有机酸对磷的化学固定与回收影响研究
|
摘要
磷是重要的矿产资源,在现有社会循环中,单向流动、不可再生,所以人类对磷的利用方式是不可持续的。如何从污水中回收磷,实现磷资源的可持续性利用的研究和实践受到水工业界、磷工业界和政府的高度重视。磷酸铵镁(MAP)结晶法和磷酸钙(CP)沉淀法是从污水中回收磷酸盐的两种主要方法。
在回收磷的工艺体系中,pH值是影响两种方法回收磷的重要因素之一,而不同pH值条件下有机酸等对磷酸铵镁结晶反应和磷酸钙沉淀反应的影响复杂,尚未有明确机理对其作出解释。本实验根据实际养猪废水成分,配制废水,进行模拟实验,观察反应过程,测定反应后溶液中N、P、Ca、Mg指标,分析结晶、沉淀产物的结构、形态和成分,对比研究不同pH值条件下有机酸(除特殊说明外,文中有机酸指乙酸、丁二酸和柠檬酸)及其浓度对MAP结晶法和CP沉淀法回收磷的影响。
实验室模拟养猪废水批次实验表明：
1.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应和CP沉淀反应中磷的最终去除率都有一定的影响,而且这种影响依次增强,氮、镁、钙的去除率与磷的去除率变化趋势基本一致,但变化趋势较平缓。
2.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应达到平衡的时间影响依次增大,不同pH值条件、不同种类和浓度的有机酸对MAP结晶沉淀反应达到平衡的时间影响效果不同；而这些有机酸浓度条件对CP沉淀反应反应速率没有明显影响。
3.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应产物的形态的影响依次增大,乙酸和柠檬酸对MAP晶体产物的结构、成分没有影响,丁二酸对结晶产物的结构有一定影响,但对其成分影响不大；除柠檬酸对CP沉淀产物的结构和成分有一定的影响以外,有机酸对CP沉淀反应沉淀产物的形态、结构、成分没有明显影响。
4.不同的pH值、有机酸和酸浓度条件下,MAP晶体在钢铁等材料上吸附固着性能远大于CP沉淀在钢铁等材料上的吸附固着性能；而且同等条件下,MAP的沉降性能要好于CP的沉降性能。
Phosphate is a very important mineral resource which obeys the rule of unidirectional flow in the material cycle process and it is non-renewable, however, the existing phosphate using method is unsustainable, so the research and practice for using phosphate in a sustainable way and recovering phosphate from wastewater draws high attention of the water industry, the phosphate industry and the government. Magnesium ammonium phosphate (MAP) crystallization and calcium phosphate (CP) precipitation recovering phosphate from wastewater are two main phosphate recovery technologies.
The system's pH value is one of the most important factors of the MAP and CP technologies, however, the systematic influence mechanisms of organic acid on the MAP and CP reaction under different pH values is unknown. Batches of simulation experiments were carried out by preparing wastewater with reference to the composition of the swine wastewater, the experiments'phenomena were observed, the N, P, Ca/Mg indexes were measured and the crystallization/precipitation products were analyzed, so as to compare the different influences of organic acids(acetate, succinate and citric in order) under different pH values on phosphate recovery by MAP crystallization and CP precipitation.
Batches of synthetic swine wastewater experiments'results showed that:
1. Solution organic acid concentration has some influence on the final removal efficiency of phosphate, and the influence increases accordingly, the final removal efficiency trend of the reaction system's N/Mg/Ca keeps consistent with that of phosphate while more gentle.
2. Solution organic acid concentration has some influence on the MAP crystallization equilibrium time and the influence increases accordingly, the influence on the MAP crystallization equilibrium time changes under different pH values and organic acid concentrations. However, it has little influence on the CP precipitation reaction rate.
3. Solution organic acid concentration has increasing influence on the product morphology of MAP crystallization; succinate acid has some influence on the products texture while acetate acid and citric acid have little influence both on their texture and components. However, organic acid concentration has almost no influence on the product morphology, texture and components of CP precipitation except that citric acid has a little effects on the product texture and components.
4. It was also observed that the MAP's adsorption capacity on steel materials (under different pH values, organic acids and their concentration) is much better than that of CP under the same reaction conditions, and it is also embodied on the settling ability of these two products.
