新型高分子絮凝剂黄原酸化壳聚糖的制备及除铜性能
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摘要
以壳聚糖(CTS)为原料,先用苯甲醛保护其C_2位上的氨基生成Schiff碱壳聚糖,再将二硫代羧基通过黄原酸化反应接枝到CTS C_6位羟基上,制备出一种新型高分子絮凝剂——黄原酸化CTS(XCTS)。采用单因素实验法考察了XCTS制备的影响因素及其制备条件,并探讨了水样中Cu~(2+)初始浓度、pH对XCTS除铜性能的影响。结果表明,当XCTS制备条件为CS_2用量2.0mL、NaOH浓度5.0%(质量分数)、预反应温度30℃、预反应时间30min、主反应温度60℃、主反应时间240min时,制得的XCTS除铜性能最好,Cu~(2+)的最高去除率可达97.7%。XCTS最佳投药量随着水样中Cu~(2+)初始质量浓度的增加而增加;Cu~(2+)的去除率随着水样pH(pH不为7.0时)升高而先增大后减小,水样pH为6.0时,Cu~(2+)去除效果最佳。
A novel macromolecule flocculant,called xanthated chitosan(XCTS),was prepared by using chitosan as raw material.Schiff-base chitosan was first synthesized by using benzaldehyde to protect the amino groups of chitosan at C_2 position,then dithiocarboxyl groups were grafted onto the hydroxyl groups of chitosan at C_6 position through xanthating reaction.The single-factor experiments were employed to investigate the influencing factors and conditions for the preparation of XCTS.The effects of initial mass concentration of Cu~(2+) and pH on the removal of Cu~(2+) with XCTS were also discussed.The results showed that the preparation conditions of XCTS were as follows:the dosage of CS_2 was 2.0 mL,the concentration of NaOH was 5.0%(mass fraction),the pre-reaction temperature was 30℃,the pre-reaction time was 30 min,the main-reaction temperature was 60℃ and the main-reaction time was240 min.Under the preparation conditions,the highest removal rate of Cu~(2+) could reach 97.7%.The optimum dosage of XCTS increased with the increase of the initial mass concentration of Cu~(2+).The removal rate of Cu~(2+) increased at first and then decreased with pH of the water samples increasing when pH was not 7.0.When pH was 6.0,the removal efficiency of Cu~(2+) was the best.
A novel macromolecule flocculant,called xanthated chitosan(XCTS),was prepared by using chitosan as raw material.Schiff-base chitosan was first synthesized by using benzaldehyde to protect the amino groups of chitosan at C_2 position,then dithiocarboxyl groups were grafted onto the hydroxyl groups of chitosan at C_6 position through xanthating reaction.The single-factor experiments were employed to investigate the influencing factors and conditions for the preparation of XCTS.The effects of initial mass concentration of Cu~(2+) and pH on the removal of Cu~(2+) with XCTS were also discussed.The results showed that the preparation conditions of XCTS were as follows:the dosage of CS_2 was 2.0 mL,the concentration of NaOH was 5.0%(mass fraction),the pre-reaction temperature was 30℃,the pre-reaction time was 30 min,the main-reaction temperature was 60℃ and the main-reaction time was240 min.Under the preparation conditions,the highest removal rate of Cu~(2+) could reach 97.7%.The optimum dosage of XCTS increased with the increase of the initial mass concentration of Cu~(2+).The removal rate of Cu~(2+) increased at first and then decreased with pH of the water samples increasing when pH was not 7.0.When pH was 6.0,the removal efficiency of Cu~(2+) was the best.
引文
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[2]张蕊,葛滢.稻壳基活性炭制备及其对重金属吸附研究[J].环境污染与防治,2011,33(1):41-45,51.
[3]邱阳.含铜废水处理法的研究进展[J].污染防治技术,2015(3):22-24.
[4]朱巨建,周衍波,张永利,等.壳聚糖的改性及其在印染废水处理中的应用[J].生态环境学报,2016,25(1):112-117.
[5]江君.壳聚糖的改性及其在含酚废水处理中的应用研究[D].南京:南京林业大学,2010.
[6]杨明平,李国斌.壳聚糖吸附处理废水中的微量铬(Ⅵ)[J].材料保护,2003,36(12):37-38.
[7]BABA Y,NOMA H,NAKAYAMA R,et al.Preparation of chitosan derivatives containing methylthiocarbamoyl and phenylthiocarbamoyl groups and their selective adsorption of copper(Ⅱ)and iron(Ⅲ)[J].Analytical Sciences,2002,18(3):359-361.
[8]武雪芬,王磊,杨焕平,等.壳聚糖2-位NH2的修饰及其对理化性能的影响[J].中南药学,2006,4(5):328-331.
[9]罗道成,易平贵,刘俊峰,等.改性壳聚糖对电镀废水中重金属离子的吸附[J].材料保护,2002,35(1):11-12.
[10]刘盛,朱红祥,王进,等.超声波法黄原酸化壳聚糖的制备[J].化工进展,2015,34(7):1956-1961.
[11]杜凤龄,王刚,徐敏,等.新型高分子螯合-絮凝剂制备条件的响应面法优化[J].中国环境科学,2015,35(4).
[12]杜凤龄.螯合-絮凝剂二硫代羧基化壳聚糖的制备及其捕集重金属性能研究[D].兰州:兰州交通大学,2015.
[13]刘立华,吴俊,令玉林,等.高分子重金属螯合絮凝剂的制备及其除Cu2+,Ni 2+的性能研究[J].湖南科技大学学报(自然科学版),2010,25(4):104-109.
[14]张翠玲,常青,黄丹.巯基乙酰壳聚糖制备条件的优化及其絮凝性能[J].工业水处理,2010,30(8):40-42,46.
[15]董炎明,王勉,吴玉松,等.壳聚糖衍生物的红外光谱分析[J].纤维素科学与技术,2001,9(2):42-56.
[16]JIN H K,LEE Y M.Synthesis and properties of diethylaminoethyl chitosan[J].Polymer,1993,34(9):1952-1957.
[17]刘立华,吴俊,李鑫,等.四乙烯五胺多(二硫代甲酸钠)的合成及其对重金属的去除性能[J].环境科学研究,2011,24(3).