一锅法溶液缩聚制备高效阳离子絮凝剂及其絮凝性能
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摘要
以丙酮、二甲胺和甲醛为原料,采用一锅法溶液缩聚制备了一种新型阳离子高分子絮凝剂CPF.通过红外、核磁共振氢谱、凝胶渗透色谱和元素分析对CPF的分子结构进行了表征,通过絮凝实验研究了CPF对水中阴离子染料的絮凝脱色效果并探讨了絮凝机理.研究表明,CPF重均分子量为1.81×10~4,拥有胺基、醇羟基、羰基和醚键等极性官能团,大量质子化胺基赋予其很高的阳离子度.CPF对酸性、直接和活性阴离子染料的絮凝脱色率均达95%以上,脱色率随溶液pH降低而升高且不受水中无机盐的影响.该絮凝行为是"吸附电中和"与"吸附架桥"效应共同作用的结果.CPF对实际印染废水同样具有良好的絮凝脱色效果,但对组分复杂的混合印染废水化学需氧量(COD)的去除率较低,因此可作为一种高效的物化处理手段与生化处理配合用于印染废水的工业化处理.
A novel cationic polymeric flocculant( CPF) was prepared by one-pot solution polycondensation using acetone,dimethylamine,formaldehyde as raw materials. The molecular structure of CPF was characterized by IR,~1H-NMR,GPC and elemental analysis. Its decoloration performance in removing anionic dyes from dye wastewater was studied by batch experiments.Meanwhile,the flocculation mechanism was discussed. Results showed that the weight-averaged molecular weight of CPF was 1. 81 × 10~4 and that CPF contained various functional groups such as amines,alcoholic hydroxyls,carbonyls and ethers. The presence of large amount of amine groups result in high cationicity of CPF through protonation. CPF' s decoloration efficiency in removing anionic dyes from dye wastewater increased with decreasing p H and was not affected by inorganic salts. Higher than 95% decoloration efficiency was achieved in treating anionic dye wastewaters containing acid,direct or reactive dyes during the flocculation experiments. The flocculation wasattributed to two simultaneous mechanisms involving adsorption by charge neutralization and aggregation by bridging. Although the COD removal rate was relatively low in the case of composite dye wastewater with complex components,the flocculation and decoloration efficiency of CPF was outstanding in treating actual dye wastewater. Therefore,CPF can be used as an effective flocculant as part of the combined physico-chemical and biological methods in treating the industrial dye wastewater.
A novel cationic polymeric flocculant( CPF) was prepared by one-pot solution polycondensation using acetone,dimethylamine,formaldehyde as raw materials. The molecular structure of CPF was characterized by IR,~1H-NMR,GPC and elemental analysis. Its decoloration performance in removing anionic dyes from dye wastewater was studied by batch experiments.Meanwhile,the flocculation mechanism was discussed. Results showed that the weight-averaged molecular weight of CPF was 1. 81 × 10~4 and that CPF contained various functional groups such as amines,alcoholic hydroxyls,carbonyls and ethers. The presence of large amount of amine groups result in high cationicity of CPF through protonation. CPF' s decoloration efficiency in removing anionic dyes from dye wastewater increased with decreasing p H and was not affected by inorganic salts. Higher than 95% decoloration efficiency was achieved in treating anionic dye wastewaters containing acid,direct or reactive dyes during the flocculation experiments. The flocculation wasattributed to two simultaneous mechanisms involving adsorption by charge neutralization and aggregation by bridging. Although the COD removal rate was relatively low in the case of composite dye wastewater with complex components,the flocculation and decoloration efficiency of CPF was outstanding in treating actual dye wastewater. Therefore,CPF can be used as an effective flocculant as part of the combined physico-chemical and biological methods in treating the industrial dye wastewater.
引文
[1] LIU H Y,YANG X G,ZHANG Y,et al. Flocculation characteristics of polyacrylamide grafted cellulose from phyllostachys heterocycla:An efficient and eco-friendly flocculant[J]. Water Research,2014,59:165-171.
[2]羊小玉,周律.混凝技术在印染废水处理中的应用及研究进展[J].化工环保,2016,36(1):1-4.YANG X Y,ZHOU L. Application and research progress of coagulation process for treatment of dyeing wastewater[J]. Environmental Protection of Chemical Industry,2016,36(1):1-4(in Chinese).
[3] YANG Z,YANG H,JIANG Z W,et al. Flocculation of both anionic and cationic dyes in aqueous solutions by the amphoteric grafting flocculant carboxymethyl chitosan-graft-polyacrylamide[J]. Journal of Hazardous Materials,2013,254-255:36-45.
[4] HOSSEIN S,NING Y,RAMIN F. Recent advances in polysaccharide bio-based flocculants[J]. Biotechnology Advances,2018,36:92-119.
[5]岳丽君,由耀辉,王碧,等.交联明胶基絮凝剂的制备及其絮凝性能[J].环境化学,2016,35(7):1507-1515.YUE L J,YOU Y H,WANG B,et al. Preparation of crosslinked gelatin-based flocculant and its flocculation performance[J].Environmental Chemistry,2016,35(7):1507-1515(in Chinese).