在回收磷的工艺体系中,pH值是影响两种方法回收磷的重要因素之一,而不同pH值条件下有机酸等对磷酸铵镁结晶反应和磷酸钙沉淀反应的影响复杂,尚未有明确机理对其作出解释。本实验根据实际养猪废水成分,配制废水,进行模拟实验,观察反应过程,测定反应后溶液中N、P、Ca、Mg指标,分析结晶、沉淀产物的结构、形态和成分,对比研究不同pH值条件下有机酸(除特殊说明外,文中有机酸指乙酸、丁二酸和柠檬酸)及其浓度对MAP结晶法和CP沉淀法回收磷的影响。
实验室模拟养猪废水批次实验表明：
1.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应和CP沉淀反应中磷的最终去除率都有一定的影响,而且这种影响依次增强,氮、镁、钙的去除率与磷的去除率变化趋势基本一致,但变化趋势较平缓。
2.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应达到平衡的时间影响依次增大,不同pH值条件、不同种类和浓度的有机酸对MAP结晶沉淀反应达到平衡的时间影响效果不同；而这些有机酸浓度条件对CP沉淀反应反应速率没有明显影响。
3.乙酸、丁二酸和柠檬酸对MAP结晶沉淀反应产物的形态的影响依次增大,乙酸和柠檬酸对MAP晶体产物的结构、成分没有影响,丁二酸对结晶产物的结构有一定影响,但对其成分影响不大；除柠檬酸对CP沉淀产物的结构和成分有一定的影响以外,有机酸对CP沉淀反应沉淀产物的形态、结构、成分没有明显影响。
4.不同的pH值、有机酸和酸浓度条件下,MAP晶体在钢铁等材料上吸附固着性能远大于CP沉淀在钢铁等材料上的吸附固着性能；而且同等条件下,MAP的沉降性能要好于CP的沉降性能。
Phosphate is a very important mineral resource which obeys the rule of unidirectional flow in the material cycle process and it is non-renewable, however, the existing phosphate using method is unsustainable, so the research and practice for using phosphate in a sustainable way and recovering phosphate from wastewater draws high attention of the water industry, the phosphate industry and the government. Magnesium ammonium phosphate (MAP) crystallization and calcium phosphate (CP) precipitation recovering phosphate from wastewater are two main phosphate recovery technologies.
The system's pH value is one of the most important factors of the MAP and CP technologies, however, the systematic influence mechanisms of organic acid on the MAP and CP reaction under different pH values is unknown. Batches of simulation experiments were carried out by preparing wastewater with reference to the composition of the swine wastewater, the experiments'phenomena were observed, the N, P, Ca/Mg indexes were measured and the crystallization/precipitation products were analyzed, so as to compare the different influences of organic acids(acetate, succinate and citric in order) under different pH values on phosphate recovery by MAP crystallization and CP precipitation.
Batches of synthetic swine wastewater experiments'results showed that:
1. Solution organic acid concentration has some influence on the final removal efficiency of phosphate, and the influence increases accordingly, the final removal efficiency trend of the reaction system's N/Mg/Ca keeps consistent with that of phosphate while more gentle.
2. Solution organic acid concentration has some influence on the MAP crystallization equilibrium time and the influence increases accordingly, the influence on the MAP crystallization equilibrium time changes under different pH values and organic acid concentrations. However, it has little influence on the CP precipitation reaction rate.
3. Solution organic acid concentration has increasing influence on the product morphology of MAP crystallization; succinate acid has some influence on the products texture while acetate acid and citric acid have little influence both on their texture and components. However, organic acid concentration has almost no influence on the product morphology, texture and components of CP precipitation except that citric acid has a little effects on the product texture and components.
4. It was also observed that the MAP's adsorption capacity on steel materials (under different pH values, organic acids and their concentration) is much better than that of CP under the same reaction conditions, and it is also embodied on the settling ability of these two products.
引文
[1]贾玉霞.规模化畜禽养殖环境影响及主要防治问题[J].环境保护科学,2002.
[2]陈素华,孙铁布,耿春女.我国畜禽养殖业引致的环境问题及主要对策[J].环境污染技术与设备,2003,4(5)：6-9.
