淀粉废水絮凝用丙烯酸钠聚合物的研究
摘要
本论文采用过硫酸钾和氨水潜在引发体系，利用水溶液聚合的方法合成了高分子量丙烯酸钠-丙烯酰胺共聚物，研究了影响聚合物分子量的各种因素，并以此聚合产物作为絮凝剂对淀粉废水进行处理，探讨最佳絮凝条件。合成絮凝剂时，共聚组分的配比、引发剂用量、反应温度、乙酸的使用、单体浓度、反应时间均影响到絮凝剂的分子量、分子链形态及水溶性，进而影响到絮凝性能。在淀粉废水最佳絮凝条件的探讨中发现，废水的酸碱性、絮凝剂分子量及投加量、助凝剂的种类及投加量、搅拌速度和时间等均对废水处理效果有明显的影响。结果表明，采用丙烯酸钠-丙烯酰胺共聚物作絮凝剂，氯化钙作助凝剂处理淀粉废水时，COD_(Cr)去除率可达50％以上，浊度去除率可达90％以上，所得到的絮体无毒，可进一步回收利用。此外，合成的丙烯酸钠-丙烯酰胺共聚物在铝厂赤泥分离及高浊水澄清中也取得了满意的效果。
The high relative molecular weight poly( sodium acrylate) was prepared by copolymerization in aqueous solution using sodium acrylate and acrylamide as raw materials and K2S2O8-NH3 redox initiation system. The product was used as flocculant to treat starch wastewater. The effects of the content of ammonia and potassium persulfate, reaction temperature, monomer concentration, mole ratio of monomers, the amount of acetic acid and pH value of system on the relative molecular weight and flocculation effect of the polymer were studied and the optimum reaction were determined. This article dealed with the influencing factors and the optimum treating condition of the starch wastewater with poly(sodium acrylate). It has been found that those factor, including the dose of flocculant and aid-flocculant, pH of wastewater, agitation speed, agitation time, etc, have significant effect on the COD and the turbidity removal. The results showed COD removal rate was no less than 50%, turbidity removal rate more than 90%, while
using sodium acrylate-acryamide copolymer as flocculant and CaC\2 as aid-flocculant. The flocculate is nonpoisonous and can be recycled. More experiment has demonstrated better efficiency of separating red mud in aluminum factories and high turbidity water treatment.
The high relative molecular weight poly( sodium acrylate) was prepared by copolymerization in aqueous solution using sodium acrylate and acrylamide as raw materials and K2S2O8-NH3 redox initiation system. The product was used as flocculant to treat starch wastewater. The effects of the content of ammonia and potassium persulfate, reaction temperature, monomer concentration, mole ratio of monomers, the amount of acetic acid and pH value of system on the relative molecular weight and flocculation effect of the polymer were studied and the optimum reaction were determined. This article dealed with the influencing factors and the optimum treating condition of the starch wastewater with poly(sodium acrylate). It has been found that those factor, including the dose of flocculant and aid-flocculant, pH of wastewater, agitation speed, agitation time, etc, have significant effect on the COD and the turbidity removal. The results showed COD removal rate was no less than 50%, turbidity removal rate more than 90%, while
using sodium acrylate-acryamide copolymer as flocculant and CaC\2 as aid-flocculant. The flocculate is nonpoisonous and can be recycled. More experiment has demonstrated better efficiency of separating red mud in aluminum factories and high turbidity water treatment.
