聚合硫酸铁的制备及在处理印染废水中的应用研究
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摘要
随着工业的发展,废水处理成为一个热门话题。近年来处理废水的方法在不断的开发并得以应用,混凝法也成为其中的主流,混凝剂的制备工艺开发及合理应用一直是生产和科研工作者努力的目标。
本论文由两部分构成:一是通过查阅大量的文献资料,对已有的絮凝剂聚合硫酸铁的合成工艺进行了总结和分析,发现过氧化氢直接氧化法制备PFS有着工艺简单、生产过程不产生二次污染物、生产周期短等优点。通过正交实验,改变合成反应中原料的投料比、反应过程的控制温度、pH值,检测产品的盐基度、全铁量,从而确定了实验室用过氧化氢直接氧化法制备聚合硫酸铁的最佳工艺参数,为其工业化生产提供了降低成本的理论依据。同时通过实验数据印证了文献所述助聚剂的加入可提高产品的盐基度这一观点。
二是利用制备得到的聚合硫酸铁(PFS)产品处理高色度、高COD印染废水,以寻求用PFS处理此类废水的最佳操作参数,为工业上实际应用提供一个理想参数,达到降低水处理成本的目的。实验数据证明,聚合硫酸铁处理这类印染废水有较好的处理效果。通过反复试验,得出结论——用聚合硫酸铁处理高色度印染废水时,絮凝剂的投加量、操作温度、溶液的酸度、搅拌速度及时间、静置时间等都会对处理水水质指标产生影响。达到最佳处理效果的操作指标为PFS的浓度120mg～160mg,温度20℃,酸度在PH值8～10范围,搅拌时间5min,静置时间30min。其中PFS的用量应根据水质指标的不同做相应的调整。若适当加入助凝剂能明显提高脱色率。
Wastewater treatment has become a hot issue with the development of industry. Recently,more and more methods to treat wastewater are developed and adopted.Among them,coagulation is the mainstream one.Producers and researchers aim to the preparation and usage of coagulant all along.
This thesis consists of two chapters.In chapter 1,the author analyzes and summarizes the available synthesis of flocculant polymeric ferric sulfate(PFS).It is easy to prepare PFS by direct oxidation of hydrogen peroxide with short production cycle,no secondary pollutants left.Through orthogonal test,the inventory ratio of raw materials,the control temperature,pH value,the basicity of detected products and total Ferro are changed,and then the optimum technology parameter of preparing PFS by direct oxidation of hydrogen peroxide in laboratory could be fixed,which is the theoretical basis of reducing cost during industrial production.Moreover,the author confirms that the basicity of products can be increased by adding promoter.
In chapter 2,this thesis focuses on treating high colority and high COD dyeing wastewater with the prepared PFS products.The author manages to provide the optimum control parameter for practice in order to reduce the cost of treatment.The experiment verifies the effectiveness of this treatment.While using PFS to treat high colority dyeing wastewater,the dosage of flocculant,the operation temperature,the acidity of solution,the agitation speed and time and the quiescent time will affect the water quality index.The best operation index is:PFS concentration with 120mg～160mg,20℃,pH 8～10,5 min for agitation and 30 min for quiescence.The dosage of PFS should be adjusted according to different water quality index.Appropriate amount of coagulant aid can help to promote the decoloration rate obviously.
本论文由两部分构成:一是通过查阅大量的文献资料,对已有的絮凝剂聚合硫酸铁的合成工艺进行了总结和分析,发现过氧化氢直接氧化法制备PFS有着工艺简单、生产过程不产生二次污染物、生产周期短等优点。通过正交实验,改变合成反应中原料的投料比、反应过程的控制温度、pH值,检测产品的盐基度、全铁量,从而确定了实验室用过氧化氢直接氧化法制备聚合硫酸铁的最佳工艺参数,为其工业化生产提供了降低成本的理论依据。同时通过实验数据印证了文献所述助聚剂的加入可提高产品的盐基度这一观点。
二是利用制备得到的聚合硫酸铁(PFS)产品处理高色度、高COD印染废水,以寻求用PFS处理此类废水的最佳操作参数,为工业上实际应用提供一个理想参数,达到降低水处理成本的目的。实验数据证明,聚合硫酸铁处理这类印染废水有较好的处理效果。通过反复试验,得出结论——用聚合硫酸铁处理高色度印染废水时,絮凝剂的投加量、操作温度、溶液的酸度、搅拌速度及时间、静置时间等都会对处理水水质指标产生影响。达到最佳处理效果的操作指标为PFS的浓度120mg～160mg,温度20℃,酸度在PH值8～10范围,搅拌时间5min,静置时间30min。其中PFS的用量应根据水质指标的不同做相应的调整。若适当加入助凝剂能明显提高脱色率。
Wastewater treatment has become a hot issue with the development of industry. Recently,more and more methods to treat wastewater are developed and adopted.Among them,coagulation is the mainstream one.Producers and researchers aim to the preparation and usage of coagulant all along.
