聚乙烯亚胺基黄原酸钠与铁盐共同处理低浊水
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摘要
以聚乙烯亚胺(PEI)为母体,通过化学反应将二硫代羧基引入到其分子链中,制备出新型高分子絮凝剂聚乙烯亚胺基黄原酸钠(PEX),采用低浊水样作为考察对象,通过絮凝实验研究PEX分别与Fe(Ⅱ)盐、Fe(Ⅲ)盐对水样中浊度的去除性能.结果表明,PEX单独处理低浊水时,水样的初始浊度和pH值对PEX除浊效果均有一定的影响,除浊效率随着初始浊度的降低而降低,随着pH值的升高而先升高后降低;当初始pH值位于PEX等电点附近时,浊度的去除率可达到最高,初始浊度为10.0,15.0,30.0NTU,浊度的去除率分别为88.46%,91.17%,92.73%.PEX与Fe盐共同除浊时浊度的去除率随着体系pH值的升高先升高后降低,投加Fe(Ⅲ)盐后浊度的去除效果总体上优于投加Fe(Ⅱ)盐后的效果.PEX与Fe盐共同除浊和PEX单独除浊时的絮凝作用机理不尽一致,Fe盐的加入可起到一定的电中和作用.
A novel macromolecule flocculant polyethyleneimine-sodium xanthogenate(PEX) was prepared by chemical reaction to graft dithiocarboxylic groups onto polyethyleneimine(PEI). The removal performance of turbidity by PEX and ferrous/ferric salts from water samples containing low turbidity was studied by using flocculation experiments. The initial turbidity and pH value had a certain effect on the removal properties of turbidity by only using PEX. The removal efficiency of turbidity decreased with the decrease of the initial turbidity of water samples, and increased at first and then decreased with the increase of pH value. When the initial pH value of the water samples approached the isoelectric point of PEX, the removal rate of turbidity was highest, and reached 88.46%, 91.17% and 92.73% at the original turbidity of 10.0, 15.0 and 30.0 NTU for the water samples, respectively. The removal rate of turbidity increased at first and then decreased with the increase of pH value after the addition of PEX and ferrous/ferric salts, and the removal efficiency of turbidity was better with ferric salts than ferrous salts. The flocculation mechanism when adding only PEX was different from the one when adding both PEX and ferrous/ferric salts, and ferrous/ferric salts played a main role of charge neutralization in the flocculation process.
A novel macromolecule flocculant polyethyleneimine-sodium xanthogenate(PEX) was prepared by chemical reaction to graft dithiocarboxylic groups onto polyethyleneimine(PEI). The removal performance of turbidity by PEX and ferrous/ferric salts from water samples containing low turbidity was studied by using flocculation experiments. The initial turbidity and pH value had a certain effect on the removal properties of turbidity by only using PEX. The removal efficiency of turbidity decreased with the decrease of the initial turbidity of water samples, and increased at first and then decreased with the increase of pH value. When the initial pH value of the water samples approached the isoelectric point of PEX, the removal rate of turbidity was highest, and reached 88.46%, 91.17% and 92.73% at the original turbidity of 10.0, 15.0 and 30.0 NTU for the water samples, respectively. The removal rate of turbidity increased at first and then decreased with the increase of pH value after the addition of PEX and ferrous/ferric salts, and the removal efficiency of turbidity was better with ferric salts than ferrous salts. The flocculation mechanism when adding only PEX was different from the one when adding both PEX and ferrous/ferric salts, and ferrous/ferric salts played a main role of charge neutralization in the flocculation process.
引文
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[14]王刚,常青.高分子重金属絮凝剂PEX捕集Ni2+及除浊性能研究[J].环境科学学报,2007,27(5):763-769.Wang G,Chang Q.Study on the trapping Ni2+ions and the removing turbidity behavior of macromolecule heavy metal flocculant PEX[J].Acta Scientiae Circumstantiae,2007,27(5):763-769.
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[16]Milyaeva O Y,Gochev G,Loglio G,et al.Influence of polyelectrolytes on dynamic surface properties of fibrinogen solutions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,532(11):108-115.
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[19]王刚,李嘉,何宝菊,等.两性高分子絮凝剂聚乙烯亚胺基黄原酸钠除浊性能[J].中国环境科学,2018,38(12):4537-4544.Wang G,Li J,He B J,et al.Removal performance for turbidity by amphoteric macromolecule flocculant with polyethyleneiminesodium xanthogenate[J].China Environmental Science,2018,38(12):4537-4544.
[20]劳德平,丁书强,倪文,等.响应面优化制备粉煤灰基PASC混凝剂性能与表征[J].中国环境科学,2018,38(12):4599-4607.Lao D P,Ding S Q,Ni W,et al.Response surface method optimization of preparation fly ash based polysilicate aluminum chloride coagulant:performance and microstructure characterization[J].China Environmental Science,2018,38(12):4599-4607.