引文
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[1]何国庆等．小麦淀粉工业废水的水质特征及酶法预处理条件研究．浙江农业学报，1997，9(5)：235～239
[2]王凯军，秦入伟．发酵工业废水处理．北京：化学工业出版社．2000
[3]王宝贞．水污染控制工程．北京：高等教育出版社，1990
[4]徐乃盐．食品工业废水的治理技术．环境保护，1992，6：22～24
[5]乌锡康．有机化工废水治理技术．北京：化学工业出版社．1999
[6]刘莱娥等．膜分离技术．北京：化学工业出版社．2000
[7]马荣俊等．工业废水的治理．中南工业大学出版社．1991
[8]刘学铭等．味精废水处理技术进展．工业水处理．1998，18(6)：1～10
[9]CN 1，217，890
[10]于伟君，石俊艳等．淀粉废水生产饲料酵母的研究．饲料工业，1991，(12)：20～21
[11]Jamuna R., SCP production and removal of organic load from cassava starch industry waste by yeasts. J. Ferment. Bioeng, 1989,67(2):126～131
[12]梁智．利用木薯淀粉废水生产单细胞蛋白的可行性探讨．饲料工业，1997，(4)：25～28
[13]何国庆，尹源明等．在小麦淀粉废水中培养白地酶的研究．中国粮油学报，1998，13(5)：33～37
[14]朱辉，何国庆．利用淀粉废水培养食用菌菌丝体的研究．中国粮油学报．1998，13(6)：35-38
[15]朱辉，何国庆，尹源明．金针菇和香菇在淀粉废水中的生长适应性．浙江农业大学学报，1997，23(6)：659～662
[16]朱辉，何国庆．金针菇在淀粉废水中发酵的营养条件研究．生物工程学报，1999，15(4)：56～62
[17]朱辉，何国庆．利用金针菇发酵处理淀粉工业废水的效果评定及产物营养成分分析．中国粮油学报，1999，14(6)：55～57
[18]Nilolavcic B. and Svardal K., Biological treatment of potato-starch wastewater-design and application of an aerobic selector. Water Science and Technology,2000,41(9):251～258
[19]余宗莲，田由芸．厌氧接触消化技术处理高浓度淀粉废水研究．青岛海洋大学学报，1997，(3)：16～20
[20]Annachhatre, Ajitp; Amatya Prasanna L.,UASB treatment of tapioca starch wastewater. Journal of Environmental Engineering, 2000,126(12):1149～1152
[21]B. N. Mishra and Anil Kumar, Anaerobic treatment of potato-starch wastewater using a foam bed bioreactor. The Genetic Engineer and Biotechnologist, 1997,17(4):165～174
[22]贺晓红等．常温纵向折流套筒式厌氧污泥床反应器处理淀粉废水的研究．给水排水，1998，(3)：36～39
[23]皇甫浩，罗德春．玉米淀粉废水处理工艺的研究．西安公路交通大学学报，1999，(3)：25～28
[24]Guan Yutao et al. Study on Twophase Anaerobic Membrane Biosystem for Starch Wastewater Treatment. Water & Wastewater Engineering, 1999,25(12):1239～1245
[25]张向京等．从药厂废水中回收粗蛋白的研究．河北工业科技，1999，16(2)6～9
[26]李亚峰等．混凝-吸附法处理淀粉废水．沈阳建筑工程学院．1999，15(1)：40～43
[27]严瑞瑄．水处理剂应用手册．北京：化学工业出版社．2000
[28]张佩芳等．脱乙酰甲壳质处理淀粉废水的实验．环境污染与防治，1990，12(3)：22～23
[29]邓述波等．微生物絮凝剂处理淀粉废水的研究．工业水处理．1999，19(5)：8～10
[30]Selmer-Olsen, E.,Ratnaveera H.C., Pehrson R. A novel treatment process for dairy wastewater with chitosan produced from shrimp-shell waste. Water Science Technology, 1996,34:33～40
[31]Jun, Hye Keong et al. Chitosan as a coacculant for recovery of proteinaceous solids from Tofu wastewater. Journal Agriculture food chemistry, 1994,42(8):1834～1838
[32]USP 5,174,903
[33]王乃芝，苏永渤．化学法处理淀粉生产废水．工业用水与废水，2000，31(1)：29～31
[34]张凡，陈青．味精淀粉废水中提取菌体蛋白初探．河南科学，1999，17(4)：419～422
[35][日]大森英三著，朱传綮译．功能性丙烯酸树脂，北京，化学工业出版社，1993
[36]化工百科全书，第一卷，85
[37]严瑞碹．水溶性高分子，北京：化学工业出版社，1998
[38]朱月群．西北工业大学博士学位论文，200l
[39]天津化工研究院絮凝剂组．高分子量聚丙烯酸钠的研制及其应用．工业水处理，1985，5(1)：6～9
