阳离子化壳聚糖改性黏土絮凝去除藻华
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摘要
壳聚糖改性黏土可以用于治理藻华,但未经改性的壳聚糖具有电荷密度小、溶解度小、pH适用范围较窄以及分子质量较小等缺点,影响了壳聚糖改性黏土除藻的性能。为了优化壳聚糖的絮凝除藻性能,以二甲基二烯丙基氯化铵为阳离子醚化剂,在微波条件下对壳聚糖进行改性合成阳离子型壳聚糖,并研究了阳离子壳聚糖溶解度随pH的变化,以及用它改性后的黏土颗粒的表面电位的变化,并对阳离子壳聚糖改性黏土和壳聚糖改性黏土的絮凝除藻性能进行比较。结果表明,阳离子壳聚糖在酸性和碱性条件下都具有很好的溶解性,经其改性后的黏土颗粒的等电点(pH 10.8)显著高于壳聚糖改性黏土的等电点(pH 9.5)。在絮凝实验中,阳离子壳聚糖改性黏土的最大除藻率达到99%,藻絮体粒径为978μm,即使在pH为10时,仍有87%的去除率。结果表明,阳离子壳聚糖改性黏土的除藻性能明显优于未改性的壳聚糖改性黏土。
Chitosan modified clay is a material which can efficiently remove harmful algal blooms. However,unmodified-chitosan has some drawbacks such as low-solubility, small-molecular weight, and narrow working pH range. To improve the property of chitosan modified clay in removing algae, a chitosan-grafted copolymer(chitosanDMDAAC) was prepared by reacting chitosan with dimethyl diallyl ammonium chloride(DMDAAC) under microwave. The solubility of chitosan-DMDAAC and Zeta potential of chitosan-DMDAAC modified clay were studied. Furthermore, the algal flocculation properties by using chitosan-DMDAAC and chitosan modified clay were also studied. The results showed that, chitosan-DMDAAC had good solubility under acidic and alkaline conditions. After modified by chitosan-DMDAAC, the isoelectric point of clay particulates reached to pH 10.8,which was larger thanchitosan modified clay(pH 9.5). In algal flocculation experiment, the maximal algal removal rate of chitosan-DMDAAC modified clay was 99%, and still reached 87% at pH 10. Furthermore, the algal flocs size of chitosan-DMDAAC modified clay was 978 μm. These indicate that the ability of chitosan-DMDAAC modified clay is better than chitosan modified clay in removing harmful algal blooms.
Chitosan modified clay is a material which can efficiently remove harmful algal blooms. However,unmodified-chitosan has some drawbacks such as low-solubility, small-molecular weight, and narrow working pH range. To improve the property of chitosan modified clay in removing algae, a chitosan-grafted copolymer(chitosanDMDAAC) was prepared by reacting chitosan with dimethyl diallyl ammonium chloride(DMDAAC) under microwave. The solubility of chitosan-DMDAAC and Zeta potential of chitosan-DMDAAC modified clay were studied. Furthermore, the algal flocculation properties by using chitosan-DMDAAC and chitosan modified clay were also studied. The results showed that, chitosan-DMDAAC had good solubility under acidic and alkaline conditions. After modified by chitosan-DMDAAC, the isoelectric point of clay particulates reached to pH 10.8,which was larger thanchitosan modified clay(pH 9.5). In algal flocculation experiment, the maximal algal removal rate of chitosan-DMDAAC modified clay was 99%, and still reached 87% at pH 10. Furthermore, the algal flocs size of chitosan-DMDAAC modified clay was 978 μm. These indicate that the ability of chitosan-DMDAAC modified clay is better than chitosan modified clay in removing harmful algal blooms.
引文
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[25] YANG Z, SHANG Y, HUANG X, et al.Cationic content effects of biodegradable amphoteric chitosan-based flocculants on the flocculation properties[J]. Journal of Environmental Science,2012,24(8):1378-1385. DOI:10.1016/S1001-0742(11)60962-5.
