低游离甲醛双氰胺甲醛缩聚物絮凝脱色剂的制备
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摘要
为了提高对废水的脱色效率,以双氰胺、甲醛和氯化铵为主要原料合成了水溶性阳离子絮凝脱色剂,考察了投料比、反应温度、反应时间等因素对絮凝脱色剂脱色效果的影响,优选了絮凝脱色剂合成的工艺条件。结果表明,双氰胺、甲醛和氯化铵物质的量比为1∶2.1∶0.9,反应温度为60℃,反应时间为2.5h,pH值为10,脱色剂用量为1.0%时所得絮凝脱色剂的脱色效果最佳。通过实验还探讨了絮凝脱色剂中游离甲醛的去除机理及最优去除方案。结果表明,先加入n(双氰胺)∶n(甲醇)=1∶2.8,再加入n(双氰胺)∶n(尿素)=1∶0.04,反应温度为50℃,反应时间为4h,可使游离甲醛含量降到0.124%,最终合成低游离甲醛、高脱色率的絮凝脱色剂。
In order to improve the efficiency of decolorization of wastewater,a water-soluble cationic dicyandiamide formaldehyde bleaching agent is synthesized with dicyandiamide,formaldehyde and ammonium chloride.The paper investigates the influence of the ratio of dosage,temperature,reaction time,etc.on the decolorization effect of the flocculant,and optimizes the process conditions for the synthesis of the flocculant.The results indicates that it could reach the optimal decolorization rate when the molar ratio of dicyandiamide to formaldehyde and ammonium chloride is 1∶2.1∶0.9,the temperature is 60 ℃,the reaction time is 2.5h,the pH value is 10,and the dosage of bleaching agent is 1.0%.The removal mechanism and optimal removal schemes of free formaldehyde are also discussed through experiment.The experimental results show that when the molar ratio of dicyandiamide and urea is 1∶0.04 after adding dicyandiamide and methyl alcohol with the ratio of 1∶2.8,the temperature is 50 ℃,and the time for the reaction is 4h,it could decrease formaldehyde to less than 0.124%,and finally theflocculant with low free formaldehyde and high efficiency of decolorization is synthesized.
In order to improve the efficiency of decolorization of wastewater,a water-soluble cationic dicyandiamide formaldehyde bleaching agent is synthesized with dicyandiamide,formaldehyde and ammonium chloride.The paper investigates the influence of the ratio of dosage,temperature,reaction time,etc.on the decolorization effect of the flocculant,and optimizes the process conditions for the synthesis of the flocculant.The results indicates that it could reach the optimal decolorization rate when the molar ratio of dicyandiamide to formaldehyde and ammonium chloride is 1∶2.1∶0.9,the temperature is 60 ℃,the reaction time is 2.5h,the pH value is 10,and the dosage of bleaching agent is 1.0%.The removal mechanism and optimal removal schemes of free formaldehyde are also discussed through experiment.The experimental results show that when the molar ratio of dicyandiamide and urea is 1∶0.04 after adding dicyandiamide and methyl alcohol with the ratio of 1∶2.8,the temperature is 50 ℃,and the time for the reaction is 4h,it could decrease formaldehyde to less than 0.124%,and finally theflocculant with low free formaldehyde and high efficiency of decolorization is synthesized.
引文
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[12]张文艺,刘明元.罗鑫,等.双氰胺-甲醛聚合物阳离子印染废水脱色剂的合成及其应用[J].过程工程学报,2010,10(6):1217-1220.ZHANG Wenyi,LIU Mingyuan,LUO Xin,et al.Synthesis of cationic decoloring agent of dicyandiamide-formaldehyde polymer and its application in dyeing wastewater[J].The Chinese Journal of Process Engineering,2010,10(6):1217-1220.
[13]GB/T 5009.1—2003,食品卫生检验方法理化部分总则[S].
[14]李陶琦,刘建利,姚逸伦,等.低游离甲醛三聚氰胺甲醛树脂的合成[J].应用化工,2009,38(10):1537-1539.LI Taoqi,LIU Jianli,YAO Yilun,et al.Synthesis of low-free methanal melamine resin[J].Applied Chemical Industry,2009,38(10):1537-1539.
[15]郑丽.甲醛祛除剂[P].中国专利:201210395688.9,2003-03-27.
[2]李敏,郭延凯,马志远,等.醌类化合物修饰电极催化强化酸性红B电解脱色研究[J].河北科技大学学报,2014,35(3):291-295.LI Min,GUO Yankai,MA Zhiyuan,et al.Research on enhanced electrolyzation-decolorization of acid red B by modified electrode with quinone compounds[J].Journal of Hebei University of Science and Technology,2014,35(3):291-295.