[40]曾之平等．聚丙烯酸钠的制备和应用．河南化工，1997，(5)8～9
[41]赵红坤等．高分量聚丙烯酸钠合成工艺条件的探讨．天然气化工，1997，22(4)：39～41
[42]Anuradha Rangarai et al. Synthesis and characterization of some water soluble polymer. Journal of Applied Polymer Science. 1997,66:45～56
[43]Martial Pabon et al. Polymerization of acrylamide in solusion and inverse emulsion: number molecular weight distribution with chain transfer agent. Polymer, 1999,40:3101～3106
[44]鲁郑全等．超高分子量速溶聚丙烯酸钠的合成与应用．河南化工．1997，(11)：9～13
[45]余学军，徐丹等．速溶高分子量聚丙烯酸钠的合成研究．化学世界，1999，(6)：310～312
[46]姚克俊，叶传辉．水溶性聚合物的研究．山东大学学报，1987，22(6)：90～96
[47]余克阳等．丙烯酸单体用氧化-还原引发剂引发还原聚合．北京化工大学学报，1995，22(4)：41～45
[48]USP 4，024，099
[49]USP 4，115，339
[50]罗健辉等．部分水解聚丙烯酰胺过滤因子研究．油田化学．1998，15(3)：261～264
[51]顾梅，朱秀林等．丙烯酰胺的微波聚合研究．高分子材料科学与工程，1997，13(5)36～39
[52]Baade W. Reichert K-H Kinetics of the dispersion polymerization of acrylamide. Europe Polymer Science, 1984,20(5): 505
[53]Candau F.,Leong YS. Kinetic study of the Polymerization of Acrylamide in inverse miroemulsion. J Polymer Sci: polymer Chem, 1985:23(1):193
[54]Barajas JH.,Hunkeler D., Heterophase water-in-oil polymerization of acrylamide by a hybrid inver-microemulsion process. Polymer, 1997:38(22):5623
[55]Dimonie MV. et al. Iverse suspension polymerization of acrylamide. Eur Polym J 1982,18(7):639
[56]Zuifang Liu, Brian W. Brooks. Inverse dispersion polymerization of acrylic acid
initiated by a water-soluble redox pair: the role of drop mixing. Polymer, 1999:40:2181～2188
[57]徐相凌，张志成等．丙烯酸钠反相乳液聚合．高分子学报，1998(2)：134～138
[58]潘智存，王晓茹等．丙烯酸系反相乳液共聚合反应的研究．清华大学学报，1998，38(6)：49～51
[59]GB 12005．10-92
[60]何曼君，陈维孝，董西侠．高分子物理．复旦大学出版社，1990
[61]潘祖仁．高分子化学．北京：化学工业出版社，1997
[62]唐康泰，潘松汉．聚丙烯酰胺结构和溶解性能．广州化工．1996，24，(3)：55～61
[63]蓝立文．高分子物理．西安：西北工业大学，1993
[64]付美龙，周克厚等。西南石油学院学报，2l(1)：71～73
[65]金熙，项成林，齐冬子．工业水处理技术问答及常用数据．北京：化学工业出版社，1997
[66]Levy N.,Magdassi S. and Bar-Or Y. Physico-chemical aspect in flocculation of bentonite suspensions by a cyanobacterial bioflocculation. Water Research, 1992:26: 249～254
[67]Jiang Yu, Huizhou Liu, Jiayong Chen. Flocculation and characterization of protein by anionic copolymer containing reactive functional groups. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000:163:225～232
[68]Kalyan K. Das. Ultra-low dosage flocculation of alumina using polyacylic acid. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2001: 182:25～33
[69]Jiang Yu, Huizhou Liu, Jiayong Chen. "Modified flocculation" of protein with a combination of anionic copolymer and polyacrylamide. Chemical Engineering Science, 1999,54: 24:5839～5843