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[27] LIM S H, HUDSON S M. Synthesis and antimicrobial activity of a water-soluble chitosan derivative with a fiber-reactive group[J].Carbohydrate Research,2004,339(2):313-319. DOI:10.1016/j.carres.2003.10.024.
[28] PAN G, CHEN J, ANDERSON D M.Modified local sands for the mitigation of harmful algal blooms[J]. Harmful Algae,2011,10(4):381-387. DOI:10.1016/j.hal.2011.01.003.
[29]杜兰平,徐崇泉,郭慎满,等.有关壳聚糖溶解性能的研究[J].化学工程师,1990(6):10-12.
[30] STRAND S P, NORDENGEN T,STGAARD K. Efficiency of chitosans applied for flocculation of different bacteria[J]. Water Research,2002,36(19):4745-4752. DOI:10.1016/S0043-1354(02)00173-2.
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[32]刘恋.壳聚糖改性黏土去除城市湖泊中藻类的研究[J].环境科学与管理,2012,37(3):83-87.
[33] SEITZINGER S P. The effect of p H on the release of phosphorus from Potomac estuary sediments:Implications for blue-green algal blooms[J]. Estuarine Coastal&Shelf Science,1991,33(4):409-418. DOI:10.1016/0272-7714(91)90065-J.
[34]张未,潘仕荣,张璇,等.聚乙二醇-壳聚糖共聚物作为基因传递载体的体外研究[J].药学学报,2008,43(8):848-854.
[35] YUAN Y, ZHANG H, PAN G. Flocculation of cyanobacterial cells using coal fly ash modified chitosan[J]. Water Research,2016,97:11-18. DOI:10.1016/j.watres.2015.12.003.
[36]张文艺,范培成,李秋艳,等.聚合氯化铝-壳聚糖复合絮凝剂的合成及在蓝藻沼液预处理中的应用[J].环境化学,2012,31(7):1057-1062.
[37]初庆娣,朱小梅,王巧敏,等.微波辅助改性壳聚糖的制备及其絮凝性能[J].环境工程学报,2016,10(12):6935-6939.DOI:10.12030/j.cjee.201508020.
[38]王锦涛.微波辐射下天然高分子接枝共聚物的合成与应用[D].南京:南京林业大学,2009.
[39] LI L, PAN G. A universal method for flocculating harmful algal blooms in marine and fresh waters using modified sand[J].Environmental Science Technology,2013,47(9):4555-4562. DOI:10.1021/es305 234d.
[40]刘艳芳,张自力,李贵霞,等.二氧化氯预氧化对藻类絮体形态的影响[J].环境科学与技术,2013,36(2):33-36.
[41]徐相超.聚合氯化铝铁高效低破损去除蓝藻细胞[D].济南:山东大学, 2015.
[42] SHANG J, LIU H, QI C, et al. Physical, mechanical properties, and structural characterization of konjac glucomannanchitosan-polypeptide adhesive blends[J]. Journal of Adhesion Science&Technology,2015,29(21):2334-2344. DOI:10.1080/01694243.2015.1066237.
[43] ROUSSY J, VAN VOOREN M, GUIBAL E. Influence of chitosan characteristics on coagulation and flocculation of organic suspensions[J]. Water research,2005,39(14):3247-3258. DOI:10.1021/acs. est.6b06281.
[44]花蓉蓉,周恭明,曹大伟.壳聚糖的絮凝性能研究进展[J].化工进展,2008,27(3):335-339.
[2] SINHA E, MICHALAK A M, BALAJI V. Eutrophication will increase during the 21st century as a result of precipitation changes[J].Science,2017,357(6349):405-405. DOI:10.1126/science.aan2409.
[3] WILKINSON G M. Eutrophication of freshwater and coastal ecosystems[EB/OL].[2018-03-10]. https://dx.doi.org/10.1016/B978-0-12-409548-9.10160-5.
[4] SECHER S. Measures to control harmful algal blooms[J]. Plymouth Student Scientist,2009,2(1):212-227.
[5] BEAULIEU S E, SENGCO M R, ANDERSON D M. Using clay to control harmful algal blooms:Deposition and resuspension of clay/algal flocs[J]. Harmful Algae,2005,4(1):123-138. DOI:10.1016/j.hal. 2003.12.008.