This thesis consists of two chapters.In chapter 1,the author analyzes and summarizes the available synthesis of flocculant polymeric ferric sulfate(PFS).It is easy to prepare PFS by direct oxidation of hydrogen peroxide with short production cycle,no secondary pollutants left.Through orthogonal test,the inventory ratio of raw materials,the control temperature,pH value,the basicity of detected products and total Ferro are changed,and then the optimum technology parameter of preparing PFS by direct oxidation of hydrogen peroxide in laboratory could be fixed,which is the theoretical basis of reducing cost during industrial production.Moreover,the author confirms that the basicity of products can be increased by adding promoter.
In chapter 2,this thesis focuses on treating high colority and high COD dyeing wastewater with the prepared PFS products.The author manages to provide the optimum control parameter for practice in order to reduce the cost of treatment.The experiment verifies the effectiveness of this treatment.While using PFS to treat high colority dyeing wastewater,the dosage of flocculant,the operation temperature,the acidity of solution,the agitation speed and time and the quiescent time will affect the water quality index.The best operation index is:PFS concentration with 120mg～160mg,20℃,pH 8～10,5 min for agitation and 30 min for quiescence.The dosage of PFS should be adjusted according to different water quality index.Appropriate amount of coagulant aid can help to promote the decoloration rate obviously.
引文
[1]严瑞煊.水处理剂应用手册[M].北京:化学工业出版社,2000.
[2]张宏仁.中国的淡水资源问题[J].环境保护,2001,(5):3-7.
[3]解振华.新世纪环境形势与对策[J].环境保护,2001,(9):3-8.
[4]国家环保总局.2000年中国环境状况公报[J].环境保护,2001,(7):3-9.
[5]奕兆坤,汤鸿霄.我国无机高分子絮凝剂产业发展现状与规划[J].工业水处理,2000,20(11):1-6.
[6]聚合硫酸铁的制备影响因素考察[J],浙江化工,2003,(34):5:17-19.
[7]R D Letterman and S G Vanderbrook.Effect of solution chemistry on coagulation with hydrolyzed Al(Ⅲ)[J].Wat.Res.,1983,17(1):195-204.
[8]A Amirtharajah and kirk M Mills.Rapid-Mix design for mechanisms of alumcoagulation [J].J.AWWA.1982,74(4):210-216.
[9]John E Van Benschoten and James K Edzwald.Chemical Aspects of Coagulation' using aluminum salts-I.Hydrolytic reactions of alum and polyaluminum chloride[J].Wat.Res.,1990,24(12):1519-1526.
[10]John E Van Benschoten and James K Edzwald.Chemical Aspects of Coagulation using aluminum salts-II.Hydrolytic reactions of alum and polyaluminum chloride[J].Wat.Res.,1990,24(12):1527-1535.
[11]J.Y.Bottero,M Axelos,D Tchoubar etal.Mechanism of formation of aluminum trihydroxide from keggin Al13 Polymers[J].J.Colloid and Interface Science,1987,117(1):47-57.
[12]吴浩汀,刘立伟.聚合硫酸铁与其它无机混凝剂性能的比较[J]水处理技术,1989,15(5):290-294.
[13]吕新之.铝的污染和危害[J].环境保护,1998,(5):38-39.
[14]汪光焘.城市供水行业2000年技术进步发展规划[M]北京:中国建筑工业出版社,1993.