[70]Anders Larsson, Charlotte Walldal. Flocculation of cationic polymer and nanosized particles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1999: 159:65～76
[71]Anders Lansson, Staffan Wall. Flocculation of cationic amylopectin starch and colloidal silicic acid. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 1998: 139:259～270
[72]Sara Stemme, Lars Odberg. Effect of colloidal silica and electrolyte on the structure of an adsorbed cationic polyelectrolyte layer. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1999: 155:145～154
[73]Tom Asselmen, Gil Garnler. The role of anionic microparticles in a poly(acrylamide) -montmorillonite flocculation aid system. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2000:170:1:79～90
[74]Ferene Csampesz. Enhanced flocculation of colloidal dispersions by polymer mixture. Chemical Engineering Journal, 2000:80:43～49
[75]Simon Biggs, Michael Habgood. Aggregate structures formed via a bridging flocculation mechanism. Chemical Engineering Journal, 2000:80:13～22
[76]Sharna M. Glover, Yaode Yan, Bridging flocculation studied by light scattering and settling. Chemical Engineering Journal, 2000:80:3～12
[77]Dematriades K. Ultrasonic attenuation spectroscopy study of flocculation in protein stabilized emulsions. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 1999,150:45～54
[78]江新民，桂康．聚丙烯酸钠在赤泥分离中的应用．轻金属，1999(6)：17～20
[1]何国庆等．小麦淀粉工业废水的水质特征及酶法预处理条件研究．浙江农业学报，1997，9(5)：235～239
[2]王凯军，秦入伟．发酵工业废水处理．北京：化学工业出版社．2000
[3]王宝贞．水污染控制工程．北京：高等教育出版社，1990
[4]徐乃盐．食品工业废水的治理技术．环境保护，1992，6：22～24
[5]乌锡康．有机化工废水治理技术．北京：化学工业出版社．1999
[6]刘莱娥等．膜分离技术．北京：化学工业出版社．2000
[7]马荣俊等．工业废水的治理．中南工业大学出版社．1991
[8]刘学铭等．味精废水处理技术进展．工业水处理．1998，18(6)：1～10
[9]CN 1，217，890
[10]于伟君，石俊艳等．淀粉废水生产饲料酵母的研究．饲料工业，1991，(12)：20～21
[11]Jamuna R., SCP production and removal of organic load from cassava starch industry waste by yeasts. J. Ferment. Bioeng, 1989,67(2):126～131
[12]梁智．利用木薯淀粉废水生产单细胞蛋白的可行性探讨．饲料工业，1997，(4)：25～28
[13]何国庆，尹源明等．在小麦淀粉废水中培养白地酶的研究．中国粮油学报，1998，13(5)：33～37
[14]朱辉，何国庆．利用淀粉废水培养食用菌菌丝体的研究．中国粮油学报．1998，13(6)：35-38
[15]朱辉，何国庆，尹源明．金针菇和香菇在淀粉废水中的生长适应性．浙江农业大学学报，1997，23(6)：659～662
[16]朱辉，何国庆．金针菇在淀粉废水中发酵的营养条件研究．生物工程学报，1999，15(4)：56～62
[17]朱辉，何国庆．利用金针菇发酵处理淀粉工业废水的效果评定及产物营养成分分析．中国粮油学报，1999，14(6)：55～57
[18]Nilolavcic B. and Svardal K., Biological treatment of potato-starch wastewater-design and application of an aerobic selector. Water Science and Technology,2000,41(9):251～258
[19]余宗莲，田由芸．厌氧接触消化技术处理高浓度淀粉废水研究．青岛海洋大学学报，1997，(3)：16～20
[20]Annachhatre, Ajitp; Amatya Prasanna L.,UASB treatment of tapioca starch wastewater. Journal of Environmental Engineering, 2000,126(12):1149～1152
