磷酸氨镁结晶的热解及循环用于处理氨氮废水的实验研究
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摘要
传统的MAP沉淀法需要镁源(如MgC12)和磷源(如Na2HPO4)作投加剂,而且由于磷酸根离子容易与钙离子生成磷酸钙沉淀,需要使用NaOH作为pH调节剂,导致MAP沉淀法处理成本高,阻碍了实际应用。因此寻求廉价的沉淀剂一直都是化学沉淀法处理氨氮废水需要解决的关键问题。
本研究根据磷酸氨镁热解产物(MAP)加热分解后能产生氨气和磷酸氢镁、磷酸镁等物质,而磷酸氢镁和硫酸镁皆可与废水中的氨氮产生结晶,从而达到再利用的目的。磷酸氨镁热解产物吸收氨氮后生成的MAP经热分解后可再生磷酸氨镁热解产物,构成MHP的循环,从而大大减少了成本。
(1)磷酸氨镁热解产物对废水中的氨氮有着良好的去除效果,特别是在高浓度废水的处理当中,在处理2000mg/l的中高浓度氨氮废水时,对水中氨氮的去除率达到90%以上。
(2)磷酸氨镁热解产物用来循环处理氨氮废水行之有效,前三次循环的氨氮去除率均保持在90%左右,具有良好的去氨氮效果。
磷酸氨镁热解产物循环处理氨氮废水操作过程当中不需要额外添加镁盐或磷盐,同时也解决了磷酸氨镁的处置问题,可谓是一举两得,具有良好的经济效益和可行性。
The traditional struvite precipitation need MgC12 and Na2HPO4 and PH regulator such as NaOH that is forbidden the calcium phosphate deposition,It result in the expensive cost of struvite precipitation.So It is important to find a cheap way to deal with the treatment of high concentration of ammonia nitrogen wastewater.
In this paper, based on ammonium can elimination from MAP to magnesium phosphates and ammonium incorporation into the magnesium phosphates. It is confirmed that magnesium hydrogen phosphate (MgHPO4) is favorably obtained from the ammonium elimination from MAP at temperatures greater than 353 K, although magnesium phosphate (Mg3(PO4)?2) and magnesium pyrophosphate (Mg2P2O7) have been suggested as possible candidates. Based on the dissolution–precipitation mechanism for the removal of aqueous ammonium with magnesium phosphates, three magnesium phosphates were employed for the removal of aqueous ammonium.
(1)MHP precipitation is effective in treatment of high concentration of ammonia nitrogen wastewater. Under the most favorible condition, the removal rate of ammonia nitrogen can comes to 90% above.
(2)The present results show that MAP can be employed as an advanced material for the removal/recovery of ammonium,although it is generally accepted that an excess of MAP obtained from the wastewater treatment can be only used as a slow-acting fertilizer.The result show that the removal rate of ammonia nitrogen is still about 90% after 3 cycles.
It is unnecessary to add magnesium salt and phosphate salt in this method,and also resolve the treatment of MAP,so it is feasibility and have a good economic benefit.
本研究根据磷酸氨镁热解产物(MAP)加热分解后能产生氨气和磷酸氢镁、磷酸镁等物质,而磷酸氢镁和硫酸镁皆可与废水中的氨氮产生结晶,从而达到再利用的目的。磷酸氨镁热解产物吸收氨氮后生成的MAP经热分解后可再生磷酸氨镁热解产物,构成MHP的循环,从而大大减少了成本。
(1)磷酸氨镁热解产物对废水中的氨氮有着良好的去除效果,特别是在高浓度废水的处理当中,在处理2000mg/l的中高浓度氨氮废水时,对水中氨氮的去除率达到90%以上。
(2)磷酸氨镁热解产物用来循环处理氨氮废水行之有效,前三次循环的氨氮去除率均保持在90%左右,具有良好的去氨氮效果。
磷酸氨镁热解产物循环处理氨氮废水操作过程当中不需要额外添加镁盐或磷盐,同时也解决了磷酸氨镁的处置问题,可谓是一举两得,具有良好的经济效益和可行性。
The traditional struvite precipitation need MgC12 and Na2HPO4 and PH regulator such as NaOH that is forbidden the calcium phosphate deposition,It result in the expensive cost of struvite precipitation.So It is important to find a cheap way to deal with the treatment of high concentration of ammonia nitrogen wastewater.