[6] YU Z M, ZOU J Z. Application of clays to removal of red tide organismsⅢ. The coagulation of kaolin on red tide organisms[J].Chinese Journal of Oceanology and Limnology,1995,13(1):62-70. DOI:10.1007/BF02845350.
[7] PAN G, ZOU H, CHEN H, et al. Removal of harmful cyanobacterial blooms in Taihu Lake using local soils. III. Factors affecting the removal efficiency and an in situ field experiment using chitosan-modified local soils[J]. Environmental Pollution,2006,141(2):206-212. DOI:10.1016/j. envpol.2005.08.047.
[8] SHI W, TAN W, WANG L, et al. Removal of Microcystis aeruginosa using cationic starch modified soils[J]. Water Research,2016,97:19-25. DOI:10.1016/j.watres.2015.06.029.
[9]曹西华,宋秀贤,俞志明.改性黏土除藻的絮凝形态学特征初步研究[J].海洋学报,2017,39(6):33-42.DOI:10.3969/j.issn.0253-4193.2017.06.004.
[10]李梁.电荷-高分子改性土壤去除有害藻及其环境意义的研究[D].北京:中国科学院大学,2014.
[11]俞志明,邹景忠,马锡年.一种提高黏土矿物去除赤潮生物能力的新方法[J].海洋与湖沼,1994,25(2):226-232.
[12]潘纲,张明明,闫海,等.黏土絮凝沉降铜绿微囊藻的动力学及其作用机理[J].环境科学,2003,24(5):1-10.DOI:10.3321/j.issn:0250-3301.2003.05.001.
[13] SENGCO M R, HAGSTR M J A, GRAN LI E, et al.Removal of Prymnesium parvum(Haptophyceae)and its toxins using clay minerals[J]. Harmful Algae,2005,4(2):261-274. DOI:10.1016/j.hal.2004.05.001.
[14] LI L, PAN G. Cyanobacterial bloom mitigation using proteins with high isoelectric point and chitosan-modified soil[J]. Journal of Applied Phycology,2015,28(1):357-363. DOI:10.1007/s 10811-015-0598-1.
[15]邹华,潘纲,陈灏.壳聚糖改性黏土对水华优势藻铜绿微囊藻的絮凝去除[J].环境科学,2004,25(6):40-43.
[16]杜胜蓝,刘文杰,臧常娟.壳聚糖-沸石复合体对铜绿微囊藻的去除效果[J].水资源保护,2013,29(4):87-90.DOI:10.3969/j.issn.10046933.2013.04.018.
[17]刘振儒,田重威.壳聚糖复合黏土矿凝聚铜绿微囊藻的研究[J].环境工程,2004,22(3):80-82.
[18]严群,韩冬雪,汪宏,等.藻类生长期对改性蛭石絮凝除藻的影响[J].环境工程学报,2017,11(3):1621-1626.DOI:10.12030/j.cjee.201511114.
[19]邹华,潘纲,阮文权.壳聚糖改性黏土絮凝除藻的机理探讨[J].环境科学与技术,2007,30(5):8-9.
[20]曹西华,宋秀贤,俞志明,等.有机改性黏土去除赤潮生物的机制研究[J].环境科学,2006,27(8):1522-1530.
[21]邹华,潘纲,程子波.黏土原位除藻技术研究[J].环境科学,2009,30(2):407-410.
[22]刘恋,陈兵,王志红.壳聚糖改性黏土对高藻水中藻类的絮凝去除[J].环境工程学报,2010,4(6):1296-1300.
[23]施国键,乔俊莲,王国强,等.活化粉煤灰改性壳聚糖絮凝除藻的研究[J].环境污染与防治,2009,31(9):45-48.
[24]王红强,李夏,张列宇.壳聚糖-粉煤灰蒸压砖粉末-化感物质复合除藻剂对铜绿微囊藻去除效能的研究[J].安全与环境工程,2017,24(5):55-59.