[3]赵万明.畜禽养殖业环境污染的原因与治理.内蒙古农业科技,2006,(5)：81～83.
[4]袁芳.磷酸铵镁结晶法磷回收工艺研究：(硕十学位论文).北京：北京科技大学,2006.
[5]廖新娣.美国养猪业粪污的处理利用[J].家畜生态,1997,18(、2)：27～30.
[6]贺晓燕.规模化畜禽养殖场污染及其治理对策探讨[J].湖北畜牧兽医,2005,(4)：7-9
[7]陈弘.畜禽养殖业污染防治及综合利用途径.福建环境,2003,20(6)：51-53
[8]熊慧欣,赵秀兰,徐轶群.规模化畜禽养殖污染的防治.家畜生态2004,25(4)：249～255
[9]金冬霞,王凯军.规模化畜禽养殖场污染防治综合对策[J].环境保护,2002,(12)：18～20.
[10]姚来银,许朝晖.养猪废水氮磷污染及其深度脱氮除磷技术探讨[J].福建环境,2003,20(1)：23-25.
[11]闵敏,黄种买.化学沉淀法去除养猪场废水中氨氮的试验研究[J].化学与生物工程,2005,(5)：27～30.
[12]廖新弟.人工湿地对猪场废水有机物处理效果的研究[J].应用生态学报,2002,(1)：113～117.
[13]寿亦丰,蔡昌达,林伟华.杭州灯塔养殖总场沼气与废水处理工程的技术特点[J].农业环境保护,2002,(1)：29～32.
[14]张从.大中型猪场沼气工程的环境影响评价[J].农业环境保护,2002,(1)：33～36.
[15]荆肇乾,吕锡武.污水处理中磷回收理论与技术[J].安全与环境工程,2005,12(1)：29-32.
[16]李博,杨持,林鹏,等.生态学[M].北京：高等教育出版社,2002.
[17]孙博雅,陈洪斌.污水处理磷回收的研究进展[J].四川环境,2007,26(1)：90-93.
[18]BengtessonM, Tillnan A M. Actors and interpretations in an environmental controversy the Swedish debate on sewage sludge use in agriculture[J]. Reour Conserv. Recy.,2004,42:65-82.
[19]Driver J. Phosphates Recovery for recycling from sewage and animal wastes [J]. Phosphorous and Potassium,1998,216:17-21.
[20]Lewis D L, Gattie D K. Pathogen risk from applying sewage sludge to land[J]. Env. Sci Tech.,2002, 36(13):286-293.
[21]郝晓地,甘一萍.排水研究新热点—从污水处理过程中回收磷.给水排水,2003,29(1)：20～24
[22]Balmer P. Phosphorous recovery-an overview of potentials and posibilities [J]. Water Sci. Tech., 2004,49(10):185-190.
[23]Duley B. Recyling phosphorous by recovery from sewage [EB/OL]. Second International Conference on the Recovery of Phosphorous from sewage and animal wastes, Noordw ijkerhout The Netherlands,2001.
[24]Liberti L, Petruzzee lli L, Florio L D. Improved REM-NUT for P-recovery [J]. Scope Newsletter, 2004,55(8).
[25]Kuzawa K, Jung Y J, Kiso Y,et al. Phosphote removal and recovery with a synthetic hydrotalcite as an adsorbent [J]. Chemosphere,2006,62:45-52.
[26]CEEP. Conference Summary, Second International Conference on the Recovery of Phosphorous from sewage and animal wastes[EB/OL]. http://www.nhm.ac.uk/research-curation/projects/.2001.
[27]Cecchi F. Treviso full scale P-recovery process[J]. Scope Newsletter,2004,55(5).
[28]Jaffer Y, Clark T A,Pearce P, et al. Potential phosphorus recovery by struvite formation[J]. Water Res,2002,36:1834-1842.
[29]Johnson A. Struvite its role in phosphorus recovery and recycling[J]. Scope Newsletter,2004,57(2).
[30]Roeleveld P, Loeffen P, Temmink H, et al. Dutch analysis for P-recovery from municipal wastewater [J]. Water Sci. Technol,2004,49(10):191-199.
[31]侯红娟,周琪.城市污水除磷技术发展[J].四川环境,2004,23(6)：41～45.
