磁性壳聚糖微球的改性研究进展及其在水处理中的应用

冯颖; 崔倩; 解玉鞠; 赵孟杰; 张建伟; 董鑫

doi:10.13801/j.cnki.fhclxb.20211105.003

磁性壳聚糖微球的改性研究进展及其在水处理中的应用

doi: 10.13801/j.cnki.fhclxb.20211105.003

沈阳化工大学　机械与动力工程学院, 沈阳 110142

基金项目: 国家自然科学基金(21406142)；辽宁省自然基金(2020-MS-230)；辽宁省教育厅科学研究项目(LJ2020036)

详细信息

通讯作者:
董鑫，博士，讲师，硕士生导师，研究方向为环境流体多相流传递理论与技术装备　E-mail: dongxin1106@syuct.edu.cn

中图分类号: TQ424.3;
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出版历程
- 收稿日期: 2021-09-28
- 修回日期: 2021-10-22
- 录用日期: 2021-10-31
- 网络出版日期: 2021-11-08
- 刊出日期: 2022-06-01

Research progress on modification of magnetic chitosan microspheres and its application in water treatment

School of Mechanical and Power Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China

摘要

摘要: 磁性壳聚糖微球(Magnetic chitosan microsphere，MCM)是一种新型吸附材料，具有独特的磁响应特性和良好的吸附性能，以其突出的环保和可控性在生物医学、食品工程和污水处理等许多领域受到高度重视。传统方法制备的MCM存在纳米粒子易溶于酸性溶液、应用范围窄等问题，因此研究者们在其优化改性方面展开了大量工作。本文从磁性纳米粒子改性和壳聚糖改性两个方面详细综述了优化MCM的研究进展，包括磁性纳米粒子的修饰与替换，壳聚糖分子印迹改性、接枝改性、金属螯合改性、烷基化改性等方法。总结了改性后MCM对废水中重金属离子、印染废料中阴阳离子染料的吸附情况和去除效果。最后讨论了改性MCM面临的问题与挑战，展望了其未来发展趋势，提出了进一步提高改性MCM应用效率的方法和设想。
- 壳聚糖微球 /
- 磁性纳米粒子 /
- 重金属 /
- 吸附剂 /
- 改性方法 /
- 废水
Abstract: Magnetic chitosan microsphere (MCM) is a new type of adsorption material, which has unique magnetic response characteristics and good adsorption performance. With its outstanding environmental protection and controllability, it has attracted high attention in many fields such as biomedicine, food engineering, sewage treatment and so on. MCM prepared by traditional methods has some problems, such as nanoparticles are easy to dissolve in acidic solution and narrow application range. Therefore, researchers have carried out a lot of work in its optimization and modification. In this paper, the research progress of optimizing MCM was reviewed in detail from two aspects: magnetic nanoparticles modification and chitosan modification, including modification and replacement of magnetic nanoparticles, chitosan molecular imprinting modification, grafting modification, metal chelation modification, alkylation modification and so on. The adsorption and removal effects of modified MCM on heavy metal ions in wastewater and ionic dyes in printing and dyeing waste were summarized. Finally, the problems and challenges faced by modified MCM were discussed. Its future development trend was prospected, and the methods and ideas to further improve the application efficiency of modified MCM were put forward.
- chitosan microspheres /
- magnetic nanoparticles /
- heavy metals /
- adsorbents /
- modification method /
- wastewater

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图 1 磁性壳聚糖微球(MCM)的制备过程

Figure 1. Preparation of magnetic chitosan microspheres (MCM)

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图 2 分子印迹聚合物制备过程(a, b, c, d, e代表模板分子上与功能单体的作用点)

Figure 2. Preparation process of molecularly imprinted polymer (a, b, c, d and d represent the interaction point between the template molecule and the functional monomer)

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图 3 不同接枝方式

Figure 3. Different grafting methods

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图 4 壳聚糖分子间氢键

Figure 4. Intermolecular hydrogen bond of chitosan

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表 1 常用交联剂的结构及特点

Table 1. Structures and characteristics of common crosslinking agents

Crosslinker	Structure	Advantage	Shortcoming	Ref.
Glutaraldehyde		Aldehyde group combines with the amino group to form a new nitrogen-carbon double bond by Schiff base reaction and cross-linking, resulting in a stable structure and increased hydrophobic strength	Two carbonyl groups are far away from each other, the crosslinking site is bound and the spatial site resistance is large, and the product is not highly crystalline	[14-16]
Sodium tripolyphosphate		Non-toxic, amino protonation cross-linked with phosphate ions to improve the chemical stability of the substance while introducing phosphate	At higher pH, the product surface is negatively charged and the phosphate dissociates, reducing the adsorption capacity	[17-19]
Glyoxal		Amino group at the C2 position reacts with the carbonyl group in the Schiff reaction, and the hydroxyl group at the C6 position reacts with the carbonyl group in the acetal reaction, which is conducive to improving the fiber strength of the product	—NH² generates —NH₃⁺, which is not suitable for strong acid environment because it is not conducive to Schiff reaction.	[20-21]
Epichlorohydrin		Carbon and chlorine bonds are broken and the hydroxyl group becomes ether after epoxy ring opening, so the cross-linking efficiency is high and the product is more stable; and the amino group is not occupied, so more sites are combined with pollutants	Suitable for alkaline environment, the preparation process should be cross-linked before neutralizing with acid	[22-23]