[3]董倩倩,刘振法,王纪代,等.复合絮凝剂与活性砂滤池协同深度处理印染废水研究及应用[J].河北工业科技,2014,31(2):129-132.DONG Qianqian,LIU Zhenfa,WANG Jidai,et al.Research and application of synergistic advanced treatment of printing and dyeing wastewater by composite flocculants and active sand filter[J].Hebei Journal of Industrial Science and Technology,2014,31(2):129-132.
[4]田习菲.醚化改性双氰胺-甲醛脱色絮凝剂的合成及应用[D].苏州:苏州大学,2014.TIAN Xifei.Synthesis and Application of Ether-Modified Dicyandiamide-Formaldehyde Bleaching Flocculant[D].Soochow:Soochow University,2014.
[5]张恒,王晓平,胡振华,等.新型淀粉接枝双氰胺甲醛缩聚物絮凝剂的制备及合成机理研究[J].中国造纸学报,2014,29(3):15-19.ZHANG Heng,WANG Xiaoping,HU Zhenhua,et al.Preparation of starch grafting dicyandiamide formaldehyde condensated polymer and the study of its synthesis mechanism[J].Transactions of China Pulp and Paper,2014,29(3):15-19.
[6]耿仁勇,吕雪川,李国轲,等.双氰胺甲醛改性脱色剂的合成及在模拟染料废水中的应用[J].化工进展,2016,35(1):308-313.GENG Renyong,LYU Xuechuan,LI Guoke,et al.Synthesis of a novel modified decolorant and its application in the treatment of simulated dyestuff wastewater[J].Chemical Industry and Engineering Progress,2016,35(1):308-313.
[7]涂盛辉,龚美青,万金保.一种新型复合絮凝剂的合成及其应用[J].工业水处理,2013,33(11):49-52.TU Shenghui,GONG Meiqing,WAN Jinbao.Synthesis of a new type of composite flocculant and its application to the treatment of coking wastewater[J].Industrial Water Treatment,2013,33(11):49-52.
[8]贺启环,张勇,方华.处理印染废水的复合混凝剂研究进展[J].工业水处理,2002,22(2):1-4.HE Qihuan,ZHANG Yong,FANG Hua.Study progress in complex coagulant of wastewater from printing and dyeing[J].Industrial Water Treatment,2002,22(2):1-4.
[9]汤继军,高枫.双氰胺-甲醛缩聚物脱色剂的研究及应用[J].工业水处理,2002,22(4):27-28.TANG Jijun,GAO Feng.Study and application of dicyandiamine-formaldehyde decolouriser[J].Industrial Water Treatment,2002,22(4):27-28.
[10]孙希孟.双氰胺-甲醛系列高分子脱色絮凝剂的合成、表征及性能研究[D].开封:河南大学,2000.SUN Ximeng.The Synthesis,Structure Characterization and Properties of Polymer Decolorizing Flocculants Madefrom Dicyandiamide and Formaldehyde[D].Kaifeng:Henan University,2000.
[11]张秀敏,纪淑娟.品红亚硫酸钠试剂在快速检测甲醛中的应用[J].沈阳农业大学学报,2007,38(2):202-206.ZHANG Xiumin,JI Shujuan.Application of fuchsin sodium sulfite in rapid detection of formaldehyde[J].Journal of Shenyang Agricultural University,2007,38(2):202-206.
[12]张文艺,刘明元.罗鑫,等.双氰胺-甲醛聚合物阳离子印染废水脱色剂的合成及其应用[J].过程工程学报,2010,10(6):1217-1220.ZHANG Wenyi,LIU Mingyuan,LUO Xin,et al.Synthesis of cationic decoloring agent of dicyandiamide-formaldehyde polymer and its application in dyeing wastewater[J].The Chinese Journal of Process Engineering,2010,10(6):1217-1220.
[13]GB/T 5009.1—2003,食品卫生检验方法理化部分总则[S].
[14]李陶琦,刘建利,姚逸伦,等.低游离甲醛三聚氰胺甲醛树脂的合成[J].应用化工,2009,38(10):1537-1539.LI Taoqi,LIU Jianli,YAO Yilun,et al.Synthesis of low-free methanal melamine resin[J].Applied Chemical Industry,2009,38(10):1537-1539.
[15]郑丽.甲醛祛除剂[P].中国专利:201210395688.9,2003-03-27.