[32]邹雪.利用鸟粪石沉淀法从含磷废水中回收磷的实验研究：(硕士学位论文).北京：北京交通大学市政与环境工程系,2006.
[33]陈瑶.以鸟粪石形式从污水处理厂同时回收氨氮和磷的研究：(硕士学位论文).湖南：湖南环境科学与工程学院,2006.
[34]周峰.鸟粪石沉淀法回收废水中磷的研究：(硕士学位论文).广东：华侨大学化学工程系,2006.
[35]马世昌.化学物质辞典[M].西安：陕西科学技术出版社.2003.
[36]日本化学会.无机化合物合成手册(第2卷)[M].安家驹,陈之川译.北京：化学工业出版社,1986,147—148.
[37]Gaterell M R, Gay R, Wilson R, et al. An economic and environmental evaluation of the opportunities for substituting phosphorus recovered from wastewater treatment works in existing UK fertilizer markets[J]. Environ. Technol.,2000,21:1067～1084
[38]Sarkar A K. Phosphate cement-based fast setting binders[J]. J. Am. Ceram. Soc. Bull.,1990, 69:234-238
[39]Munch E V, Barr K. Controlled struvite crystallization for removing phosphorus from anaerobic digester sidestreams[J]. Water Res.,2001,35:151～159
[40]袁鹏,宋永会,袁芳,等.磷酸铵镁结晶法去除和回收养猪废水中营养元素的实验研究[J].环境科学学报,2007,27(7)：1128-1133.
[41]彭剑锋,宋永会,袁鹏,等.SPRR工艺回收养猪废水营养元素研究[J].农业环境科学学报,2007,26(6)：2173-2178.
[42]霍守亮,席北斗,刘鸿亮,等.磷酸按镁沉淀法去除与回收废水中氮磷的应用研究进展[J].化工进展,2007,26(3)：371-375.
[43]王建森,宋永会,袁鹏,等.基于PHREEQ C程序的磷酸铰镁结晶法污水处理工艺模型化研究[J].环境科学学报,2006,26(2)：208-213.
[44]Jiansen Wang, Yonghui Song, Peng Yuan, et al. Modeling the crystallization of magnesium ammonium phosphate for phosphorus recovery[J]. Chemospere,2006,65:1182～1187.
[45]Yonghui Song, Peng Yuan,Binghui Zheng, et al. Nutrients removal and recovery by crystallization of magnesium ammonium phosphate from synthetic swine wastewater [J]. Chemospere,2007,69:319～324.
[46]Shu L, Schneider P, Jegatheesan V, et al. An economic evaluation of Phosphorous Recovery as Stuvite from digester supernatant [J]. Bioresource Technology,2006,97(17):2211～2216.
[47]Gaterell M R, Gay R,Wilson R, et al. An economic and environmental evaluation of the opportunities for substituting phosphorus recovered from waste water treatment works in existing UK fertilizer market[J]. Environ.technol.,2000,21:1067～1084.
[48]Luz E de-Basham, Yoav Basham. Recent advances in removing phosphorus from waste water and its future use as fertilizer[J]. Water res.,2004,38:4222～4246.
[49]任南琪,王爱杰等编著.厌氧生物技术原理与应用[M].北京：化学工业出版社,2004.
[50]张自杰,林荣忱,金儒霖编.排水工程(第四版)[M].北京：中国建筑工业出版社,2000.
[51]陈瑶,李小明,曾光明,等.以磷酸钙盐的形式从污水处理厂回收磷的研究[J].环境科学与管理,2006,31(4)：110-112.
[52]汪慧贞,王绍贵.以磷酸钙盐形式从污水厂回收磷研究[J].中国给排水,2006,22(9)：93-96.
[53]Brett, S., Guy, J., Morse, G.K., et al. Phosphorus Removal and Recovery Technologies. London:Selper publications,1997.
[54]CEEP. Phosphorus recovery for recycling from sewage and animal manures, Summary of the Second International Conference on Recovery of Phosphates from Sewage and Animal Wastes. Noordwijkerhout, The Netherlands,2001.
[55]CEEP. Phosphate recovery-Where do we stand today? SCOPE Newsletter 2001,41 (1).
