改性纤维快速氧化除锰研究
|
摘要
在水污染日益严重的今天,地下水等重要水源中常含有过量的锰;由于铁性质与锰相近,铁锰往往同时存在,严重影响其使用价值。一方面,锰的过量摄入对人体有慢性毒害。另一方面,锰和铁异味大,还引起色度。
除锰一直是一项重要的研究课题,人们已在这一领域取得不少成果。但锰氧化需要的氧化电位较高,难以完全被氧化分离去除,如何在极短时间内实现锰的高效去除使其符合现代社会的需要,仍是一个急需解决的问题。
顺应膜处理这一新兴水处理技术的发展与普及,本文通过快速高效氧化处理与膜高效分离性能结合,试探索一条除锰的新路。通过对聚合纤维进行金属氧化物改性处理,利用其吸附、催化氧化等机能,实现次氯酸钠催化氧化和高锰酸钠强氧化下的快速除锰。
试验证明改性纤维无需熟化即能达到甚至超过成熟锰砂的吸附效果,尤其对高锰浓度吸附更有优势。改性纤维中锰氧化物的含量与对锰吸附能力呈正比上升关系,但与铁的吸附量无关。改性纤维对铁的吸附要比锰快,吸附量也更大,在多离子条件下吸附具有选择性,吸附量依次为Fe>Mn>NH4-N>K。改性纤维的吸附等温线符合Freundlich吸附式,对锰的吸附符合单配位反应。
改性纤维能提高次氯酸钠催化氧化锰去除率20倍,强氧化锰去除率20%。在催化氧化、强氧化除锰过程的影响分析基础上,证明了快速除锰的有效性和可行性。
在催化氧化过程中,改性纤维上的锰氧化物起着MnO(OH)2自催化剂的作用和良好的吸附作用。通过添加改性纤维,能达到反应时间15s时锰去除率95%以上,铁去除率100%。铁锰同时存在时去除更
Nowadays, the water pollution is so serious that vital water resource such as groundwater is polluted by Manganese; since Iron is similar with Manganese in characters, they always exist geological simultaneity which has strong negative impact on the application of water resource.
The removal of Manganese is always a key issue and plenty of achievement has been accomplished. But because of the high oxidation potential from Manganese (sub 2) ion to Manganese oxide, it is quite hard to be completely oxidized so as to be removed. Therefore, how to remove Manganese in a very short reaction time in order to meet the demand of modern society is still an urgent task.
Combining the membrane treatment– the sunrise technology in water treatment and high-efficiency oxidation, we try to find a new solution for the removal of Manganese.
Metal oxide is coated on the polymeric fiber to produce metal oxide coated fiber (MOCF). With the adsorption and catalysis ability of MOCF, oxidant such as NaClO(in catalysis-oxidation), NaMnO4 and KMnO4(in strong oxidation) is dosed to realize removal of manganese in a few seconds.
Without acclimatization, MOCF is proven to have equal even better adsorption capacity than mature Manganese-Sand, especially in high Manganese concentration. MOCF also have the selective adsorption ability in multi-ion raw water, with the adsorption capacity Fe>Mn> NH4-N>K. The sorption of Manganese obeys the Freundlich Sorption Isotherm, and acts as monodentate surface complex.
MOCF can improve the removal rate of Manganese in catalysis- oxidation by 20 times, and that in strong oxidation by 20%; the flexibility
除锰一直是一项重要的研究课题,人们已在这一领域取得不少成果。但锰氧化需要的氧化电位较高,难以完全被氧化分离去除,如何在极短时间内实现锰的高效去除使其符合现代社会的需要,仍是一个急需解决的问题。
顺应膜处理这一新兴水处理技术的发展与普及,本文通过快速高效氧化处理与膜高效分离性能结合,试探索一条除锰的新路。通过对聚合纤维进行金属氧化物改性处理,利用其吸附、催化氧化等机能,实现次氯酸钠催化氧化和高锰酸钠强氧化下的快速除锰。
试验证明改性纤维无需熟化即能达到甚至超过成熟锰砂的吸附效果,尤其对高锰浓度吸附更有优势。改性纤维中锰氧化物的含量与对锰吸附能力呈正比上升关系,但与铁的吸附量无关。改性纤维对铁的吸附要比锰快,吸附量也更大,在多离子条件下吸附具有选择性,吸附量依次为Fe>Mn>NH4-N>K。改性纤维的吸附等温线符合Freundlich吸附式,对锰的吸附符合单配位反应。
改性纤维能提高次氯酸钠催化氧化锰去除率20倍,强氧化锰去除率20%。在催化氧化、强氧化除锰过程的影响分析基础上,证明了快速除锰的有效性和可行性。
在催化氧化过程中,改性纤维上的锰氧化物起着MnO(OH)2自催化剂的作用和良好的吸附作用。通过添加改性纤维,能达到反应时间15s时锰去除率95%以上,铁去除率100%。铁锰同时存在时去除更
Nowadays, the water pollution is so serious that vital water resource such as groundwater is polluted by Manganese; since Iron is similar with Manganese in characters, they always exist geological simultaneity which has strong negative impact on the application of water resource.