[15]崔福义,胡明成,张燕.我国部分城市饮用水中铝含量调查[J]中国给水排水,2002,18(1):5-8.
[16]S K Mittal and R K Ratra.Toxic effect ions on biochemical oxygen demand[J].Wat.Res.,2000,34(1):147-152.
[17]Joseph B H,Laverne C,Edward E L.Influence of pH and aluminum on developing brook trout in a low calcium water[J].Environ.Pollut.,1987,43:63-73.
[18]Christan Volk,Kimberly Bell,Eva Ibahim etal.Impact of enhanced and optimized coagulation on removed of organic matter and its biodegradable fraction in drinking water[J].Wat.Res.,2000,34(12):3247-3257.
[19]Nibal S Abuzaid and Aarif H Elmubarak.Coagulation of polymeric waste water discharged by chemical factory[J].Wat.Res.,1999,33(2):521-529.
[20]Fenny A M,Nelence A H,Serah K L.Hydroxylated ferric sulfate-an aluminum salt alternative[J].Water Supplv,1992,10(4):167-174.
[21]娄金生.水污染治理新工艺设计[M].北京:海洋出版社,1999.
[22]何义亮等.聚合硫酸铁处理制革废水[J].水处理技术,1995,21(3):175-178.
[23]曹德身等.铁盐活性污泥法处理印染废水的探索,水处理技术[J].1986,12(6):337-342.
[24]秦安荣.聚合硫酸铁的絮凝特性及其在环境保护中的应用[J].上海环境科学,1987,(01):24-29.
[25]汪多仁.一步法制备固体聚合硫酸铁新工艺[J].化工环保,1997,(4):211-214.
[26]陈益明.新型固体聚合硫酸铁在处理乳化液中的应用[J].工业水处理,1993,13(3):24-25.
[27]陈立丰.有机高分子絮凝剂和聚铁絮凝剂处理高浊度原水的研究[J].水处理技术,1999,25(1):49-53
[28]李风亭.国外氮氧化物催化法合成聚合硫酸铁新工艺[J].工业水处理,1998,18(5):9-10.
[29]雷华,袁书玉.无机絮凝剂聚合硫酸铁制备方法的评价[J].环境保护,1997,(4):15-16.
[30]阮复昌,公国庆,莫炳禄等.聚合硫酸铁的生产技术与效益评价[J].广东化工,1995,(2):4-6.
[31]陈辅君.无机高分子混凝剂聚合硫酸铁的制备新工艺[J].中国给水排水,1995,11(1):32-35.
[32]白玉兴,刘君,李杨.聚合硫酸铁合成中催化剂的研究[J].工业水处理,1996,16(2):9-11.
[33]林冰,廖为鑫,汪林.一种新的聚合硫酸铁的生产方法[P].CN1053222A:1991-07-24.
[34]章振,李安德.高效混凝剂净水灵的开发及应用[J].石油炼制与化工,1985,26(7):60-62.
[35]K M Allal,M Ocuchefoun,M Boumahrez.Oxidation of iron(Ⅲ)sulphate and use in water treatment[J].J.ofChem.Tech.and Biotech.,1996,34(10):151-159.
[36]Femuson,W J.Manufacture of aqueous ferric sulfate solutions and their use in water purification[P].GB2226561,1990-06-11.
[37]解立平,徐向荣.无机絮凝剂一聚合硫酸铁生产方法综述[J].环境与开发,2000,15(4):9-10.
[38]武道吉,陈冬辰,李风亭.国外制造聚合硫酸铁的新方法[J].化工环保,1997,(5):277-280.
[39]国家环保局、纺织工业部编.纺织印染废水一我国几种工业废水治理技术研究[M].北京:化学工业出版社,1988.
[40]王振东,张志祥.印染废水的污染与控制[J].环境科学与技术,2001,(1):21.
[41]Subbotina E A,Tarasevich Y I,Orazmuradov A O.Adsorption of direct dyes on organically substituted montmorillonite.Izu.Akad Nauk Turkm.SSR,Ser.Fiz.-Tekh.,Khim.Geol.Nauk 1985,(3):105108
[42]余颖,庄源益,邹其猛等.有机絮凝剂对水中染料的絮凝作用探讨明[J].环境化学,2000,19(2):142-147.
