天然植物絮凝剂的制备及应用研究
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摘要
水污染是目前全世界所面临的严峻挑战,污水絮凝处理是解决水污染的有效途径。与传统絮凝剂相比,天然高分子絮凝剂具有高效、无毒、易降解、无二次污染和用途广泛等特点。木粉改性阳离子絮凝剂和木粉改性两性絮凝剂是新型的天然高分子絮凝剂,在食品、农业、化工、环保等领域有着广泛的应用。
本文制备了木粉改性植物阳离子絮凝剂SUSM-a和木粉改性植物两性絮凝剂,对制备工艺进行了优化研究,并把这两种植物絮凝剂用于自制污水、洗煤废水和含氯废水的处理,对最佳处理工艺和处理结果进行了研究,并对这两种植物絮凝剂的制备和絮凝机理进行了初步探索,获得了以下结论：
1.木粉改性植物阳离子絮凝剂SUSM-a的最佳制备工艺为,木粉/NaOH质量比为2：1,木粉/醚化剂质量比为1.5：1时,反应温度40℃,反应时间为3.5h。
2.采用SUSM-a处理洗煤废水,洗煤废水的浊度、CODCr、固体悬浮物的去除率分别可达到96.8%、69.3%、97.9%。最佳工艺条件为：pH为6～8,SUSM -a和聚铝的投入量分别为10mg/L和5mg/L。经过复配和反复吸附,SAUM-a对含氯废水也有一定的处理效果,氯去除率可达到36.3%。通过对制备条件的改进和改进后的研究可以发现,SAUM-al更有中试和投产的价值。
3.接枝共聚反应合成木粉改性两性絮凝剂的最佳反应条件为：AM/木粉(重量比)为2：1,引发剂用量为羧甲基化产物量的2%,反应时间为1.5h,反应温度为60℃; Mannich反应的最佳反应条件是：胺/醛(摩尔比)为1.5：1,反应时间为1h,反应温度为50℃。
4.采用木粉改性植物两性絮凝剂处理自制污水的最佳工艺条件是：PAC和两性絮凝剂投放量分别为5mg/L和12.5mg/L,搅拌速度为200r/min,静置时间为7.5min, pH适用范围较广,最终污水的浊度可达到5左右；处理洗煤废水的最佳工艺条件是：PAC与两性絮凝剂投放量分别为5mg/L和15mg/L,搅拌速度为200r/min,静置时间为5min、pH适用范围比较广,最终污水的COD去除率可达65%以上,固体悬浮物的去除率可达90%以上；处理含氯废水的最佳工艺条件是：PAC和两性絮凝剂投放量分别为5mg/L和10mg/L,搅拌速度为250r/min,静置时间为10min,在酸性的条件下效果比较好,最终氯离子去除率可达30%以上。
Tt is a serious challenge of the water pollution for all over the word. Flocculantion is a process widely used for waste-water treatment in home and abroad. Compared with the traditional flocculants, the natural polymer flocculant has the characters of efficiency, non-toxic, readily biodegradable, no secondary pollution, and widely used.They are new natural polymer flocculants both the cationic flocculant and the gender flocculant modified. They are widely used in parts of food, agriculture, chemical industry and environmental protection.
The cationic flocculant which is called SUSM-a and the gender flocculant modified by wood flour were prepared in this article. We optimized the preparation process and applied the two kinds of plants flocculants in waste-water made by myself, coal washing waste-water and chlorine Wastewater treatment. We studied the treatment process and the results and found the best one. And we also did a preliminary exploration on the mechanism of flocculants. At last we accessed to the following conclusions.
1. The best preparation process of the cationic flocculant modified by natural flour is that the mass ratio of wood-powder and NaOH is 2:1, the mass ratio of wood-powder and etherifying agent is 1.5:1,the temperature in reaction is 40℃,the reaction time is three hours and a half, we can synthetize SUSA-a.