[6] YANG Z L,LIU X X,GAO B Y,et al. Flocculation kinetics and floc characteristics of dye wastewater by polyferric chloride–polyepichlorohydrin–dimethylamine composite flocculant[J]. Separation and Purification Technology,2013,118:583-590.
[7] TAO L,GUANG P,CUI J X,et al. Synthesis of a terpolymer based on chitosan and lignin as an effective flocculant for dye removal[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2018,537:149-154.
[8] LU L H,PAN Z D,HAO N,et al. A novel acrylamide-free flocculant and its application for sludge dewatering[J]. Water Research,2014,57:304-312.
[9]田秉晖,栾兆坤,潘纲.阳离子聚电解质聚二甲基二烯丙基氯化铵的絮凝机理初探[J].环境科学学报,2007,27(11):1874-1881.TIAN B H,LUAN Z K,PAN G. Flocculation mechanism of the cationic polyelectrolyte-polydiallylaimethy lammonium chloride(PDADMAC)[J]. Acta Scientiae Circumstantiae,2007,27(11):1874-1881(in Chinese).
[10]郝海艳,王刚,徐敏,等.响应面法优化制备螯合絮凝剂巯基乙酰化聚丙烯酰胺[J].环境化学,2016,35(6):1269-1279.HAO H Y,WANG G,XU M,et al. Optimization of preparation conditions of chelating flocculant with mercaptoacetyl polyacrylamide by response surface methodology[J]. Environmental Chemistry,2016,35(6):1269-1279(in Chinese).
[11] QUAN,X G,WANG,H Y. Preparation of a novel coal gangue-polyacrylamide hybrid flocculant and its flocculation performance[J].Chinese Journal of Chemical Engineering,2014,22(9):1055-1060.
[12]陈浩凡,潘仕荣,胡瑜,等.胶体滴定法测定羧甲基壳聚糖的取代度[J].分析测试学报,2003,22(6):70-73.CHEN H F,PAN S R,HU Y,et al. The determination of substitution degree of carboxymethyl chitosan by colloid titration[J]. Journal of instrumental analysis,2003,22(6):70-73(in Chinese).
[13]胡跃飞,林国强.现代有机反应第二卷——碳氮键的生成反应[M].北京:化学工业出版社,2008.HU Y F,LIN G Q. Contemporary organic reaction Vol.2 C-N bond formation[M]. Beijing:Chemical Industry Press,2008(in Chinese).
[14] LIU Y,ZHENG Y,WANG A Q. Enhanced adsorption of Methylene Blue from aqueous solution by chitosan-g-poly(acrylic acid)/vermiculite hydrogel composites[J]. Journal of Environmental Sciences,2010,22:486-493.
[15] SARKAR A K,GHORAI S P,ABHAY S,et al. Modified amylopectin based flocculant for the treatment of synthetic effluent and industrial wastewaters[J]. International Journal of Biological Macromolecules,2015,72:356-363.
[16] MISHRA A,BAJPAI M. The flocculation performance of Tamarindus mucilage in relation to removal of vat and direct dyes[J]. Bioresource Technology,2006,97(8):1055-1059.
[17] LI W W,ZHOU W Z,ZHANG Y Z,et al. Flocculation behavior and mechanism of an exopolysaccharide from the deep-sea psychrophilic bacterium Pseudoalteromonas sp. SM9913[J]. Bioresource Technology,2008,99(15):6893-6899.
[18] GUO K Y,GAO B Y,LI R H,et al. Flocculation performance of lignin-based flocculant during reactive blue dye removal:comparison with commercial flocculants[J]. Environmental Science and Pollution Research,2017,25(3):2083-2095.
[19] YANG Z,LI H J,YAN H,et al. Evaluation of a novel chitosan-based flocculant with high flocculation performance,low toxicity and good floc properties[J]. Journal of Hazardous Materials,2014,276:480-488.
[20] SZYGULA A,GBUIBAL E,PALACIN M A,et al. Removal of an anionic dye(Acid Blue 92)by coagulation-flocculation using chitosan[J]. Journal of Environmental Management,2009,90(10):2979-2986.
[21] SOMASUNDARAN P,RUNKANA V. Investigation of the flocculation of colloidal suspensions by controlling adsorbed layer microstructure and population balance modelling[J]. Chemical Engineering Research and Design,2005,83(7):905-914.
[2]羊小玉,周律.混凝技术在印染废水处理中的应用及研究进展[J].化工环保,2016,36(1):1-4.YANG X Y,ZHOU L. Application and research progress of coagulation process for treatment of dyeing wastewater[J]. Environmental Protection of Chemical Industry,2016,36(1):1-4(in Chinese).
[3] YANG Z,YANG H,JIANG Z W,et al. Flocculation of both anionic and cationic dyes in aqueous solutions by the amphoteric grafting flocculant carboxymethyl chitosan-graft-polyacrylamide[J]. Journal of Hazardous Materials,2013,254-255:36-45.