[21]Yang W H,Zuo B C,Li J Y,et al.Studies on the stability of fourmembered ring chelates Part V.The stability of dialkyl dithiocarbamate chelates[J].Spectrochim Acta Part A,1996,52:1915-1919.
[22]贾玉岩,高宝玉,卢磊,等.二硫代氨基甲酸盐的絮凝作用机理及除油性能[J].中国环境科学,2009,29(2):201-206.Jia Y Y,Gao B Y,Lu L,et al.Flocculation mechanism and oil removal performance of dithiocarbamate[J].China Environmental Science,2009,29(2):201-206.
[23]常青.水处理絮凝学[M].2版.北京:化学工业出版社,2011:58-60.Chang Q.Water treatment flocculation(2nd ed)[M].Beijing:Chemical Industry Press,2011:58-60.
[24]徐晓军.化学絮凝剂作用原理[M].北京:科学出版社,2005:128-129.Xu X J.Action principle of chemical flocculant[M].Beijing:Science Press,2005:128-129.
[25]张明月,曾辉平,吕育锋,等.高铁盐与亚铁盐混凝除As(III)性能的对比研究[J].中国环境科学,2017,37(5):1798-1804.Zhang M Y,Zeng H P,Lv Y F,et al.Comparison of arsenite removal processes by ferric salts and ferrous salts[J].China Environmental Science,2017,37(5):1798-1804.
[26]罗勤慧.配位化学[M].北京:科学出版社,2012:141-142.Luo Q H.Coordination chemistry[M].Beijing:Science Press,2012:141-142.
[2]洪云,徐慧.不同混凝剂处理低温低浊水[J].环境工程学报,2015,9(9):4421-4426.Hong Y,Xu H.Treatment of raw water with low turbidity and low temperature using different coagulants[J].Chinese Journal of Environmental Engineering,2015,9(9):4421-4426.
[3]汪志永,戴红玲,周政,等.低温低浊水处理技术的研究与应用[J].水处理技术,2016,42(10):20-24.Wang Z Y,Dai H L,Zhou Z,et al.Research and application of low temperature and low turbidity water treatment technology[J].Technology of Water Treatment,2016,42(10):20-24.
[4]Zhang Z,Jing R,HE S R,et al.Coagulation of low temperature and low turbidity water:Adjusting basicity of polyaluminum chloride(PAC)and using chitosan as coagulant aid[J].Separation and Purification Technology,2018,206:131-139.
[5]李冬梅,施周,金同轨,等.阳离子型聚合物对低温低浊水的絮凝效果与形态学特性[J].环境科学学报,2007,27(6):1013-1019.Li D M,Shi Z,Jin T G,et al.Flocculation efficiencies and morphological properties of cationic polymers in the treatment of low temperature and low turbidity raw water[J].Acta Scientiae Circumstantiae,2007,27(6):1013-1019.
[6]刘占孟,叶鑫,聂发辉.复合絮凝剂处理冬季低温低浊水的效果及其微观形态[J].中国给水排水,2016,32(3):61-65.Liu Z M,Ye X,Nie F H.Flocculation performance and microstructural morphology of PFM-PDMDAAC for treatment of raw water with low temperature and low turbidity in winter[J].China Water&Wastewater,2016,32(3):61-65.
[7]谢菁,陈有军,毕哲,等.铁铝复配混凝剂处理低温低浊水[J].环境工程学报,2014,8(9):3546-3552.Xie J,Chen Y J,Bi Z,et al.Coagulation of a low temperature and turbidity raw source water by Fe-Al composite coagulants[J].Chinese Journal of Environmental Engineering,2014,8(9):3546-3552.
[8]王燕,高宝玉,岳钦艳,等.铁盐类无机有机复合絮凝剂的水解特性及脱色效能[J].环境化学,2006,25(6):730-734.Wang Y,Gao B Y,Yue Q Y,et al.Hydrolysate of composite flocculant prepared from Fe(Ⅲ)inorganic flocculants and organic flocculants[J].Environmental Chemistry,2006,25(6):730-734.
[9]曹百川,高宝玉,许春华,等.pH对铁盐混凝剂处理黄河水效果及生成絮体的影响[J].科学通报,2010,55(9):758-763.Cao B C,Gao B Y,Xu C H,et al.Effects of pH on coagulation behavior and floc properties in Yellow River water treatment using ferric based coagulants[J].Chinese Science Bulletin,2010,55(9):758-763.