2. In the application for coal washing waste-water treatment, it turn out to be that the removal rates of turbidity, CODCr and suspended solids in the coal washing waste water is 96.8%,69.3% and 97.9%.When the pH value is 6 to 8, the dosage of SUSM-a is 10mg/L, the poly-aluminum dose is 5mg/L, is the best treatment process. It results that the SAUM-a has an effect in dealing with the chlorinated waste water treatment after a complex and repeated adsorption. The removal rate of chlorinated can reach 36.3%.We improved the preparation conditions and did some research found that SAUM-a1 has more pilot and production value.
3.The gender flocculant modified by wood-flour is made in copolymerization reaction. When the mass ratio of AM and wood-flour is 2:1,2% of the product amount of carboxy-methyl for the amount of initiator, the reaction time is 1.5h, the reaction temperature is 60℃,the react condition is the best. When the mole ration of amine and formaldehyde is 1.5:1, the reaction time is one hour, the reaction temperature is 50℃,it is the best condition for Mannich reaction.
4. Applied the gender flocculant modified by flour to the treatment of waste-water made by myself, when the dosage of PAC and gender flocculant were 5mg/L and 12.5mg/L, the stirring speed was 200r/min, hold 7.5min is best process condition. The turbidity of the final effluent can reach about 5 with wide pH. In dealing with the coal washing waste-water, the best process conditions were that the amount of PAC and gender flocculant were 5mg/L and 15mg/L, the stirring speed was 200r/min, hold 5min.Finally,the COD removal of the final effluent was more than 65%,the ss removal rate can be above 90%.The treatment of chlorinated waste-water's optimum conditions is that the input dosage of PAC and gender flocculent were 5mg/L and lOmg/L, the stirring speed was 250r/min, hold 10min.The results turn out to be better in acidic surroundings, and the final removal rate of chloride ion was more than 30%.
本文制备了木粉改性植物阳离子絮凝剂SUSM-a和木粉改性植物两性絮凝剂,对制备工艺进行了优化研究,并把这两种植物絮凝剂用于自制污水、洗煤废水和含氯废水的处理,对最佳处理工艺和处理结果进行了研究,并对这两种植物絮凝剂的制备和絮凝机理进行了初步探索,获得了以下结论：
1.木粉改性植物阳离子絮凝剂SUSM-a的最佳制备工艺为,木粉/NaOH质量比为2：1,木粉/醚化剂质量比为1.5：1时,反应温度40℃,反应时间为3.5h。
2.采用SUSM-a处理洗煤废水,洗煤废水的浊度、CODCr、固体悬浮物的去除率分别可达到96.8%、69.3%、97.9%。最佳工艺条件为：pH为6～8,SUSM -a和聚铝的投入量分别为10mg/L和5mg/L。经过复配和反复吸附,SAUM-a对含氯废水也有一定的处理效果,氯去除率可达到36.3%。通过对制备条件的改进和改进后的研究可以发现,SAUM-al更有中试和投产的价值。
3.接枝共聚反应合成木粉改性两性絮凝剂的最佳反应条件为：AM/木粉(重量比)为2：1,引发剂用量为羧甲基化产物量的2%,反应时间为1.5h,反应温度为60℃; Mannich反应的最佳反应条件是：胺/醛(摩尔比)为1.5：1,反应时间为1h,反应温度为50℃。
4.采用木粉改性植物两性絮凝剂处理自制污水的最佳工艺条件是：PAC和两性絮凝剂投放量分别为5mg/L和12.5mg/L,搅拌速度为200r/min,静置时间为7.5min, pH适用范围较广,最终污水的浊度可达到5左右；处理洗煤废水的最佳工艺条件是：PAC与两性絮凝剂投放量分别为5mg/L和15mg/L,搅拌速度为200r/min,静置时间为5min、pH适用范围比较广,最终污水的COD去除率可达65%以上,固体悬浮物的去除率可达90%以上；处理含氯废水的最佳工艺条件是：PAC和两性絮凝剂投放量分别为5mg/L和10mg/L,搅拌速度为250r/min,静置时间为10min,在酸性的条件下效果比较好,最终氯离子去除率可达30%以上。
Tt is a serious challenge of the water pollution for all over the word. Flocculantion is a process widely used for waste-water treatment in home and abroad. Compared with the traditional flocculants, the natural polymer flocculant has the characters of efficiency, non-toxic, readily biodegradable, no secondary pollution, and widely used.They are new natural polymer flocculants both the cationic flocculant and the gender flocculant modified. They are widely used in parts of food, agriculture, chemical industry and environmental protection.