In this paper, based on ammonium can elimination from MAP to magnesium phosphates and ammonium incorporation into the magnesium phosphates. It is confirmed that magnesium hydrogen phosphate (MgHPO4) is favorably obtained from the ammonium elimination from MAP at temperatures greater than 353 K, although magnesium phosphate (Mg3(PO4)?2) and magnesium pyrophosphate (Mg2P2O7) have been suggested as possible candidates. Based on the dissolution–precipitation mechanism for the removal of aqueous ammonium with magnesium phosphates, three magnesium phosphates were employed for the removal of aqueous ammonium.
(1)MHP precipitation is effective in treatment of high concentration of ammonia nitrogen wastewater. Under the most favorible condition, the removal rate of ammonia nitrogen can comes to 90% above.
(2)The present results show that MAP can be employed as an advanced material for the removal/recovery of ammonium,although it is generally accepted that an excess of MAP obtained from the wastewater treatment can be only used as a slow-acting fertilizer.The result show that the removal rate of ammonia nitrogen is still about 90% after 3 cycles.
It is unnecessary to add magnesium salt and phosphate salt in this method,and also resolve the treatment of MAP,so it is feasibility and have a good economic benefit.
引文
[1]刘小澜.?化学沉淀法处理焦化高浓度氨氮废水技术与工业应用探讨.(硕士学位论文).?湖南:湖南大学,2004.
[2] J.A. Dean (Ed.), Lange’s Handbook for Chemistry, McGraw–Hill,New York, 1985, p. 72.
[3] E. Pentlicka-Raj, Environ. Protect. Eng. 14 (1988) 5.
[4]?徐远,蒋京东,马三剑,刘锋.?鸟粪石结晶沉淀法处理氨氮废水的研究与应用[J].?污染防治技术.,2006,23(6):23—25.?
[5]?史世庄,王香平等.?化学沉淀法脱除焦化废水中的氨氮[J].?武汉科技大学学报.?2004,27(1):28—29.? ?
[6]?刘小澜,王继徽,黄稳水,等.化学沉淀法去除焦化废水中的氨氮.化工环保,2004,?24(1):46一49?
[7] Lowenthal R E, Kornmuller, URC,et al.Modelling struvite precipitation in anaerobic treatment system. Wat.Sci.Tech.1994,30:107—116.
[8]李晓萍,刘小波,金向军等.?化肥厂高浓度氨氮废水的处理和回用[J].?吉林大学学报.?2006,44(2):295——297.
[9]?Kenichi E.,Kaoru I.and Kyoji T.Ammonia Removal from Wastewaters,Japan Kokai 77 04 649,App1.,75/80,1975,538
[10]?胡孙林,钟理.?氨氮废水处理技术.现代化工[J].?2001,21?(6):47—52?
[11]?许国强,曾光明,殷建伟等.?氨氮废水处理技术现状及发展[J].?湖南有色金属,2002,(2):29—33?
[12] Blank Regina,Fischwasser Klaus.Verfahren zur entfernung yon ammonium aus industrieabwaessern.Ger(East)DD294,003
[13]高廷耀,顾国维主编.水污染控制工程下册(第二版).北京:高等教育出版社,1999.?
[14]?孙锦宜.?含氮废水处理技术及运用[M].?北京:化学工业出版社.?2003,244—249.?
[15]?刘大鹏.?化学沉淀法处理高浓度氨氮废水动力学研究及工艺条件优化.(硕士学位论文).?湖南:湖南大学,2004.?
[16]王?昊,周康根,赵?婷,刘荣义.?以Ca(OH)2为pH调节剂的磷酸氢镁吸附法处理氨氮废水的研究.?污染防治技术.?2007,4?