The removal of Manganese is always a key issue and plenty of achievement has been accomplished. But because of the high oxidation potential from Manganese (sub 2) ion to Manganese oxide, it is quite hard to be completely oxidized so as to be removed. Therefore, how to remove Manganese in a very short reaction time in order to meet the demand of modern society is still an urgent task.
Combining the membrane treatment– the sunrise technology in water treatment and high-efficiency oxidation, we try to find a new solution for the removal of Manganese.
Metal oxide is coated on the polymeric fiber to produce metal oxide coated fiber (MOCF). With the adsorption and catalysis ability of MOCF, oxidant such as NaClO(in catalysis-oxidation), NaMnO4 and KMnO4(in strong oxidation) is dosed to realize removal of manganese in a few seconds.
Without acclimatization, MOCF is proven to have equal even better adsorption capacity than mature Manganese-Sand, especially in high Manganese concentration. MOCF also have the selective adsorption ability in multi-ion raw water, with the adsorption capacity Fe>Mn> NH4-N>K. The sorption of Manganese obeys the Freundlich Sorption Isotherm, and acts as monodentate surface complex.
MOCF can improve the removal rate of Manganese in catalysis- oxidation by 20 times, and that in strong oxidation by 20%; the flexibility
引文
[1] 高洁、张杰, 地下水除铁除锰技术研究, 哈尔滨商业大学学报自然科学版, 2003,19(5):546-548.
[2] BOUWER EJ, CROUE PB. Biological processes in drinking water treatment J .JOURNAL AWWA, 1998, 9 : 82 - 93.
[3] 日本水道協会水道統計編纂専門委員会,水道統計の経年分析,水道協会雑誌,1998,第 767 号, pp46-88.
[4] 厚生省監修:平成 8 年度水道統計(水質編),(社)日本水道協会,1998,pp2-3.
[5] 张杰、戴镇生,地下水除锰除铁现代观,给水排水,1996,22(10):13-16.
[6] 水道維持管理指針, 日本水道協会,1998,pp130.
[7] 刘志琪、梁相钦、宁瑞珠等,CJ/T206-2005,城市供水水质标准,建设部.
[8] 李梅玲、张锡根、阎葆瑞等,GB/T 14848-93,中华人民共和国国家标准地下水质量标准, 地质矿产部.
[9] 水質基準，平成 4 年 12 月 21 日,厚生省令第 23 号.
[10] 无机化学(第二版), 华南工学院,1985 年.
[11] Larry D. Benefield, Joseph F. Judkins. Jr. Process Chemistry for Water and Wastewater treatment, Prenctice-Hall, Inc., 1982.
[12] 高井雄,用水の除铁?除マンガン処理(2),用水と廃水，1987,24(3):14-21.
[13] WHO 飲料水水質ガイドライン(第 2 版),日本水道協会,1994.
[14] 张吉库、傅金祥、周华斌,地下水除铁除锰技术与发展趋势,沈阳建筑工程学院学报自然科学版,2003.7,119(13).
[15] 藤田贤二,曝気ろ過池によるマンガンの除去,水道協会雑誌,1983,第 703 号,pp31-39.
[16] Gregory Dean, Kenneth Carlson, Oxidation of Dissolved Manganese in Natural Waters, Proc AWWA Annu Conf., 1996,1996(c),pp453-470.
[17] William R.Knocke, Kinetics of Manganese and Iron Oxidation by Potassium Permanganate and Chlorine Dioxide, Journal AWWA, June 1991, pp80-87.
[18] 杨宏涛、陈萍、霍俊萍,关于地下水除铁除锰技术的探讨,黑龙江水利科技,2003,No3:32-33.
[19] 陆少鸣、朱争亮、杨立,臭氧—生物活性炭工艺处理含锰源水,中国给水排水,2004 Vol.20:53-54.
[20] 高井雄,中西弘,用水の除铁?除マンガン処理,産業用水調査会，1987.
[21] 李圭白,地下水除铁除锰的若干新发展,给水排水,1983.3.
[22] 范懋功,地下水接触氧化除铁除锰中催化剂的形态,中国给水排水,1985.3.