The cationic flocculant which is called SUSM-a and the gender flocculant modified by wood flour were prepared in this article. We optimized the preparation process and applied the two kinds of plants flocculants in waste-water made by myself, coal washing waste-water and chlorine Wastewater treatment. We studied the treatment process and the results and found the best one. And we also did a preliminary exploration on the mechanism of flocculants. At last we accessed to the following conclusions.
1. The best preparation process of the cationic flocculant modified by natural flour is that the mass ratio of wood-powder and NaOH is 2:1, the mass ratio of wood-powder and etherifying agent is 1.5:1,the temperature in reaction is 40℃,the reaction time is three hours and a half, we can synthetize SUSA-a.
2. In the application for coal washing waste-water treatment, it turn out to be that the removal rates of turbidity, CODCr and suspended solids in the coal washing waste water is 96.8%,69.3% and 97.9%.When the pH value is 6 to 8, the dosage of SUSM-a is 10mg/L, the poly-aluminum dose is 5mg/L, is the best treatment process. It results that the SAUM-a has an effect in dealing with the chlorinated waste water treatment after a complex and repeated adsorption. The removal rate of chlorinated can reach 36.3%.We improved the preparation conditions and did some research found that SAUM-a1 has more pilot and production value.
3.The gender flocculant modified by wood-flour is made in copolymerization reaction. When the mass ratio of AM and wood-flour is 2:1,2% of the product amount of carboxy-methyl for the amount of initiator, the reaction time is 1.5h, the reaction temperature is 60℃,the react condition is the best. When the mole ration of amine and formaldehyde is 1.5:1, the reaction time is one hour, the reaction temperature is 50℃,it is the best condition for Mannich reaction.
4. Applied the gender flocculant modified by flour to the treatment of waste-water made by myself, when the dosage of PAC and gender flocculant were 5mg/L and 12.5mg/L, the stirring speed was 200r/min, hold 7.5min is best process condition. The turbidity of the final effluent can reach about 5 with wide pH. In dealing with the coal washing waste-water, the best process conditions were that the amount of PAC and gender flocculant were 5mg/L and 15mg/L, the stirring speed was 200r/min, hold 5min.Finally,the COD removal of the final effluent was more than 65%,the ss removal rate can be above 90%.The treatment of chlorinated waste-water's optimum conditions is that the input dosage of PAC and gender flocculent were 5mg/L and lOmg/L, the stirring speed was 250r/min, hold 10min.The results turn out to be better in acidic surroundings, and the final removal rate of chloride ion was more than 30%.
引文
[1]苏腾等.净水技术,2000(3)：7-9.
[2]吕锦玲.天然高分子植物胶絮凝剂的制备及应用研究[D].昆明理工大学.2005.
[3]迟春娟.液-液萃取法处理高氯难降解有机废水[D].浙江工业大学.1998.
[4]刘建兰,钱惠芬,张东明,陈亚萍.聚铝架凝制的研究进展[D].化工时刊.2001(11)：16-18.
[5]王东升.中过给水排水,1997,13(5)：20-21.
[6]崔蕴霞等.工业水处理,1998,18(3)：8-9.
[7]Bottero J Yet al.J.Phys.chem.,1980,84:29-33.
[8]吴绍情等.工业水处理,1994,14(3)：1-3.
[9]范瑾初.混凝技术.北京：中国环境科学出版社,1992：10-16.
[10]胡万里等.工业水处理,1995,15(1)：7-9.
[11]于尔捷译.国外环境科学技术,1995(1)：11-14.
[12]李为群等.环境污染与防治,1997,19(3)：32-35.
[13]史建国.聚合硫酸铁的研制与应用[J].水利电力劳动保护,1996,6(2)：28-30.