[17]?Bings Hubert,Lehmkuhl Josef.Process for recovery of ammonia from process and waste waters. Eur.Pat.Appl,EP490,396?
[18]?湖南化工研究所.?钙镁磷肥分析方法.?北京:石油化工出版社,1976,203—205?
[19]?沈耀良,王宝贞编著.废水生物处理新技术——理论与应用(第二版).北京:中国环境科学出版社,2006.
[20] [日]宗宫功.污水除磷脱氮技术[M].北京:中国环境科学出版社. 1987,3—6.
[21]袁芳.磷酸铵镁结晶法从养猪废水中回收氮磷营养元素的研究.(硕士学位论文).北京:北京科技大学,2006.
[22] Lowenthal R E, Kornmuller, URC,et al.Modelling struvite precipitation in anaerobic treatment system. Wat.Sci.Tech.1994,30:107—116.
[23]尚爱安.垃圾渗滤液处理技术研究(硕士学位论文).上海:华东理工大学,2004.
[24]黄稳水.以缓释肥形式回收石化废水中氨氮的研究(硕士学位论文).湖南:湖南大学,2004.
[25]张文成,安立超.焦化废水脱氮处理技术进展[J].环境污染治理技术与设备,2004,5(3):23—24.
[26] Abdelrazig B E I, Sharp J H. Phase changes on heating ammonium magnesium phosphate hydrates. Thermochimica Acta, 1988,129:197-215
[27]张书军,冯晓西,乌锡康,姚重华.磷酸铵镁沉淀法脱氮机理应用及沉淀剂循环[J].环境污染治理技术与设备, 2006,7(7):129—130.
[28] Shigeru Sugiyama , Masahiko Yokoyama. Removal of aqueous ammonium with magnesium phosphates obtained from the ammonium-elimination of magnesium ammonium phosphate Journal of Colloid and Interface Science 292 (2005) 133–138
[29]吕锡武,李峰,稻森悠平.氨氮废水处理过程中的好氧反硝化研究[J].给水排水, 2000,26(4):17—20.
[30]徐远.鸟粪石结晶法对氨氮废水处理的实验研究(硕士学位论文).江苏:苏州科技学院,2007.
[31] Boran Z,Kazuo Y. Seasonal Change of Mocrobial Population and Activities in a Building Wastewater Reuse System Using a Membrane Seperation Activated Sludge Process.Wat.Sci.Tech. 1996,34(5&6): 295—302.
[32] Ohlinger K N,Young T M and Schroeder E D,Kinetics effects on preferential struvite accumulation in wastewater. Journal of Environmental Engineering.1999,125(8):730—737.
[33]钟理,詹怀宇,D.O.Hill.化学沉淀法除去废水中的氨氮及其反应的探讨[J].重庆环境科学,2000,22(6):54—55.
[2] J.A. Dean (Ed.), Lange’s Handbook for Chemistry, McGraw–Hill,New York, 1985, p. 72.
[3] E. Pentlicka-Raj, Environ. Protect. Eng. 14 (1988) 5.
[4]?徐远,蒋京东,马三剑,刘锋.?鸟粪石结晶沉淀法处理氨氮废水的研究与应用[J].?污染防治技术.,2006,23(6):23—25.?
[5]?史世庄,王香平等.?化学沉淀法脱除焦化废水中的氨氮[J].?武汉科技大学学报.?2004,27(1):28—29.? ?
[6]?刘小澜,王继徽,黄稳水,等.化学沉淀法去除焦化废水中的氨氮.化工环保,2004,?24(1):46一49?
[7] Lowenthal R E, Kornmuller, URC,et al.Modelling struvite precipitation in anaerobic treatment system. Wat.Sci.Tech.1994,30:107—116.
[8]李晓萍,刘小波,金向军等.?化肥厂高浓度氨氮废水的处理和回用[J].?吉林大学学报.?2006,44(2):295——297.