[23] 福永明,高井雄,`接触ろ過マンガン法における除マンガン触媒.水道協会雑誌, 1982,第578 号,pp42-50.
[24] 松井佳彦,丹保宪仁等,塩素-マンガン砂法によるマンガン除去の動力学 I,1986,第621 号,pp31-43.
[25] 松井佳彦,丹保宪仁等,塩素-マンガン砂法によるマンガン除去の動力学 II,1986,第622 号,pp15-22.
[26] 李波、梁丽娜,地热水除铁除锰工艺研究,环境保护科学,2001,27(4):21-22.
[27] 鲍志戎等,自来水厂除锰滤料的催化活性分析,环境科学,1997,18(1):38-41.
[28] 中国市政工程东北设计研究院,生物固锰除锰成套技术研究报告,2001.
[29] 松下滋等,铁バクテリアによる除鉄?除マンガン装置の開発,工業用水,1996,第 459号,pp2-10.
[30] Naeem Qureshi, Al Bames, Pilot Study Points to Iron/Manganese Removal, Water Engineering & Management, 1994,pp18-20.
[31] 徐荣安,膜技术在饮用水深度处理中的应用,水处理技术,1999 (10).
[32] 蒋绍阶、石长恩、江志贤,膜过滤技术用于饮用水消毒可行性探讨,重庆环境科学,2003,25(4):42-45.
[33] 小规模水道における膜ろ過施設導入ガイドライン，水道技術研究センター,1997,pp16-17.
[34] 三宅伸也,琵琶湖水を原水とする UF 膜ろ過净水プロセスの水質净化性能,土木学会第 49 回講演会講演集,1994,pp1010-1011.
[35] 吉川慎一,マンガンにより闭塞した中空糸膜の薬液洗净方法の検討,第 5 回卫生工学论文集,北海道大学卫生工学会,1997,pp252-255.
[36] 神保吉次,净水处理における膜利用技術の開発,膜分離技術の水処理への応用，日本水環境学会関西支部,1993,pp21-23.
[37] Iron and manganese removal by a membrane filtration system Jimbo, Y; Goto, K Water Science & Technology: Water Supply [Water Sci. Techno. Water Supply]. 2001, Vol. 1, no. 5, pp. 357-364.
[38] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理に関する基礎研究,環境工学研究論文集,1993,Vol30,pp311-316
[39] 後藤光亀等,高濃度鉄?マンガン含有地下水の連続膜ろ過に関する実験的研究,環境工学研究論文集,1994,Vol31,pp161-166.
[40] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理の化学洗浄特性，環境工学研究論文集,1997,Vol34, pp102-107.
[41] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理の化学洗浄特性，環境工学研究論文集,1995,Vol32.
[42] Baldwin, B.S., Jacobsen, D.A. Iron and manganese removal by membrane filtration - Seekonk Water District experience. Journal of New England Water Works Association. Vol. 117, no. 1, pp. 15-21. Mar. 2003
[43] Carl Schneider, Robert P. Huehmer, Peter Johns. Microfiltration for Removal of Manganese from Surface Water.
[44] Lee, Se-Han; Lee, Shun-Hwa; Lee, Chul-Hee. Riverbank Filtration: Removal of Iron, Manganese and Hardness. Journal of Water and Environment Technology, J. Water Environ. Technol. 2003, Vol. 1, no. 2, pp. 133-140.
[45] Hans S. Posselt and Frederick J. Anderson, Walter J. Weber, Jr. Cation Sorption on Colloidal Hydrous Manganese Dioxide,1998.
[46] Knocke W.R., Hamon, J. R.. Soluble manganese removal on oxide-coated filter media. Journal American Water Works Association. 1988, 80(12), pp65-70.
[47] Knocke, W. R., Occiano, S. C., Hungate, R. Removal of soluble manganese by oxide-coatedfilter media: sorption rate and removal mechanism issues. Journal American Water Works Association, 1991, 83(8), 64-69.
[48] 邓慧萍,改性滤料在给水处理中的应用研究,同济大学学报,1995,23(4):427-431.
[49] Dingfang Liu, John J. Sansalone, Jonathan Kolich. Divalent Heavy Metal Removal Using Manganese Oxide Coated. WER and WEFTEC Research Symposium, 05 June 2001.
[50] 朱步遥、赵振国,界面化学基础,北京,化学工业出版社,1996.
[51] 章燕豪,吸附作用,上海科技技术出版社,1989.
[52] 汤鸿霄,水废水化学基础,中国建筑工业出版社,1997.
[53] 李攀,复合改性滤料强化除锰的试验研究,[学位论文], 哈尔滨, 哈尔滨工业大学, 2002.
