纳米纤维素去除水体系重金属离子的研究进展

doi:10.16085/j.issn.1000-6613.2018-1991

摘要/Abstract

摘要：

水体系重金属污染治理是目前全世界所面临的一个重大挑战。传统治理方法由于成本高、效率低等问题已不符合当今社会可持续发展战略。纳米纤维素凭借其来源丰富、可再生、化学反应活性高、比表面积大、密度低等优点，在水体系重金属离子去除领域有着光明的应用前景。然而，纳米纤维素吸附材料在水体系重金属去除领域还存在吸附量较低，吸附选择性、再生性、性能稳定性较差，制备成本较高等问题，这限制了其在水体系重金属离子去除领域的工业化应用。通过改性和结构设计不断提高纳米纤维素材料的吸附效率是行之有效的途径，本文从化学改性和结构设计两方面出发，系统地综述了纳米纤维素在水体系重金属离子去除领域的研究现状，并对其中存在的科学技术问题进行总结。最后，展望了纳米纤维素在水体系重金属离子去除领域的发展趋势。

关键词: 重金属离子, 纳米纤维素, 吸附, 化学改性, 结构设计

Abstract:

Heavy metal pollution treatment in water is one of the great challenges all over the world. Traditional treatment methods cannot meet the growing requirements of the sustainable development of our society because of high treatment cost and low efficiency. Nanocellulose has advantages of earth abundance, excellent chemical reactivity, large specific surface area, and relatively low density, and demonstrates its foreseeable applications in the removal of heavy metal ions in water. However, removing metal ions in water by nanocellulose adsorbents remains a challenge due to its low adsorption capacity, poor selectivity, poor reproducibility, and performance instability, which restricts its commercial applications. One of the effective methods to enhance the adsorption efficiency is by modifying the surface properties of nanocellulose and/or designing the structure of nanocellulose absorbents. This review first covered the recent advances in nanocellulose for removing heavy metal ions in water in terms of chemical modifications and structural design of nanocellulose. Then, the scientific problems existing in this field were summarized in detail. Finally, the future development trend of nanocellulose in the field of heavy metal ions removal in water was envisioned.

Key words: heavy metal ion, nanocellulose, adsorption, chemical modification, structural design

中图分类号:

覃发梅, 邱学青, 孙川, 丁子先, 方志强. 纳米纤维素去除水体系重金属离子的研究进展[J]. 化工进展, 2019, 38(07): 3390-3401.

Famei QIN, Xueqing QIU, Chuan SUN, Zixian DING, Zhiqiang FANG. Research progress in nanocellulose for the removal of heavy metal ions in water[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3390-3401.

图/表 9

图1 3种纳米纤维素的微观形貌图[10,11,12]

图2 纤维素分子结构[32]及其改性示意图

表1 CNF改性及其重金属离子的吸附性能

一次改性	二次改性	活性位点	吸附量/mg·g^-1
一次改性	二次改性	活性位点	V	Cr³⁺	Cr(VI)	Fe³⁺	Co²⁺	Ni²⁺	Cu²⁺	Zn²⁺	Ag⁺	Cd²⁺	Pb²⁺	Hg²⁺	$U O 2 2 +$
机械分解	—	羟基	—	14^[35]	—	—	—	0^[35]	13^[35]，24.8^[39]	4^[35]	15^[40]	—	17^[41]	—	—
丝光化^[16]	酯化	羧基	—	—	—	—	5	4.6	4.7	5	—	5	—	—	—
氧化	聚合 + 硅烷化	羧基+氨基	—	—	—	—	—	—	52^[18]	—	—	—	—	—	—
	硅烷化	羧基、巯基	—	—	87.5^[42]	—	—	—	—	—	—	—	137.7^[42]	—	—
		羧基	—	8.9^[43]，58^[35]	—	—	—	8.6^[43]	112^[35]	66^[35]	—	9.7^[43]	9.4^[43]	—	167^[44]
		醛基	—	—	—	—	—	—	38	—	—	—	158	—	—
酯化		磷酸基+ 羧基^[19]	—	—	—	73	—	—	114	—	120	—	—	—	—
		磷酸基	10^[31]	—	—	—	—	—	—	—	—	—	—	—	—
		磺酸基	—	—	—	—	—	—	—	—	—	—	249^[41]	—	—
硅烷化	氧化	巯基 + 羧基	—	—	—	—	—	—	—	—	—	—	—	729.9^[18]	—
		氨基^[17]	—	—	—	—	—	156.3	195.6	—	—	405.6	—	—	—
接枝共聚	氧化	羧基 + 氨基	—	—	—	—	—	—	52^[45]	—	—	—	—	—	—
		羧基^[35]	—	—	—	—	—	117	57.5^[39]	138	—	135	165	—	—

表1 CNF改性及其重金属离子的吸附性能

一次改性	二次改性	活性位点	吸附量/mg·g^-1
一次改性	二次改性	活性位点	V	Cr³⁺	Cr(VI)	Fe³⁺	Co²⁺	Ni²⁺	Cu²⁺	Zn²⁺	Ag⁺	Cd²⁺	Pb²⁺	Hg²⁺	$U O 2 2 +$
机械分解	—	羟基	—	14^[35]	—	—	—	0^[35]	13^[35]，24.8^[39]	4^[35]	15^[40]	—	17^[41]	—	—
丝光化^[16]	酯化	羧基	—	—	—	—	5	4.6	4.7	5	—	5	—	—	—
氧化	聚合 + 硅烷化	羧基+氨基	—	—	—	—	—	—	52^[18]	—	—	—	—	—	—
	硅烷化	羧基、巯基	—	—	87.5^[42]	—	—	—	—	—	—	—	137.7^[42]	—	—
		羧基	—	8.9^[43]，58^[35]	—	—	—	8.6^[43]	112^[35]	66^[35]	—	9.7^[43]	9.4^[43]	—	167^[44]
		醛基	—	—	—	—	—	—	38	—	—	—	158	—	—
酯化		磷酸基+ 羧基^[19]	—	—	—	73	—	—	114	—	120	—	—	—	—
		磷酸基	10^[31]	—	—	—	—	—	—	—	—	—	—	—	—
		磺酸基	—	—	—	—	—	—	—	—	—	—	249^[41]	—	—
硅烷化	氧化	巯基 + 羧基	—	—	—	—	—	—	—	—	—	—	—	729.9^[18]	—
		氨基^[17]	—	—	—	—	—	156.3	195.6	—	—	405.6	—	—	—
接枝共聚	氧化	羧基 + 氨基	—	—	—	—	—	—	52^[45]	—	—	—	—	—	—
		羧基^[35]	—	—	—	—	—	117	57.5^[39]	138	—	135	165	—	—

图3 纳米纤维素复合膜制备及其重金属吸附过程示意图[58]

图4 水凝胶的形成机理示意图[61]

图5 水凝胶的制备过程示意图[62]

图6 气凝胶制备的常见方法[64]

图7 气凝胶制备示意图[65]

图8 纳米纤维素微球制备改性及其重金属离子吸附示意图[68]

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