[56]Council of European Communities (EC). Directive Concerning Urban Wastewater Treatment (91/271/EEC) Off. J. L135/40,1991.
[57]Driver, J., Lijmbach, D., Steen, I. Why recover phosphorus for recycling, and how? Environ. Technol.1999,20:651-662.
[58]Durrant, A.E., Scrimshaw, M.D., Stratful, I., et al. Review of the feasability of recovering phosphate from wastewater for use as a raw material by the phosphate industry. Environ. Technol.1999,20:749-758.
[59]Valsami-Jones, E. Phosphorus in wastewaters:is there a potential for recovery as calcium phosphate? Chimica Oggi (Chemistry Today) 2002,5:52-55.
[60]Song, Y.H. Precipitation chemistry of calcium phosphate for phosphorus recovery. Schriftenreihe des ISWW 111. Karlsruhe:Institutsverlag Siedlungswasserwirtschaft der Universitat Karlsruhe,2003.
[61]Piekema, P.G., Gaastra, S.B. Upgrading of a wastewater treatment plant in The Netherlands: combination of several nutrient removal processes. European Water Pollution Control 1993, 3:21-26.
[62]Giesen, A. Crystallisation process enables environmental friendly phosphate removal at low costs. Environ. Technol.1999,20:759-775.
[63]Parsons, S.A., Wall, F., Doyle, J., et al. Assessing the potential for struvite recovery at sewage treatment works. Environ. Technol.2001,22:1279-1286.
[64]Jaffer, Y., Clark, T.A., Pearce P., et al. Potential phosphorus recovery by stuvite formation. Water Res.2002,36:1834-1842.
[65]Schultze-Rettmer, R., Yamari, T. Experiment with the process of precipitation of magnesium-ammonium-phosphate out of various waste waters. Vom Wasser 1988,71:41-54.
[66]Bridger, GL., Salutsky, M.L., Starostka, R.W. Metal amonium phosphates as fertilizers. American Chemical Society 1961,10:181-188.
[67]Koritskaya, T.D., Remen, R.Y. Magnesium ammonium phosphates as a complex fertilizer. Master of Engineering Sciences.64-14364. O.T.S.-U.S., Dept of Commerce.
[68]Bouropoulos, N.C., Koutsoukos, P.G. Spontaneous precipitation of struvite from aqueous solutions. J. Crystal Growth 2000,213:381-388.
[69]Kabdasli, I., Tunay, O., Osturk, I., et al. Ammonia removal from young landfill-leachate by magnesium ammonium phosphate precipitation and air stripping. Water Sci. Technol.2000, 41:237-240
[70]Li, X.Z., Hao, X.D. Ammonium removal from landfill leachate by chemical precipitation. Waste Management 1999,19:409-415.
[71]黄稳水,王继徽,刘小澜,等.磷酸铵镁法预处理高浓度氨氮废水的研究.工业水处理2003,23(10)：34—36.
[72]孙体昌,张建云,松全元.废水中氨氮沉淀的影响因素.北京科技大学学报2004,26(1)：11一14.
[73]李才辉,冯晓西,乌锡康.MAP结晶法处理氨氮废水最佳条件的研究.上海环境科学2003,22(6)：389—392,445,446.
[74]刘大鹏,王继徽,刘晓澜,等.MAP结晶法处理焦化废水中氨氮的pH值影响.工业水处理2004,24(1)：44—47.
[75]Kabdasli, I., Tunay, O., Cetin, M.S., et al. Assessment of magnesium ammonium phosphate precipitation for the treatment of leather tanning industry wastewaters. Water Sci. Technol. 2002,46:231-239.
[76]仝武刚,王继徽.磷酸铵镁除磷脱氮技术.工业用水与废水2002,33(5)：5—6.
[77]李金页,郑平.鸟粪石沉淀法在废水除磷脱氮中的应用..中国沼气2004,22(1)：7—8.
[78]陈利德,王思.浅议污水厂的磷回收.环境工程2004,22(4)：26—28.
[79]Van der Houwen, J.A.M., Valsami-Jones, E. The application of calcium phosphate precipitation chemistry to phosphorus recovery:the influence of organic ligands. Environ. Technol.2001,22:1325-1335.
[2]陈素华,孙铁布,耿春女.我国畜禽养殖业引致的环境问题及主要对策[J].环境污染技术与设备,2003,4(5)：6-9.