[54] é.S. Pessim, L.C.C. Hahne, M.M.R. Castro. HEAVY METALS ADSORPTION BY MANGANESE DIOXIDE FROM AQUEOUS SOLUTIONS.Brazilian Congress of Phase Eguilibrium and Fluid Properties for Chemical Process Design.
[55] Dingfang Liu; John J. Sansalone, Cartledge. Adsorption Characteristics of Oxide Coated Buoyant Media for Storm Water Treatment. II: Equilibria and Kinetic Models. JOURNAL OF ENVIRONMENTAL ENGINEERING (C) ASCE / APRIL 2004,pp383-390
[56] Lee, Se-Han; Lee, Shun-Hwa; Park, Yung-Kyu. Riverbank Filtration: Removal of Iron, Manganese and Hardness. Journal of Water and Environment Technology. 2003. Vol. 1, no. 2, pp. 133-140.
[2] BOUWER EJ, CROUE PB. Biological processes in drinking water treatment J .JOURNAL AWWA, 1998, 9 : 82 - 93.
[3] 日本水道協会水道統計編纂専門委員会,水道統計の経年分析,水道協会雑誌,1998,第 767 号, pp46-88.
[4] 厚生省監修:平成 8 年度水道統計(水質編),(社)日本水道協会,1998,pp2-3.
[5] 张杰、戴镇生,地下水除锰除铁现代观,给水排水,1996,22(10):13-16.
[6] 水道維持管理指針, 日本水道協会,1998,pp130.
[7] 刘志琪、梁相钦、宁瑞珠等,CJ/T206-2005,城市供水水质标准,建设部.
[8] 李梅玲、张锡根、阎葆瑞等,GB/T 14848-93,中华人民共和国国家标准地下水质量标准, 地质矿产部.
[9] 水質基準，平成 4 年 12 月 21 日,厚生省令第 23 号.
[10] 无机化学(第二版), 华南工学院,1985 年.
[11] Larry D. Benefield, Joseph F. Judkins. Jr. Process Chemistry for Water and Wastewater treatment, Prenctice-Hall, Inc., 1982.
[12] 高井雄,用水の除铁?除マンガン処理(2),用水と廃水，1987,24(3):14-21.
[13] WHO 飲料水水質ガイドライン(第 2 版),日本水道協会,1994.
[14] 张吉库、傅金祥、周华斌,地下水除铁除锰技术与发展趋势,沈阳建筑工程学院学报自然科学版,2003.7,119(13).
[15] 藤田贤二,曝気ろ過池によるマンガンの除去,水道協会雑誌,1983,第 703 号,pp31-39.
[16] Gregory Dean, Kenneth Carlson, Oxidation of Dissolved Manganese in Natural Waters, Proc AWWA Annu Conf., 1996,1996(c),pp453-470.
[17] William R.Knocke, Kinetics of Manganese and Iron Oxidation by Potassium Permanganate and Chlorine Dioxide, Journal AWWA, June 1991, pp80-87.
[18] 杨宏涛、陈萍、霍俊萍,关于地下水除铁除锰技术的探讨,黑龙江水利科技,2003,No3:32-33.
[19] 陆少鸣、朱争亮、杨立,臭氧—生物活性炭工艺处理含锰源水,中国给水排水,2004 Vol.20:53-54.
[20] 高井雄,中西弘,用水の除铁?除マンガン処理,産業用水調査会，1987.
[21] 李圭白,地下水除铁除锰的若干新发展,给水排水,1983.3.
[22] 范懋功,地下水接触氧化除铁除锰中催化剂的形态,中国给水排水,1985.3.
[23] 福永明,高井雄,`接触ろ過マンガン法における除マンガン触媒.水道協会雑誌, 1982,第578 号,pp42-50.
[24] 松井佳彦,丹保宪仁等,塩素-マンガン砂法によるマンガン除去の動力学 I,1986,第621 号,pp31-43.
[25] 松井佳彦,丹保宪仁等,塩素-マンガン砂法によるマンガン除去の動力学 II,1986,第622 号,pp15-22.
[26] 李波、梁丽娜,地热水除铁除锰工艺研究,环境保护科学,2001,27(4):21-22.
[27] 鲍志戎等,自来水厂除锰滤料的催化活性分析,环境科学,1997,18(1):38-41.
[28] 中国市政工程东北设计研究院,生物固锰除锰成套技术研究报告,2001.
[29] 松下滋等,铁バクテリアによる除鉄?除マンガン装置の開発,工業用水,1996,第 459号,pp2-10.