[43]宫世国,陶秀成,方金一.新型混凝脱色剂(ASD-II)的研制及其在印染废水处理中的应用[J].工业水处理,1993,13(5):16-19.
[44]尚国平等.改进的电解一气浮法处理印染废水[J].化工环保,1993,13(5):285-288.
[45]陈鸿林等.混凝沉淀一二氧化氯氧化法处理印染废水明[J].化工环保,1999,19(4):223-225.
[46]中华人民共和国国家标准GB 14591-2006 2-7.
[47]解立平等.聚合硫酸铁盐基度与絮凝性能关系的研究[J].工业水处理,2001,21(1):26-28.
[48]全国红,林红卫等.印染废水处理和综合利用技术[J].给水排水,2000,26(2):40-42.
[49]杨书铭,纺织印染工业废水治理技术[M].化学工业出版社,2002.
[50]戴日成.印染废水水质特征及处理技术综述[J].给水排水,2000,26(10):33.
[51]吴祖望.染色化学基础.大连理工大学化工学院教材[M].1994,29-31,184.
[52]黄长盾,杨西昆,汪凯民.印染废水处理[M].北京:纺织工业出版社,1987,1-10.
[53]汤鸿霄,无机高分子絮凝剂的几点新认识[J].工业水处理,1997,17(4):1-6.
[54]沈澄英,骆丽君.正交法研究PFS和PAM对印染废水的处理[J].天津化工,2003,17(5):30-32.
[2]张宏仁.中国的淡水资源问题[J].环境保护,2001,(5):3-7.
[3]解振华.新世纪环境形势与对策[J].环境保护,2001,(9):3-8.
[4]国家环保总局.2000年中国环境状况公报[J].环境保护,2001,(7):3-9.
[5]奕兆坤,汤鸿霄.我国无机高分子絮凝剂产业发展现状与规划[J].工业水处理,2000,20(11):1-6.
[6]聚合硫酸铁的制备影响因素考察[J],浙江化工,2003,(34):5:17-19.
[7]R D Letterman and S G Vanderbrook.Effect of solution chemistry on coagulation with hydrolyzed Al(Ⅲ)[J].Wat.Res.,1983,17(1):195-204.
[8]A Amirtharajah and kirk M Mills.Rapid-Mix design for mechanisms of alumcoagulation [J].J.AWWA.1982,74(4):210-216.
[9]John E Van Benschoten and James K Edzwald.Chemical Aspects of Coagulation' using aluminum salts-I.Hydrolytic reactions of alum and polyaluminum chloride[J].Wat.Res.,1990,24(12):1519-1526.
[10]John E Van Benschoten and James K Edzwald.Chemical Aspects of Coagulation using aluminum salts-II.Hydrolytic reactions of alum and polyaluminum chloride[J].Wat.Res.,1990,24(12):1527-1535.
[11]J.Y.Bottero,M Axelos,D Tchoubar etal.Mechanism of formation of aluminum trihydroxide from keggin Al13 Polymers[J].J.Colloid and Interface Science,1987,117(1):47-57.
[12]吴浩汀,刘立伟.聚合硫酸铁与其它无机混凝剂性能的比较[J]水处理技术,1989,15(5):290-294.
[13]吕新之.铝的污染和危害[J].环境保护,1998,(5):38-39.
[14]汪光焘.城市供水行业2000年技术进步发展规划[M]北京:中国建筑工业出版社,1993.
[15]崔福义,胡明成,张燕.我国部分城市饮用水中铝含量调查[J]中国给水排水,2002,18(1):5-8.
[16]S K Mittal and R K Ratra.Toxic effect ions on biochemical oxygen demand[J].Wat.Res.,2000,34(1):147-152.
[17]Joseph B H,Laverne C,Edward E L.Influence of pH and aluminum on developing brook trout in a low calcium water[J].Environ.Pollut.,1987,43:63-73.
[18]Christan Volk,Kimberly Bell,Eva Ibahim etal.Impact of enhanced and optimized coagulation on removed of organic matter and its biodegradable fraction in drinking water[J].Wat.Res.,2000,34(12):3247-3257.