[14]李善仁,李凤亭.无机和有机复合高分子絮凝剂的现状和发展方向[J].煤矿环境保护,2001,10(2)：15-19.
[15]Brian A, Jane B. Soluble Polymers in WaterofPurificartion[J].Prog Polym Sci 1995, 20(6):1014-1016.
[16]Wong Shing Hydrophilic Dispersion Polyners of Diaflyldinethyl Ammonium Chloride and A crylamide for the Clarification of Drinking Process Water US,6019904[P].2000-02-01.
[17]刘明华编.有机高分子絮凝剂的制备及应用[M].北京：化学工业出版社,2006：145-190.
[18]唐琼,张新申,李正飞.有机高分子改性阳离子絮凝剂的开发与应用前景[J].中国皮革,2002,31(21)：29-32.
[19]韩庆昌,娄金生,王芳,刘海波.有机高分子复合絮凝剂的研究进展与发展趋势[A].南京大学学报,2007,21(2)：34-36.
[20]秦丽娟陈夫山.有机高分子絮凝剂的研究进展及发展趋势.天京科技大学,2004,35(1)：41-43.
[21]巩冠群,张英杰,伊家贵,等.共聚有机强阳离子絮凝剂的开发及应用[J].石化技术与应用,2005,23(20)：138-141.
[22]Song B K, ChoM S, Yoon K Jetal Dispersion polymerization of acrylan icle with quaternary ammonium cation ic comonomer in aqueous solution [J].Journal of Applied Polymer Science, 2003,87(7):1101-1108
[23]Richardson Acrylanicle diallyl dinethyl ammonium chloride copolymers as inproved dewatering acids formineralprocessing US,4673511[P].1987-06-16.
[24]仁海静,陈文纳,温庆林,等.高阳离子度有机絮凝剂的合成[J].化工技术与开发,2004,33(1)：7-10.
[25]Rath S K, Singh R P. On the characterization of grafted and ungragted starch, amylose,and amylopectin[J]. Journal of Applied Polyner Science,1998,70(9):1795-1810.
[26]周玉燕,潘丽娟,郑瑛,等。p环糊精与丙烯酰胺的接枝化合物及其对水中污染物的絮凝作用[J].化工环保,2003,23 (6):362-366.
[27]Karnakar N C, Rath SK, Satry B S,etal investigation on glocculation characteristics of polysacchardebased graft copolymers in coal fines suspension [J]. Journal of Applied Polymer Science,1998,70.2619-2625.
[28]PalS,MalD,Singh R P. Cation ic starchr an effective floccylating agent [J]. Carbohydrate Polymer, 2005,59(4):417-423.
[29]盛雪芹,丁永生,公维民,等.天然改性阳离子絮凝剂制备及性能研究[J].大连海事大学学报,2002,28(4)：72-75.
[30]秋增昌,王海毅.木质素的应用研究现状与进展[J].西南造纸,2004,33(3)：29-33.
[31]尹华,肖锦.多功能水处理剂研究进展[J].工业水处理,1995,15(2)：1-2.
[32]甘光奉,甘莉.天然改性有机物高分子絮凝剂研究进展[J].石油与天然气化工,1996,25(1)：55-57.
[33]冯玉杰,金永新.壳聚糖季铵盐处理玉米酒精清槽液的研究[J].环境污染与防治,2002,24(3)：129-131.
[34]刘维俊.壳聚糖对硅藻土悬浮液带电粒子体系的絮凝行为[J].太原理工大学学报,2001,32(6)：654-656.
[35]张延安,赵乃仁,张继荣,等.用壳聚糖絮凝剂去除水中汞[J].东北大学学报：自然科学版,1997(1)：68-71.
[36]陈亮,吴重亮,陈东辉.芘荧光探针法研究壳聚糖絮凝机理[J].环境保护科学,2002,114(28)：40-45.
[37]周玉燕,潘丽娟,郑瑛,等.β环糊精与聚丙烯酰胺的接枝化合物及其对水中污染物的絮凝作用 [J].化工环保,200323(6)：362-366.