[30] Naeem Qureshi, Al Bames, Pilot Study Points to Iron/Manganese Removal, Water Engineering & Management, 1994,pp18-20.
[31] 徐荣安,膜技术在饮用水深度处理中的应用,水处理技术,1999 (10).
[32] 蒋绍阶、石长恩、江志贤,膜过滤技术用于饮用水消毒可行性探讨,重庆环境科学,2003,25(4):42-45.
[33] 小规模水道における膜ろ過施設導入ガイドライン，水道技術研究センター,1997,pp16-17.
[34] 三宅伸也,琵琶湖水を原水とする UF 膜ろ過净水プロセスの水質净化性能,土木学会第 49 回講演会講演集,1994,pp1010-1011.
[35] 吉川慎一,マンガンにより闭塞した中空糸膜の薬液洗净方法の検討,第 5 回卫生工学论文集,北海道大学卫生工学会,1997,pp252-255.
[36] 神保吉次,净水处理における膜利用技術の開発,膜分離技術の水処理への応用，日本水環境学会関西支部,1993,pp21-23.
[37] Iron and manganese removal by a membrane filtration system Jimbo, Y; Goto, K Water Science & Technology: Water Supply [Water Sci. Techno. Water Supply]. 2001, Vol. 1, no. 5, pp. 357-364.
[38] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理に関する基礎研究,環境工学研究論文集,1993,Vol30,pp311-316
[39] 後藤光亀等,高濃度鉄?マンガン含有地下水の連続膜ろ過に関する実験的研究,環境工学研究論文集,1994,Vol31,pp161-166.
[40] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理の化学洗浄特性，環境工学研究論文集,1997,Vol34, pp102-107.
[41] 後藤光亀等,高濃度鉄?マンガン含有地下水の膜ろ過処理の化学洗浄特性，環境工学研究論文集,1995,Vol32.
[42] Baldwin, B.S., Jacobsen, D.A. Iron and manganese removal by membrane filtration - Seekonk Water District experience. Journal of New England Water Works Association. Vol. 117, no. 1, pp. 15-21. Mar. 2003
[43] Carl Schneider, Robert P. Huehmer, Peter Johns. Microfiltration for Removal of Manganese from Surface Water.
[44] Lee, Se-Han; Lee, Shun-Hwa; Lee, Chul-Hee. Riverbank Filtration: Removal of Iron, Manganese and Hardness. Journal of Water and Environment Technology, J. Water Environ. Technol. 2003, Vol. 1, no. 2, pp. 133-140.
[45] Hans S. Posselt and Frederick J. Anderson, Walter J. Weber, Jr. Cation Sorption on Colloidal Hydrous Manganese Dioxide,1998.
[46] Knocke W.R., Hamon, J. R.. Soluble manganese removal on oxide-coated filter media. Journal American Water Works Association. 1988, 80(12), pp65-70.
[47] Knocke, W. R., Occiano, S. C., Hungate, R. Removal of soluble manganese by oxide-coatedfilter media: sorption rate and removal mechanism issues. Journal American Water Works Association, 1991, 83(8), 64-69.
[48] 邓慧萍,改性滤料在给水处理中的应用研究,同济大学学报,1995,23(4):427-431.
[49] Dingfang Liu, John J. Sansalone, Jonathan Kolich. Divalent Heavy Metal Removal Using Manganese Oxide Coated. WER and WEFTEC Research Symposium, 05 June 2001.
[50] 朱步遥、赵振国,界面化学基础,北京,化学工业出版社,1996.
[51] 章燕豪,吸附作用,上海科技技术出版社,1989.
[52] 汤鸿霄,水废水化学基础,中国建筑工业出版社,1997.
[53] 李攀,复合改性滤料强化除锰的试验研究,[学位论文], 哈尔滨, 哈尔滨工业大学, 2002.
[54] é.S. Pessim, L.C.C. Hahne, M.M.R. Castro. HEAVY METALS ADSORPTION BY MANGANESE DIOXIDE FROM AQUEOUS SOLUTIONS.Brazilian Congress of Phase Eguilibrium and Fluid Properties for Chemical Process Design.
[55] Dingfang Liu; John J. Sansalone, Cartledge. Adsorption Characteristics of Oxide Coated Buoyant Media for Storm Water Treatment. II: Equilibria and Kinetic Models. JOURNAL OF ENVIRONMENTAL ENGINEERING (C) ASCE / APRIL 2004,pp383-390
[56] Lee, Se-Han; Lee, Shun-Hwa; Park, Yung-Kyu. Riverbank Filtration: Removal of Iron, Manganese and Hardness. Journal of Water and Environment Technology. 2003. Vol. 1, no. 2, pp. 133-140.