[10]张萌,邱琳,于晓晴,等.亚铁盐与高铁盐除磷工艺的对比研究[J].高校化学工程学报,2013,27(3):519-525.Zhang M,Qiu L,Yu X Q,et al.Comparison of phosphorus removal processes by ferrous salts and ferric salts[J].Journal of Chemical Engineering of Chinese Universities,2013,27(3):519-525.
[11]常青.絮凝学研究的新领域-具有重金属捕集功能的高分子絮凝剂[J].环境科学学报,2015,35(1):1-11.Chang Q.New research area of flocculation in water treatment―macromolecule flocculant with the function of trapping heavy metal[J].Acta Scientiae Circumstantiae,2015,35(1):1-11.
[12]Wang G,Chang Q,Han X T,et al.Removal of Cr(VI)from aqueous solution by flocculant with the capacity of reduction and chelation[J].Journal of Hazardous Materials,2013,248-249:115-121.
[13]王刚,常青.新型高分子絮凝剂对水中有机配位汞的捕集性能[J].中国环境科学,2012,32(5):837-842.Wang G,Chang Q.Performance of trapping mercury combined with organic coordination agent in water by novel macromolecule flocculant[J].China Environmental Science,2012,32(5):837-842.
[14]王刚,常青.高分子重金属絮凝剂PEX捕集Ni2+及除浊性能研究[J].环境科学学报,2007,27(5):763-769.Wang G,Chang Q.Study on the trapping Ni2+ions and the removing turbidity behavior of macromolecule heavy metal flocculant PEX[J].Acta Scientiae Circumstantiae,2007,27(5):763-769.
[15]国家环境保护总局《水与废水监测分析方法》编委会.水与废水监测分析方法[M].4版.北京:中国环境科学出版社,2002:368-370.State Environmental Protection Administration of China.Water and waste water monitoring and analysis method(4th ed)[M].Beijing:China Environmental Science Press,2002:368-370.
[16]Milyaeva O Y,Gochev G,Loglio G,et al.Influence of polyelectrolytes on dynamic surface properties of fibrinogen solutions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,532(11):108-115.
[17]Tong J G,Wei Z Y,Yang H L,et al.Study on the phase transition behaviors of thermoresponsive hyperbranched polyampholytes in water[J].Polymer,2016,84(2):107-116.
[18]Bekturov E A,Kudaibergenov S E,Rafikov S R.Synthetic polymeric ampholytes in solution[J].Journal of Macromolecular Science,1990,30(2):233-303.
[19]王刚,李嘉,何宝菊,等.两性高分子絮凝剂聚乙烯亚胺基黄原酸钠除浊性能[J].中国环境科学,2018,38(12):4537-4544.Wang G,Li J,He B J,et al.Removal performance for turbidity by amphoteric macromolecule flocculant with polyethyleneiminesodium xanthogenate[J].China Environmental Science,2018,38(12):4537-4544.
[20]劳德平,丁书强,倪文,等.响应面优化制备粉煤灰基PASC混凝剂性能与表征[J].中国环境科学,2018,38(12):4599-4607.Lao D P,Ding S Q,Ni W,et al.Response surface method optimization of preparation fly ash based polysilicate aluminum chloride coagulant:performance and microstructure characterization[J].China Environmental Science,2018,38(12):4599-4607.
[21]Yang W H,Zuo B C,Li J Y,et al.Studies on the stability of fourmembered ring chelates Part V.The stability of dialkyl dithiocarbamate chelates[J].Spectrochim Acta Part A,1996,52:1915-1919.
[22]贾玉岩,高宝玉,卢磊,等.二硫代氨基甲酸盐的絮凝作用机理及除油性能[J].中国环境科学,2009,29(2):201-206.Jia Y Y,Gao B Y,Lu L,et al.Flocculation mechanism and oil removal performance of dithiocarbamate[J].China Environmental Science,2009,29(2):201-206.
[23]常青.水处理絮凝学[M].2版.北京:化学工业出版社,2011:58-60.Chang Q.Water treatment flocculation(2nd ed)[M].Beijing:Chemical Industry Press,2011:58-60.
[24]徐晓军.化学絮凝剂作用原理[M].北京:科学出版社,2005:128-129.Xu X J.Action principle of chemical flocculant[M].Beijing:Science Press,2005:128-129.
[25]张明月,曾辉平,吕育锋,等.高铁盐与亚铁盐混凝除As(III)性能的对比研究[J].中国环境科学,2017,37(5):1798-1804.Zhang M Y,Zeng H P,Lv Y F,et al.Comparison of arsenite removal processes by ferric salts and ferrous salts[J].China Environmental Science,2017,37(5):1798-1804.
[26]罗勤慧.配位化学[M].北京:科学出版社,2012:141-142.Luo Q H.Coordination chemistry[M].Beijing:Science Press,2012:141-142.
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