[38]Entry J A, Phillips I, stratton H, etal Efficacy of polyacrylan ide +Al2(SO4)3and polyacry ide+CaO to filter Microorganisms and Nutrients from aninal wastewater[J]. Environmental Polution, 2003,12(1):453-462.
[39]Nacheva P M, Bustillos L T, Camperos E R,et al Characterization and Coagylation- Flocculation Treatability of Mexico City Wastewater A pplying Ferric Chlorde and Polymers [J].Wat Sci Tech,1996,34(3):235-247.
[40]江霜英,高廷耀,张文均.复合混凝剂CAF的研制与净水效果实验[J].化工环保,2000,20(5)：32-35.
[41]宋辉,聂新卫,马希晨.改性天然高分子与无机高分子复配絮凝剂PMC的研制[J].大连轻工学院学报,2003,22(2)：91-93.
[42]张凯松,周启星,吴伟民.铝盐-淀粉复合絮凝剂污水处理效果实验[J].应用生态学报,2004,15(8)：1443-1446.
[43]郑怀礼.生物絮凝剂和絮凝技术[M].北京：化学工业出版社,2004,1.
[44]马放.环境生物技术[M].北京：化学工业出版社,2003.
[45]湛含辉,张晓琪,湛雪辉,等.水处理中微生物絮凝剂的研究进展及方法[J].2002,16(4)：103-104.
[46]杨廷梅,周富春.微生物絮凝剂-絮凝剂发展的新方向[J].2002,21(1)：129-132.
[47]唐晓萍.微生物絮凝剂应用于污水处理过程中的优化分析[J].重庆大学学报,2002,25(7)：118-121.
[48]邓述波,余刚,蒋展鹏,等.微生物絮凝剂在给水处理中的应用研究[J].中国给水排水,2001,17(2)
[49]陈元彩,肖锦.[J].四川环境,2004,23(4)：12-14.
[50]Pal S,MalD,Singh R P.[J].Carbohydrate Polymers,2005,59:417-423.
[51]Khalil MI, Farag S.[J].Starch,1998,50 (6):267-272.
[52]曲有杰,陈捷,丁永生,等。[J].大连海事大学学报,2004,30(4)：47-50.
[53]王琛,陈杰溶,宗刚,等.[J].化工进展,2003,22(11)：1217-1221.
[54]王琛,陈杰溶.[J].水处理技术,2005,31(8)：21-23.
[55]马希晨,邰玉蕾.[J].精细石油化工,2002,(2)：13-15.
[56]许映军,丁永生,公维民,等.[J].应用化学,2004,21(5)：498-501.
[57]唐星华,舒红英,吴再国.[J].水处理技术,2005,31(9)：52-55.
[58]胡瑞,周华,李田霞,陈存华.[J].化工进展,2006,25(6)：600-603.
[59]永泽满等编,高分子水处理剂(下),陈振兴译,化学工业出版社,1985年第1版,285页.
[60]Susumu Kawamura,Effectiveness of Natural Polyedectrolytes in Water Treatment, JOURNALAWWA,1991(10):88-91.
[61]马希晨,吴星娥,曹亚峰.淀粉基两性天然高分子改性絮凝剂的合成[J].吉林大学学报：理学版,2004,42(2)：273-277.
[62]Guo-zhen Zheng et.al.,Interactions and chain mobilities of O-Carboxymerhy1-O-2-(diethulamino) ethylcellulose in aqueous solutions, Polymer,1996,37(9):1629-1634.
[63]Guo-zhen Zheng et.al.,Inter-and Intra-molercular Ionic interactions of Polyamphllyte. Carboxymethul 2-diethy laminoethylcellulose,Polymer International,1994,34:241-248.
[64]张黎明等,水溶性两性纤维素衍生物,应用化学,1998,15(4)：5-8.
[65]董岁明,孟燕,具梅.物理化学实验[M].西安：陕西科学技术出版社,2007：5-89.
[66]奚旦立,孙裕生,刘秀英编著.环境检测[M].北京：高等教育出版社,2004：549-550,562-564.