[9]?Kenichi E.,Kaoru I.and Kyoji T.Ammonia Removal from Wastewaters,Japan Kokai 77 04 649,App1.,75/80,1975,538
[10]?胡孙林,钟理.?氨氮废水处理技术.现代化工[J].?2001,21?(6):47—52?
[11]?许国强,曾光明,殷建伟等.?氨氮废水处理技术现状及发展[J].?湖南有色金属,2002,(2):29—33?
[12] Blank Regina,Fischwasser Klaus.Verfahren zur entfernung yon ammonium aus industrieabwaessern.Ger(East)DD294,003
[13]高廷耀,顾国维主编.水污染控制工程下册(第二版).北京:高等教育出版社,1999.?
[14]?孙锦宜.?含氮废水处理技术及运用[M].?北京:化学工业出版社.?2003,244—249.?
[15]?刘大鹏.?化学沉淀法处理高浓度氨氮废水动力学研究及工艺条件优化.(硕士学位论文).?湖南:湖南大学,2004.?
[16]王?昊,周康根,赵?婷,刘荣义.?以Ca(OH)2为pH调节剂的磷酸氢镁吸附法处理氨氮废水的研究.?污染防治技术.?2007,4?
[17]?Bings Hubert,Lehmkuhl Josef.Process for recovery of ammonia from process and waste waters. Eur.Pat.Appl,EP490,396?
[18]?湖南化工研究所.?钙镁磷肥分析方法.?北京:石油化工出版社,1976,203—205?
[19]?沈耀良,王宝贞编著.废水生物处理新技术——理论与应用(第二版).北京:中国环境科学出版社,2006.
[20] [日]宗宫功.污水除磷脱氮技术[M].北京:中国环境科学出版社. 1987,3—6.
[21]袁芳.磷酸铵镁结晶法从养猪废水中回收氮磷营养元素的研究.(硕士学位论文).北京:北京科技大学,2006.
[22] Lowenthal R E, Kornmuller, URC,et al.Modelling struvite precipitation in anaerobic treatment system. Wat.Sci.Tech.1994,30:107—116.
[23]尚爱安.垃圾渗滤液处理技术研究(硕士学位论文).上海:华东理工大学,2004.
[24]黄稳水.以缓释肥形式回收石化废水中氨氮的研究(硕士学位论文).湖南:湖南大学,2004.
[25]张文成,安立超.焦化废水脱氮处理技术进展[J].环境污染治理技术与设备,2004,5(3):23—24.
[26] Abdelrazig B E I, Sharp J H. Phase changes on heating ammonium magnesium phosphate hydrates. Thermochimica Acta, 1988,129:197-215
[27]张书军,冯晓西,乌锡康,姚重华.磷酸铵镁沉淀法脱氮机理应用及沉淀剂循环[J].环境污染治理技术与设备, 2006,7(7):129—130.
[28] Shigeru Sugiyama , Masahiko Yokoyama. Removal of aqueous ammonium with magnesium phosphates obtained from the ammonium-elimination of magnesium ammonium phosphate Journal of Colloid and Interface Science 292 (2005) 133–138
[29]吕锡武,李峰,稻森悠平.氨氮废水处理过程中的好氧反硝化研究[J].给水排水, 2000,26(4):17—20.
[30]徐远.鸟粪石结晶法对氨氮废水处理的实验研究(硕士学位论文).江苏:苏州科技学院,2007.
[31] Boran Z,Kazuo Y. Seasonal Change of Mocrobial Population and Activities in a Building Wastewater Reuse System Using a Membrane Seperation Activated Sludge Process.Wat.Sci.Tech. 1996,34(5&6): 295—302.
[32] Ohlinger K N,Young T M and Schroeder E D,Kinetics effects on preferential struvite accumulation in wastewater. Journal of Environmental Engineering.1999,125(8):730—737.
[33]钟理,詹怀宇,D.O.Hill.化学沉淀法除去废水中的氨氮及其反应的探讨[J].重庆环境科学,2000,22(6):54—55.
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