[19]Nibal S Abuzaid and Aarif H Elmubarak.Coagulation of polymeric waste water discharged by chemical factory[J].Wat.Res.,1999,33(2):521-529.
[20]Fenny A M,Nelence A H,Serah K L.Hydroxylated ferric sulfate-an aluminum salt alternative[J].Water Supplv,1992,10(4):167-174.
[21]娄金生.水污染治理新工艺设计[M].北京:海洋出版社,1999.
[22]何义亮等.聚合硫酸铁处理制革废水[J].水处理技术,1995,21(3):175-178.
[23]曹德身等.铁盐活性污泥法处理印染废水的探索,水处理技术[J].1986,12(6):337-342.
[24]秦安荣.聚合硫酸铁的絮凝特性及其在环境保护中的应用[J].上海环境科学,1987,(01):24-29.
[25]汪多仁.一步法制备固体聚合硫酸铁新工艺[J].化工环保,1997,(4):211-214.
[26]陈益明.新型固体聚合硫酸铁在处理乳化液中的应用[J].工业水处理,1993,13(3):24-25.
[27]陈立丰.有机高分子絮凝剂和聚铁絮凝剂处理高浊度原水的研究[J].水处理技术,1999,25(1):49-53
[28]李风亭.国外氮氧化物催化法合成聚合硫酸铁新工艺[J].工业水处理,1998,18(5):9-10.
[29]雷华,袁书玉.无机絮凝剂聚合硫酸铁制备方法的评价[J].环境保护,1997,(4):15-16.
[30]阮复昌,公国庆,莫炳禄等.聚合硫酸铁的生产技术与效益评价[J].广东化工,1995,(2):4-6.
[31]陈辅君.无机高分子混凝剂聚合硫酸铁的制备新工艺[J].中国给水排水,1995,11(1):32-35.
[32]白玉兴,刘君,李杨.聚合硫酸铁合成中催化剂的研究[J].工业水处理,1996,16(2):9-11.
[33]林冰,廖为鑫,汪林.一种新的聚合硫酸铁的生产方法[P].CN1053222A:1991-07-24.
[34]章振,李安德.高效混凝剂净水灵的开发及应用[J].石油炼制与化工,1985,26(7):60-62.
[35]K M Allal,M Ocuchefoun,M Boumahrez.Oxidation of iron(Ⅲ)sulphate and use in water treatment[J].J.ofChem.Tech.and Biotech.,1996,34(10):151-159.
[36]Femuson,W J.Manufacture of aqueous ferric sulfate solutions and their use in water purification[P].GB2226561,1990-06-11.
[37]解立平,徐向荣.无机絮凝剂一聚合硫酸铁生产方法综述[J].环境与开发,2000,15(4):9-10.
[38]武道吉,陈冬辰,李风亭.国外制造聚合硫酸铁的新方法[J].化工环保,1997,(5):277-280.
[39]国家环保局、纺织工业部编.纺织印染废水一我国几种工业废水治理技术研究[M].北京:化学工业出版社,1988.
[40]王振东,张志祥.印染废水的污染与控制[J].环境科学与技术,2001,(1):21.
[41]Subbotina E A,Tarasevich Y I,Orazmuradov A O.Adsorption of direct dyes on organically substituted montmorillonite.Izu.Akad Nauk Turkm.SSR,Ser.Fiz.-Tekh.,Khim.Geol.Nauk 1985,(3):105108
[42]余颖,庄源益,邹其猛等.有机絮凝剂对水中染料的絮凝作用探讨明[J].环境化学,2000,19(2):142-147.
[43]宫世国,陶秀成,方金一.新型混凝脱色剂(ASD-II)的研制及其在印染废水处理中的应用[J].工业水处理,1993,13(5):16-19.
[44]尚国平等.改进的电解一气浮法处理印染废水[J].化工环保,1993,13(5):285-288.
[45]陈鸿林等.混凝沉淀一二氧化氯氧化法处理印染废水明[J].化工环保,1999,19(4):223-225.
[46]中华人民共和国国家标准GB 14591-2006 2-7.
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