[67]张锦柱编著.工业分析[M].重庆：重庆大学出版社,1997：79-80.
[68]陈菊勤,关一峰等.工业水处理,1993,13(5)：23-26.
[69]马放,李淑更,金文标,等.微生物絮凝剂的研究现状及发展趋势[J].工业用水与废水,2002,33(1)：7-9.
[70]马放,张金凤,远立江,等.复合型生物絮凝剂成分分析及其絮凝机理的研究[J].环境科学学报,2005,25(11)：1491-1496.
[71]陶然,杨朝晖,曾光明,等.微生物絮凝剂及其絮凝微生物的研究进展[J].微生物学杂志,2005,25(4)：82-88.
[72]Levy N Y, Magdassi V S.Floccylation of Bentonite Particles by a Cyanobacterial Bioflocculant [J].Colloids and Surfaces,1990,48:337-349.
[73]Mabire F,et al.Flocculation properties of some water-soluble cationic copolymers toward silica suspensions.J.Colloid Interface Sci.,1984,97(1):120-123.
[74]佐藤T.等著,江龙等译.聚合物吸附对胶态分散体系稳定性的影响.北京：科学出版社,1988,103.
[75]永泽满等著,陈振兴译.高分子水处理剂(下卷).北京：化学出版社,1985,80.
[76]C.Ovenden,H.Xiao,Flocculation behaviour and mechanisms of cationic inorganic microparticle/polymer systems, Colloid Surf. A 197 (2002) J.225-234
[2]吕锦玲.天然高分子植物胶絮凝剂的制备及应用研究[D].昆明理工大学.2005.
[3]迟春娟.液-液萃取法处理高氯难降解有机废水[D].浙江工业大学.1998.
[4]刘建兰,钱惠芬,张东明,陈亚萍.聚铝架凝制的研究进展[D].化工时刊.2001(11)：16-18.
[5]王东升.中过给水排水,1997,13(5)：20-21.
[6]崔蕴霞等.工业水处理,1998,18(3)：8-9.
[7]Bottero J Yet al.J.Phys.chem.,1980,84:29-33.
[8]吴绍情等.工业水处理,1994,14(3)：1-3.
[9]范瑾初.混凝技术.北京：中国环境科学出版社,1992：10-16.
[10]胡万里等.工业水处理,1995,15(1)：7-9.
[11]于尔捷译.国外环境科学技术,1995(1)：11-14.
[12]李为群等.环境污染与防治,1997,19(3)：32-35.
[13]史建国.聚合硫酸铁的研制与应用[J].水利电力劳动保护,1996,6(2)：28-30.
[14]李善仁,李凤亭.无机和有机复合高分子絮凝剂的现状和发展方向[J].煤矿环境保护,2001,10(2)：15-19.
[15]Brian A, Jane B. Soluble Polymers in WaterofPurificartion[J].Prog Polym Sci 1995, 20(6):1014-1016.
[16]Wong Shing Hydrophilic Dispersion Polyners of Diaflyldinethyl Ammonium Chloride and A crylamide for the Clarification of Drinking Process Water US,6019904[P].2000-02-01.
[17]刘明华编.有机高分子絮凝剂的制备及应用[M].北京：化学工业出版社,2006：145-190.
[18]唐琼,张新申,李正飞.有机高分子改性阳离子絮凝剂的开发与应用前景[J].中国皮革,2002,31(21)：29-32.
[19]韩庆昌,娄金生,王芳,刘海波.有机高分子复合絮凝剂的研究进展与发展趋势[A].南京大学学报,2007,21(2)：34-36.
[20]秦丽娟陈夫山.有机高分子絮凝剂的研究进展及发展趋势.天京科技大学,2004,35(1)：41-43.
[21]巩冠群,张英杰,伊家贵,等.共聚有机强阳离子絮凝剂的开发及应用[J].石化技术与应用,2005,23(20)：138-141.