[25] YANG Z, SHANG Y, HUANG X, et al.Cationic content effects of biodegradable amphoteric chitosan-based flocculants on the flocculation properties[J]. Journal of Environmental Science,2012,24(8):1378-1385. DOI:10.1016/S1001-0742(11)60962-5.
[26]向斯,刘世昌,赵以军,等. p H值及黏土密度对壳聚糖改性絮凝剂除藻效果的影响[J].中国环境科学,2015,35(5):1520-1525.
[27] LIM S H, HUDSON S M. Synthesis and antimicrobial activity of a water-soluble chitosan derivative with a fiber-reactive group[J].Carbohydrate Research,2004,339(2):313-319. DOI:10.1016/j.carres.2003.10.024.
[28] PAN G, CHEN J, ANDERSON D M.Modified local sands for the mitigation of harmful algal blooms[J]. Harmful Algae,2011,10(4):381-387. DOI:10.1016/j.hal.2011.01.003.
[29]杜兰平,徐崇泉,郭慎满,等.有关壳聚糖溶解性能的研究[J].化学工程师,1990(6):10-12.
[30] STRAND S P, NORDENGEN T,STGAARD K. Efficiency of chitosans applied for flocculation of different bacteria[J]. Water Research,2002,36(19):4745-4752. DOI:10.1016/S0043-1354(02)00173-2.
[31] DIVAKARAN R, PILLAI V N S. Flocculation of algae using chitosan[J]. Journal of Applied Phycology, 2002,14(5):419-422.DOI:10.1023/A:1022137023257.
[32]刘恋.壳聚糖改性黏土去除城市湖泊中藻类的研究[J].环境科学与管理,2012,37(3):83-87.
[33] SEITZINGER S P. The effect of p H on the release of phosphorus from Potomac estuary sediments:Implications for blue-green algal blooms[J]. Estuarine Coastal&Shelf Science,1991,33(4):409-418. DOI:10.1016/0272-7714(91)90065-J.
[34]张未,潘仕荣,张璇,等.聚乙二醇-壳聚糖共聚物作为基因传递载体的体外研究[J].药学学报,2008,43(8):848-854.
[35] YUAN Y, ZHANG H, PAN G. Flocculation of cyanobacterial cells using coal fly ash modified chitosan[J]. Water Research,2016,97:11-18. DOI:10.1016/j.watres.2015.12.003.
[36]张文艺,范培成,李秋艳,等.聚合氯化铝-壳聚糖复合絮凝剂的合成及在蓝藻沼液预处理中的应用[J].环境化学,2012,31(7):1057-1062.
[37]初庆娣,朱小梅,王巧敏,等.微波辅助改性壳聚糖的制备及其絮凝性能[J].环境工程学报,2016,10(12):6935-6939.DOI:10.12030/j.cjee.201508020.
[38]王锦涛.微波辐射下天然高分子接枝共聚物的合成与应用[D].南京:南京林业大学,2009.
[39] LI L, PAN G. A universal method for flocculating harmful algal blooms in marine and fresh waters using modified sand[J].Environmental Science Technology,2013,47(9):4555-4562. DOI:10.1021/es305 234d.
[40]刘艳芳,张自力,李贵霞,等.二氧化氯预氧化对藻类絮体形态的影响[J].环境科学与技术,2013,36(2):33-36.
[41]徐相超.聚合氯化铝铁高效低破损去除蓝藻细胞[D].济南:山东大学, 2015.
[42] SHANG J, LIU H, QI C, et al. Physical, mechanical properties, and structural characterization of konjac glucomannanchitosan-polypeptide adhesive blends[J]. Journal of Adhesion Science&Technology,2015,29(21):2334-2344. DOI:10.1080/01694243.2015.1066237.
[43] ROUSSY J, VAN VOOREN M, GUIBAL E. Influence of chitosan characteristics on coagulation and flocculation of organic suspensions[J]. Water research,2005,39(14):3247-3258. DOI:10.1021/acs. est.6b06281.
[44]花蓉蓉,周恭明,曹大伟.壳聚糖的絮凝性能研究进展[J].化工进展,2008,27(3):335-339.