[3]赵万明.畜禽养殖业环境污染的原因与治理.内蒙古农业科技,2006,(5)：81～83.
[4]袁芳.磷酸铵镁结晶法磷回收工艺研究：(硕十学位论文).北京：北京科技大学,2006.
[5]廖新娣.美国养猪业粪污的处理利用[J].家畜生态,1997,18(、2)：27～30.
[6]贺晓燕.规模化畜禽养殖场污染及其治理对策探讨[J].湖北畜牧兽医,2005,(4)：7-9
[7]陈弘.畜禽养殖业污染防治及综合利用途径.福建环境,2003,20(6)：51-53
[8]熊慧欣,赵秀兰,徐轶群.规模化畜禽养殖污染的防治.家畜生态2004,25(4)：249～255
[9]金冬霞,王凯军.规模化畜禽养殖场污染防治综合对策[J].环境保护,2002,(12)：18～20.
[10]姚来银,许朝晖.养猪废水氮磷污染及其深度脱氮除磷技术探讨[J].福建环境,2003,20(1)：23-25.
[11]闵敏,黄种买.化学沉淀法去除养猪场废水中氨氮的试验研究[J].化学与生物工程,2005,(5)：27～30.
[12]廖新弟.人工湿地对猪场废水有机物处理效果的研究[J].应用生态学报,2002,(1)：113～117.
[13]寿亦丰,蔡昌达,林伟华.杭州灯塔养殖总场沼气与废水处理工程的技术特点[J].农业环境保护,2002,(1)：29～32.
[14]张从.大中型猪场沼气工程的环境影响评价[J].农业环境保护,2002,(1)：33～36.
[15]荆肇乾,吕锡武.污水处理中磷回收理论与技术[J].安全与环境工程,2005,12(1)：29-32.
[16]李博,杨持,林鹏,等.生态学[M].北京：高等教育出版社,2002.
[17]孙博雅,陈洪斌.污水处理磷回收的研究进展[J].四川环境,2007,26(1)：90-93.
[18]BengtessonM, Tillnan A M. Actors and interpretations in an environmental controversy the Swedish debate on sewage sludge use in agriculture[J]. Reour Conserv. Recy.,2004,42:65-82.
[19]Driver J. Phosphates Recovery for recycling from sewage and animal wastes [J]. Phosphorous and Potassium,1998,216:17-21.
[20]Lewis D L, Gattie D K. Pathogen risk from applying sewage sludge to land[J]. Env. Sci Tech.,2002, 36(13):286-293.
[21]郝晓地,甘一萍.排水研究新热点—从污水处理过程中回收磷.给水排水,2003,29(1)：20～24
[22]Balmer P. Phosphorous recovery-an overview of potentials and posibilities [J]. Water Sci. Tech., 2004,49(10):185-190.
[23]Duley B. Recyling phosphorous by recovery from sewage [EB/OL]. Second International Conference on the Recovery of Phosphorous from sewage and animal wastes, Noordw ijkerhout The Netherlands,2001.
[24]Liberti L, Petruzzee lli L, Florio L D. Improved REM-NUT for P-recovery [J]. Scope Newsletter, 2004,55(8).
[25]Kuzawa K, Jung Y J, Kiso Y,et al. Phosphote removal and recovery with a synthetic hydrotalcite as an adsorbent [J]. Chemosphere,2006,62:45-52.
[26]CEEP. Conference Summary, Second International Conference on the Recovery of Phosphorous from sewage and animal wastes[EB/OL]. http://www.nhm.ac.uk/research-curation/projects/.2001.
[27]Cecchi F. Treviso full scale P-recovery process[J]. Scope Newsletter,2004,55(5).
[28]Jaffer Y, Clark T A,Pearce P, et al. Potential phosphorus recovery by struvite formation[J]. Water Res,2002,36:1834-1842.
[29]Johnson A. Struvite its role in phosphorus recovery and recycling[J]. Scope Newsletter,2004,57(2).
[30]Roeleveld P, Loeffen P, Temmink H, et al. Dutch analysis for P-recovery from municipal wastewater [J]. Water Sci. Technol,2004,49(10):191-199.