[4] HOSSEIN S,NING Y,RAMIN F. Recent advances in polysaccharide bio-based flocculants[J]. Biotechnology Advances,2018,36:92-119.
[5]岳丽君,由耀辉,王碧,等.交联明胶基絮凝剂的制备及其絮凝性能[J].环境化学,2016,35(7):1507-1515.YUE L J,YOU Y H,WANG B,et al. Preparation of crosslinked gelatin-based flocculant and its flocculation performance[J].Environmental Chemistry,2016,35(7):1507-1515(in Chinese).
[6] YANG Z L,LIU X X,GAO B Y,et al. Flocculation kinetics and floc characteristics of dye wastewater by polyferric chloride–polyepichlorohydrin–dimethylamine composite flocculant[J]. Separation and Purification Technology,2013,118:583-590.
[7] TAO L,GUANG P,CUI J X,et al. Synthesis of a terpolymer based on chitosan and lignin as an effective flocculant for dye removal[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2018,537:149-154.
[8] LU L H,PAN Z D,HAO N,et al. A novel acrylamide-free flocculant and its application for sludge dewatering[J]. Water Research,2014,57:304-312.
[9]田秉晖,栾兆坤,潘纲.阳离子聚电解质聚二甲基二烯丙基氯化铵的絮凝机理初探[J].环境科学学报,2007,27(11):1874-1881.TIAN B H,LUAN Z K,PAN G. Flocculation mechanism of the cationic polyelectrolyte-polydiallylaimethy lammonium chloride(PDADMAC)[J]. Acta Scientiae Circumstantiae,2007,27(11):1874-1881(in Chinese).
[10]郝海艳,王刚,徐敏,等.响应面法优化制备螯合絮凝剂巯基乙酰化聚丙烯酰胺[J].环境化学,2016,35(6):1269-1279.HAO H Y,WANG G,XU M,et al. Optimization of preparation conditions of chelating flocculant with mercaptoacetyl polyacrylamide by response surface methodology[J]. Environmental Chemistry,2016,35(6):1269-1279(in Chinese).
[11] QUAN,X G,WANG,H Y. Preparation of a novel coal gangue-polyacrylamide hybrid flocculant and its flocculation performance[J].Chinese Journal of Chemical Engineering,2014,22(9):1055-1060.
[12]陈浩凡,潘仕荣,胡瑜,等.胶体滴定法测定羧甲基壳聚糖的取代度[J].分析测试学报,2003,22(6):70-73.CHEN H F,PAN S R,HU Y,et al. The determination of substitution degree of carboxymethyl chitosan by colloid titration[J]. Journal of instrumental analysis,2003,22(6):70-73(in Chinese).
[13]胡跃飞,林国强.现代有机反应第二卷——碳氮键的生成反应[M].北京:化学工业出版社,2008.HU Y F,LIN G Q. Contemporary organic reaction Vol.2 C-N bond formation[M]. Beijing:Chemical Industry Press,2008(in Chinese).
[14] LIU Y,ZHENG Y,WANG A Q. Enhanced adsorption of Methylene Blue from aqueous solution by chitosan-g-poly(acrylic acid)/vermiculite hydrogel composites[J]. Journal of Environmental Sciences,2010,22:486-493.
[15] SARKAR A K,GHORAI S P,ABHAY S,et al. Modified amylopectin based flocculant for the treatment of synthetic effluent and industrial wastewaters[J]. International Journal of Biological Macromolecules,2015,72:356-363.
[16] MISHRA A,BAJPAI M. The flocculation performance of Tamarindus mucilage in relation to removal of vat and direct dyes[J]. Bioresource Technology,2006,97(8):1055-1059.
[17] LI W W,ZHOU W Z,ZHANG Y Z,et al. Flocculation behavior and mechanism of an exopolysaccharide from the deep-sea psychrophilic bacterium Pseudoalteromonas sp. SM9913[J]. Bioresource Technology,2008,99(15):6893-6899.
[18] GUO K Y,GAO B Y,LI R H,et al. Flocculation performance of lignin-based flocculant during reactive blue dye removal:comparison with commercial flocculants[J]. Environmental Science and Pollution Research,2017,25(3):2083-2095.
[19] YANG Z,LI H J,YAN H,et al. Evaluation of a novel chitosan-based flocculant with high flocculation performance,low toxicity and good floc properties[J]. Journal of Hazardous Materials,2014,276:480-488.
[20] SZYGULA A,GBUIBAL E,PALACIN M A,et al. Removal of an anionic dye(Acid Blue 92)by coagulation-flocculation using chitosan[J]. Journal of Environmental Management,2009,90(10):2979-2986.
[21] SOMASUNDARAN P,RUNKANA V. Investigation of the flocculation of colloidal suspensions by controlling adsorbed layer microstructure and population balance modelling[J]. Chemical Engineering Research and Design,2005,83(7):905-914.