[22]Song B K, ChoM S, Yoon K Jetal Dispersion polymerization of acrylan icle with quaternary ammonium cation ic comonomer in aqueous solution [J].Journal of Applied Polymer Science, 2003,87(7):1101-1108
[23]Richardson Acrylanicle diallyl dinethyl ammonium chloride copolymers as inproved dewatering acids formineralprocessing US,4673511[P].1987-06-16.
[24]仁海静,陈文纳,温庆林,等.高阳离子度有机絮凝剂的合成[J].化工技术与开发,2004,33(1)：7-10.
[25]Rath S K, Singh R P. On the characterization of grafted and ungragted starch, amylose,and amylopectin[J]. Journal of Applied Polyner Science,1998,70(9):1795-1810.
[26]周玉燕,潘丽娟,郑瑛,等。p环糊精与丙烯酰胺的接枝化合物及其对水中污染物的絮凝作用[J].化工环保,2003,23 (6):362-366.
[27]Karnakar N C, Rath SK, Satry B S,etal investigation on glocculation characteristics of polysacchardebased graft copolymers in coal fines suspension [J]. Journal of Applied Polymer Science,1998,70.2619-2625.
[28]PalS,MalD,Singh R P. Cation ic starchr an effective floccylating agent [J]. Carbohydrate Polymer, 2005,59(4):417-423.
[29]盛雪芹,丁永生,公维民,等.天然改性阳离子絮凝剂制备及性能研究[J].大连海事大学学报,2002,28(4)：72-75.
[30]秋增昌,王海毅.木质素的应用研究现状与进展[J].西南造纸,2004,33(3)：29-33.
[31]尹华,肖锦.多功能水处理剂研究进展[J].工业水处理,1995,15(2)：1-2.
[32]甘光奉,甘莉.天然改性有机物高分子絮凝剂研究进展[J].石油与天然气化工,1996,25(1)：55-57.
[33]冯玉杰,金永新.壳聚糖季铵盐处理玉米酒精清槽液的研究[J].环境污染与防治,2002,24(3)：129-131.
[34]刘维俊.壳聚糖对硅藻土悬浮液带电粒子体系的絮凝行为[J].太原理工大学学报,2001,32(6)：654-656.
[35]张延安,赵乃仁,张继荣,等.用壳聚糖絮凝剂去除水中汞[J].东北大学学报：自然科学版,1997(1)：68-71.
[36]陈亮,吴重亮,陈东辉.芘荧光探针法研究壳聚糖絮凝机理[J].环境保护科学,2002,114(28)：40-45.
[37]周玉燕,潘丽娟,郑瑛,等.β环糊精与聚丙烯酰胺的接枝化合物及其对水中污染物的絮凝作用 [J].化工环保,200323(6)：362-366.
[38]Entry J A, Phillips I, stratton H, etal Efficacy of polyacrylan ide +Al2(SO4)3and polyacry ide+CaO to filter Microorganisms and Nutrients from aninal wastewater[J]. Environmental Polution, 2003,12(1):453-462.
[39]Nacheva P M, Bustillos L T, Camperos E R,et al Characterization and Coagylation- Flocculation Treatability of Mexico City Wastewater A pplying Ferric Chlorde and Polymers [J].Wat Sci Tech,1996,34(3):235-247.
[40]江霜英,高廷耀,张文均.复合混凝剂CAF的研制与净水效果实验[J].化工环保,2000,20(5)：32-35.
[41]宋辉,聂新卫,马希晨.改性天然高分子与无机高分子复配絮凝剂PMC的研制[J].大连轻工学院学报,2003,22(2)：91-93.
[42]张凯松,周启星,吴伟民.铝盐-淀粉复合絮凝剂污水处理效果实验[J].应用生态学报,2004,15(8)：1443-1446.
[43]郑怀礼.生物絮凝剂和絮凝技术[M].北京：化学工业出版社,2004,1.
[44]马放.环境生物技术[M].北京：化学工业出版社,2003.
[45]湛含辉,张晓琪,湛雪辉,等.水处理中微生物絮凝剂的研究进展及方法[J].2002,16(4)：103-104.
[46]杨廷梅,周富春.微生物絮凝剂-絮凝剂发展的新方向[J].2002,21(1)：129-132.