[31]侯红娟,周琪.城市污水除磷技术发展[J].四川环境,2004,23(6)：41～45.
[32]邹雪.利用鸟粪石沉淀法从含磷废水中回收磷的实验研究：(硕士学位论文).北京：北京交通大学市政与环境工程系,2006.
[33]陈瑶.以鸟粪石形式从污水处理厂同时回收氨氮和磷的研究：(硕士学位论文).湖南：湖南环境科学与工程学院,2006.
[34]周峰.鸟粪石沉淀法回收废水中磷的研究：(硕士学位论文).广东：华侨大学化学工程系,2006.
[35]马世昌.化学物质辞典[M].西安：陕西科学技术出版社.2003.
[36]日本化学会.无机化合物合成手册(第2卷)[M].安家驹,陈之川译.北京：化学工业出版社,1986,147—148.
[37]Gaterell M R, Gay R, Wilson R, et al. An economic and environmental evaluation of the opportunities for substituting phosphorus recovered from wastewater treatment works in existing UK fertilizer markets[J]. Environ. Technol.,2000,21:1067～1084
[38]Sarkar A K. Phosphate cement-based fast setting binders[J]. J. Am. Ceram. Soc. Bull.,1990, 69:234-238
[39]Munch E V, Barr K. Controlled struvite crystallization for removing phosphorus from anaerobic digester sidestreams[J]. Water Res.,2001,35:151～159
[40]袁鹏,宋永会,袁芳,等.磷酸铵镁结晶法去除和回收养猪废水中营养元素的实验研究[J].环境科学学报,2007,27(7)：1128-1133.
[41]彭剑锋,宋永会,袁鹏,等.SPRR工艺回收养猪废水营养元素研究[J].农业环境科学学报,2007,26(6)：2173-2178.
[42]霍守亮,席北斗,刘鸿亮,等.磷酸按镁沉淀法去除与回收废水中氮磷的应用研究进展[J].化工进展,2007,26(3)：371-375.
[43]王建森,宋永会,袁鹏,等.基于PHREEQ C程序的磷酸铰镁结晶法污水处理工艺模型化研究[J].环境科学学报,2006,26(2)：208-213.
[44]Jiansen Wang, Yonghui Song, Peng Yuan, et al. Modeling the crystallization of magnesium ammonium phosphate for phosphorus recovery[J]. Chemospere,2006,65:1182～1187.
[45]Yonghui Song, Peng Yuan,Binghui Zheng, et al. Nutrients removal and recovery by crystallization of magnesium ammonium phosphate from synthetic swine wastewater [J]. Chemospere,2007,69:319～324.
[46]Shu L, Schneider P, Jegatheesan V, et al. An economic evaluation of Phosphorous Recovery as Stuvite from digester supernatant [J]. Bioresource Technology,2006,97(17):2211～2216.
[47]Gaterell M R, Gay R,Wilson R, et al. An economic and environmental evaluation of the opportunities for substituting phosphorus recovered from waste water treatment works in existing UK fertilizer market[J]. Environ.technol.,2000,21:1067～1084.
[48]Luz E de-Basham, Yoav Basham. Recent advances in removing phosphorus from waste water and its future use as fertilizer[J]. Water res.,2004,38:4222～4246.
[49]任南琪,王爱杰等编著.厌氧生物技术原理与应用[M].北京：化学工业出版社,2004.
[50]张自杰,林荣忱,金儒霖编.排水工程(第四版)[M].北京：中国建筑工业出版社,2000.
[51]陈瑶,李小明,曾光明,等.以磷酸钙盐的形式从污水处理厂回收磷的研究[J].环境科学与管理,2006,31(4)：110-112.
[52]汪慧贞,王绍贵.以磷酸钙盐形式从污水厂回收磷研究[J].中国给排水,2006,22(9)：93-96.
[53]Brett, S., Guy, J., Morse, G.K., et al. Phosphorus Removal and Recovery Technologies. London:Selper publications,1997.
[54]CEEP. Phosphorus recovery for recycling from sewage and animal manures, Summary of the Second International Conference on Recovery of Phosphates from Sewage and Animal Wastes. Noordwijkerhout, The Netherlands,2001.
[55]CEEP. Phosphate recovery-Where do we stand today? SCOPE Newsletter 2001,41 (1).
