ion-exchange fiber with amino groups [J]. Journal of Applied Polymer Science, 2008,110(6):3934-3940.
[16]宫慧芝,高双,罗姚佳,等.环境中条件致病菌对无机砷毒性降解作用[J].中国公共卫生,2008,24(4)：454.
[17]Balasubramanian N, Kojima T, Basha A, et al. Removal of arsenic from aqueous solution using electrocoagulation [J]. Journal of Hazardous Materials, 2009,167(1-3):966-969.
[18]Zongo I, Maiga AH, Wethe J, et al. Electrocoagulation for the treatment of textile wastewaters with Al or Fe electrodes:Compared variations of COD levels, turbidity and absorbance [J]. Journal of Hazardous Materials,2009, 169(1-3):70-76.
[19]杨凡.关于膜技术在饮用水除砷处理中的研究与应用[J].科技资讯,2009,18：7-8.
[20]Wang XW, Liu WJ, Li DS, et al. Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane:effects of arsenic concentration, pH, and co-existing ions[J]. Frontiers of Environmental Science & Engineering in China,2009,3(4):428-433.
[21]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,22(4)：743-747.
[22]Park H, Kanel SR, Choi HC. Arsenic Removal by Nano-scale Zero Valent Iron and how it is Affected by Natural Organic Matter [J]. Environmental Applications of Nanoscale and Microscale Reactive Metal Particles,2009, 1027(8):135-161.