[21]B. N. Mishra and Anil Kumar, Anaerobic treatment of potato-starch wastewater using a foam bed bioreactor. The Genetic Engineer and Biotechnologist, 1997,17(4):165～174
[22]贺晓红等．常温纵向折流套筒式厌氧污泥床反应器处理淀粉废水的研究．给水排水，1998，(3)：36～39
[23]皇甫浩，罗德春．玉米淀粉废水处理工艺的研究．西安公路交通大学学报，1999，(3)：25～28
[24]Guan Yutao et al. Study on Twophase Anaerobic Membrane Biosystem for Starch Wastewater Treatment. Water & Wastewater Engineering, 1999,25(12):1239～1245
[25]张向京等．从药厂废水中回收粗蛋白的研究．河北工业科技，1999，16(2)6～9
[26]李亚峰等．混凝-吸附法处理淀粉废水．沈阳建筑工程学院．1999，15(1)：40～43
[27]严瑞瑄．水处理剂应用手册．北京：化学工业出版社．2000
[28]张佩芳等．脱乙酰甲壳质处理淀粉废水的实验．环境污染与防治，1990，12(3)：22～23
[29]邓述波等．微生物絮凝剂处理淀粉废水的研究．工业水处理．1999，19(5)：8～10
[30]Selmer-Olsen, E.,Ratnaveera H.C., Pehrson R. A novel treatment process for dairy wastewater with chitosan produced from shrimp-shell waste. Water Science Technology, 1996,34:33～40
[31]Jun, Hye Keong et al. Chitosan as a coacculant for recovery of proteinaceous solids from Tofu wastewater. Journal Agriculture food chemistry, 1994,42(8):1834～1838
[32]USP 5,174,903
[33]王乃芝，苏永渤．化学法处理淀粉生产废水．工业用水与废水，2000，31(1)：29～31
[34]张凡，陈青．味精淀粉废水中提取菌体蛋白初探．河南科学，1999，17(4)：419～422
[35][日]大森英三著，朱传綮译．功能性丙烯酸树脂，北京，化学工业出版社，1993
[36]化工百科全书，第一卷，85
[37]严瑞碹．水溶性高分子，北京：化学工业出版社，1998
[38]朱月群．西北工业大学博士学位论文，200l
[39]天津化工研究院絮凝剂组．高分子量聚丙烯酸钠的研制及其应用．工业水处理，1985，5(1)：6～9
[40]曾之平等．聚丙烯酸钠的制备和应用．河南化工，1997，(5)8～9
[41]赵红坤等．高分量聚丙烯酸钠合成工艺条件的探讨．天然气化工，1997，22(4)：39～41
[42]Anuradha Rangarai et al. Synthesis and characterization of some water soluble polymer. Journal of Applied Polymer Science. 1997,66:45～56
[43]Martial Pabon et al. Polymerization of acrylamide in solusion and inverse emulsion: number molecular weight distribution with chain transfer agent. Polymer, 1999,40:3101～3106
[44]鲁郑全等．超高分子量速溶聚丙烯酸钠的合成与应用．河南化工．1997，(11)：9～13
[45]余学军，徐丹等．速溶高分子量聚丙烯酸钠的合成研究．化学世界，1999，(6)：310～312
[46]姚克俊，叶传辉．水溶性聚合物的研究．山东大学学报，1987，22(6)：90～96
[47]余克阳等．丙烯酸单体用氧化-还原引发剂引发还原聚合．北京化工大学学报，1995，22(4)：41～45
[48]USP 4，024，099
[49]USP 4，115，339
[50]罗健辉等．部分水解聚丙烯酰胺过滤因子研究．油田化学．1998，15(3)：261～264
[51]顾梅，朱秀林等．丙烯酰胺的微波聚合研究．高分子材料科学与工程，1997，13(5)36～39
[52]Baade W. Reichert K-H Kinetics of the dispersion polymerization of acrylamide. Europe Polymer Science, 1984,20(5): 505
[53]Candau F.,Leong YS. Kinetic study of the Polymerization of Acrylamide in inverse miroemulsion. J Polymer Sci: polymer Chem, 1985:23(1):193
[54]Barajas JH.,Hunkeler D., Heterophase water-in-oil polymerization of acrylamide by a hybrid inver-microemulsion process. Polymer, 1997:38(22):5623
[55]Dimonie MV. et al. Iverse suspension polymerization of acrylamide. Eur Polym J 1982,18(7):639
[56]Zuifang Liu, Brian W. Brooks. Inverse dispersion polymerization of acrylic acid