[56]Council of European Communities (EC). Directive Concerning Urban Wastewater Treatment (91/271/EEC) Off. J. L135/40,1991.
[57]Driver, J., Lijmbach, D., Steen, I. Why recover phosphorus for recycling, and how? Environ. Technol.1999,20:651-662.
[58]Durrant, A.E., Scrimshaw, M.D., Stratful, I., et al. Review of the feasability of recovering phosphate from wastewater for use as a raw material by the phosphate industry. Environ. Technol.1999,20:749-758.
[59]Valsami-Jones, E. Phosphorus in wastewaters:is there a potential for recovery as calcium phosphate? Chimica Oggi (Chemistry Today) 2002,5:52-55.
[60]Song, Y.H. Precipitation chemistry of calcium phosphate for phosphorus recovery. Schriftenreihe des ISWW 111. Karlsruhe:Institutsverlag Siedlungswasserwirtschaft der Universitat Karlsruhe,2003.
[61]Piekema, P.G., Gaastra, S.B. Upgrading of a wastewater treatment plant in The Netherlands: combination of several nutrient removal processes. European Water Pollution Control 1993, 3:21-26.
[62]Giesen, A. Crystallisation process enables environmental friendly phosphate removal at low costs. Environ. Technol.1999,20:759-775.
[63]Parsons, S.A., Wall, F., Doyle, J., et al. Assessing the potential for struvite recovery at sewage treatment works. Environ. Technol.2001,22:1279-1286.
[64]Jaffer, Y., Clark, T.A., Pearce P., et al. Potential phosphorus recovery by stuvite formation. Water Res.2002,36:1834-1842.
[65]Schultze-Rettmer, R., Yamari, T. Experiment with the process of precipitation of magnesium-ammonium-phosphate out of various waste waters. Vom Wasser 1988,71:41-54.
[66]Bridger, GL., Salutsky, M.L., Starostka, R.W. Metal amonium phosphates as fertilizers. American Chemical Society 1961,10:181-188.
[67]Koritskaya, T.D., Remen, R.Y. Magnesium ammonium phosphates as a complex fertilizer. Master of Engineering Sciences.64-14364. O.T.S.-U.S., Dept of Commerce.
[68]Bouropoulos, N.C., Koutsoukos, P.G. Spontaneous precipitation of struvite from aqueous solutions. J. Crystal Growth 2000,213:381-388.
[69]Kabdasli, I., Tunay, O., Osturk, I., et al. Ammonia removal from young landfill-leachate by magnesium ammonium phosphate precipitation and air stripping. Water Sci. Technol.2000, 41:237-240
[70]Li, X.Z., Hao, X.D. Ammonium removal from landfill leachate by chemical precipitation. Waste Management 1999,19:409-415.
[71]黄稳水,王继徽,刘小澜,等.磷酸铵镁法预处理高浓度氨氮废水的研究.工业水处理2003,23(10)：34—36.
[72]孙体昌,张建云,松全元.废水中氨氮沉淀的影响因素.北京科技大学学报2004,26(1)：11一14.
[73]李才辉,冯晓西,乌锡康.MAP结晶法处理氨氮废水最佳条件的研究.上海环境科学2003,22(6)：389—392,445,446.
[74]刘大鹏,王继徽,刘晓澜,等.MAP结晶法处理焦化废水中氨氮的pH值影响.工业水处理2004,24(1)：44—47.
[75]Kabdasli, I., Tunay, O., Cetin, M.S., et al. Assessment of magnesium ammonium phosphate precipitation for the treatment of leather tanning industry wastewaters. Water Sci. Technol. 2002,46:231-239.
[76]仝武刚,王继徽.磷酸铵镁除磷脱氮技术.工业用水与废水2002,33(5)：5—6.
[77]李金页,郑平.鸟粪石沉淀法在废水除磷脱氮中的应用..中国沼气2004,22(1)：7—8.
[78]陈利德,王思.浅议污水厂的磷回收.环境工程2004,22(4)：26—28.
[79]Van der Houwen, J.A.M., Valsami-Jones, E. The application of calcium phosphate precipitation chemistry to phosphorus recovery:the influence of organic ligands. Environ. Technol.2001,22:1325-1335.