[47]唐晓萍.微生物絮凝剂应用于污水处理过程中的优化分析[J].重庆大学学报,2002,25(7)：118-121.
[48]邓述波,余刚,蒋展鹏,等.微生物絮凝剂在给水处理中的应用研究[J].中国给水排水,2001,17(2)
[49]陈元彩,肖锦.[J].四川环境,2004,23(4)：12-14.
[50]Pal S,MalD,Singh R P.[J].Carbohydrate Polymers,2005,59:417-423.
[51]Khalil MI, Farag S.[J].Starch,1998,50 (6):267-272.
[52]曲有杰,陈捷,丁永生,等。[J].大连海事大学学报,2004,30(4)：47-50.
[53]王琛,陈杰溶,宗刚,等.[J].化工进展,2003,22(11)：1217-1221.
[54]王琛,陈杰溶.[J].水处理技术,2005,31(8)：21-23.
[55]马希晨,邰玉蕾.[J].精细石油化工,2002,(2)：13-15.
[56]许映军,丁永生,公维民,等.[J].应用化学,2004,21(5)：498-501.
[57]唐星华,舒红英,吴再国.[J].水处理技术,2005,31(9)：52-55.
[58]胡瑞,周华,李田霞,陈存华.[J].化工进展,2006,25(6)：600-603.
[59]永泽满等编,高分子水处理剂(下),陈振兴译,化学工业出版社,1985年第1版,285页.
[60]Susumu Kawamura,Effectiveness of Natural Polyedectrolytes in Water Treatment, JOURNALAWWA,1991(10):88-91.
[61]马希晨,吴星娥,曹亚峰.淀粉基两性天然高分子改性絮凝剂的合成[J].吉林大学学报：理学版,2004,42(2)：273-277.
[62]Guo-zhen Zheng et.al.,Interactions and chain mobilities of O-Carboxymerhy1-O-2-(diethulamino) ethylcellulose in aqueous solutions, Polymer,1996,37(9):1629-1634.
[63]Guo-zhen Zheng et.al.,Inter-and Intra-molercular Ionic interactions of Polyamphllyte. Carboxymethul 2-diethy laminoethylcellulose,Polymer International,1994,34:241-248.
[64]张黎明等,水溶性两性纤维素衍生物,应用化学,1998,15(4)：5-8.
[65]董岁明,孟燕,具梅.物理化学实验[M].西安：陕西科学技术出版社,2007：5-89.
[66]奚旦立,孙裕生,刘秀英编著.环境检测[M].北京：高等教育出版社,2004：549-550,562-564.
[67]张锦柱编著.工业分析[M].重庆：重庆大学出版社,1997：79-80.
[68]陈菊勤,关一峰等.工业水处理,1993,13(5)：23-26.
[69]马放,李淑更,金文标,等.微生物絮凝剂的研究现状及发展趋势[J].工业用水与废水,2002,33(1)：7-9.
[70]马放,张金凤,远立江,等.复合型生物絮凝剂成分分析及其絮凝机理的研究[J].环境科学学报,2005,25(11)：1491-1496.
[71]陶然,杨朝晖,曾光明,等.微生物絮凝剂及其絮凝微生物的研究进展[J].微生物学杂志,2005,25(4)：82-88.
[72]Levy N Y, Magdassi V S.Floccylation of Bentonite Particles by a Cyanobacterial Bioflocculant [J].Colloids and Surfaces,1990,48:337-349.
[73]Mabire F,et al.Flocculation properties of some water-soluble cationic copolymers toward silica suspensions.J.Colloid Interface Sci.,1984,97(1):120-123.
[74]佐藤T.等著,江龙等译.聚合物吸附对胶态分散体系稳定性的影响.北京：科学出版社,1988,103.
[75]永泽满等著,陈振兴译.高分子水处理剂(下卷).北京：化学出版社,1985,80.
[76]C.Ovenden,H.Xiao,Flocculation behaviour and mechanisms of cationic inorganic microparticle/polymer systems, Colloid Surf. A 197 (2002) J.225-234