initiated by a water-soluble redox pair: the role of drop mixing. Polymer, 1999:40:2181～2188
[57]徐相凌，张志成等．丙烯酸钠反相乳液聚合．高分子学报，1998(2)：134～138
[58]潘智存，王晓茹等．丙烯酸系反相乳液共聚合反应的研究．清华大学学报，1998，38(6)：49～51
[59]GB 12005．10-92
[60]何曼君，陈维孝，董西侠．高分子物理．复旦大学出版社，1990
[61]潘祖仁．高分子化学．北京：化学工业出版社，1997
[62]唐康泰，潘松汉．聚丙烯酰胺结构和溶解性能．广州化工．1996，24，(3)：55～61
[63]蓝立文．高分子物理．西安：西北工业大学，1993
[64]付美龙，周克厚等。西南石油学院学报，2l(1)：71～73
[65]金熙，项成林，齐冬子．工业水处理技术问答及常用数据．北京：化学工业出版社，1997
[66]Levy N.,Magdassi S. and Bar-Or Y. Physico-chemical aspect in flocculation of bentonite suspensions by a cyanobacterial bioflocculation. Water Research, 1992:26: 249～254
[67]Jiang Yu, Huizhou Liu, Jiayong Chen. Flocculation and characterization of protein by anionic copolymer containing reactive functional groups. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000:163:225～232
[68]Kalyan K. Das. Ultra-low dosage flocculation of alumina using polyacylic acid. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2001: 182:25～33
[69]Jiang Yu, Huizhou Liu, Jiayong Chen. "Modified flocculation" of protein with a combination of anionic copolymer and polyacrylamide. Chemical Engineering Science, 1999,54: 24:5839～5843
[70]Anders Larsson, Charlotte Walldal. Flocculation of cationic polymer and nanosized particles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1999: 159:65～76
[71]Anders Lansson, Staffan Wall. Flocculation of cationic amylopectin starch and colloidal silicic acid. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 1998: 139:259～270
[72]Sara Stemme, Lars Odberg. Effect of colloidal silica and electrolyte on the structure of an adsorbed cationic polyelectrolyte layer. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1999: 155:145～154
[73]Tom Asselmen, Gil Garnler. The role of anionic microparticles in a poly(acrylamide) -montmorillonite flocculation aid system. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2000:170:1:79～90
[74]Ferene Csampesz. Enhanced flocculation of colloidal dispersions by polymer mixture. Chemical Engineering Journal, 2000:80:43～49
[75]Simon Biggs, Michael Habgood. Aggregate structures formed via a bridging flocculation mechanism. Chemical Engineering Journal, 2000:80:13～22
[76]Sharna M. Glover, Yaode Yan, Bridging flocculation studied by light scattering and settling. Chemical Engineering Journal, 2000:80:3～12
[77]Dematriades K. Ultrasonic attenuation spectroscopy study of flocculation in protein stabilized emulsions. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 1999,150:45～54
[78]江新民，桂康．聚丙烯酸钠在赤泥分离中的应用．轻金属，1999(6)：17～20