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表 2 不同材料对磁性Fe₃O₄纳米粒子的修饰效果

Table 2. Modification effects of different materials on magnetic Fe₃O₄ nanoparticles

Modifying substance	Modification effect	Experimental result	Advantage	Ref.
Oleic acid	It is spherical and becomes larger in size and evenly dispersed	When the reaction temperature was 31℃, 400 nm microspheres were prepared, showing high sensitivity	Reduce surface energy without changing crystal structure and improve magnetic nanoparticle dispersion	[24]
SiO₂	SiO₂uniformly coated magnetic nanoparticles	When pH=2.0, the maximum adsorption capacity of Cr(Ⅵ) is 236.4 mg·g⁻¹	Improve the acid resistance of adsorbent, reduce the content of magnetic particles, and still ensure the smooth separation	[25]
Attapulgite	Nanoparticles were successfully attached to the rod	When pH is adjusted to 0.97%, the maximum adsorption rate of Pd⁴⁺ and Pd²⁺ is 0.98%	High density adsorption of iron ions on the rocks, while retaining a large number of adsorption sites for polyelectrolytes	[26]
Phase change material	Phase change material and magnetic iron oxide were encapsulated in chitosan microspheres at the same time	Enthalpy of crystallization at 30 and 32°C and the enthalpy of melting at 43℃ dropped to 75.0 and 73.0 J·g⁻¹, respectively	Combination of the two substances as a core effectively enriches the functionality and applicability of chitosan, while increasing the magnetic	[27]

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表 3 部分新型粒子替换Fe₃O₄ 粒子的实例

Table 3. Examples of some new particles replacing Fe₃O₄

Magnetic particle	Product characteristic	Experimental result	Ref.
CoFe₂O₄	Uniform dispersion of magnetic particles, excellent magnetic response, good adsorption characteristics	At the end of adsorption, the solution was nearly colorless and the maximum desorption efficiency was about 92.85%	[28]
MnFe₂O₄	Does not damage the structure of the position itself, and at the same time has a synergistic effect on the adsorption performance of chitosan and MnFe₂O₄	Maximum removal efficiency of MB at pH=6.0 and initial concentration of 671.4 mol·L⁻¹ was 96.4%, and the maximum adsorption capacity was about 85.3 mg·g⁻¹	[29]
Co_0.5NiFe₂O₄	Excellent core-shell structure and magnetic response performance	Maximum decolorization rate of cationic dyes reached over 95.0% at a dose of 20 mg·g⁻¹	[30]
Magnetic graphene oxide	Preparation of composite products of graphene oxide and iron oxide for solid-liquid separation by external magnetic field and high adsorption of pollutants	Average adsorption capacity of the product was 80.8 mg·g⁻¹; the maximum desorption efficiency was 86.3 mg·g⁻¹ at 40℃ and pH=6.8	[31]

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表 4 磁性壳聚糖微球(MCM)分子印迹改性

Table 4. Molecular imprinting modification of magnetic chitosan microspheres (MCM)

Template molecule	Crosslinking agent	Advantage	Results of control experiments	Results of control experiments	Ref.
Cu²⁺	Epichlorohydrin	Cu²⁺ cross-linked with I-CM, breaking the coordination of —NH₂ and —OH, decreasing crystallization ability and acid solubility	Surface leveling of the blank control was completely soluble in acetic acid, and the adsorption rate was about 36.7%	At 80℃ and pH=5.0, the initial mass concentration of Cu²⁺ was 338.7 mg·L⁻¹ and the product adsorption amount was 72.8 mg·g⁻¹	[33]
2,4,6 Trichlorophenol	Ethylene glycol dimethacrylate	A large number of binding sites to improve product stability and recognition	Maximum adsorption of the product was about 58.0 mg·g⁻¹ at 25℃ and pH=2.0-6.0	Maximum adsorption of the product was about 75.0 mg·g⁻¹ at 25℃ and pH=2.0-6.0	[34]
Uranyl ion	N. N- Methylene bisacrylamide	C=C bond interacts with uranyl ion and the binding energy increases, electrostatic attraction between phosphoric acid and lanthanum, effective adsorption of uranium by phosphoric acid and N-isopropylacrylamide	Maximum adsorption capacity was 105.0 mg·g⁻¹ at 25℃ and pH=6.0	At 25℃ and pH=6.0, the maximum adsorption amount was 232.0 mg·g-1 and U(VI) was reduced to U(IV)	[35]
Piroxicam (PIX)	Ethylene glycol dimethyl acetamide	Cavity fits to the target template, PIX has high affinity to the active site and forms stable hydrogen bonds with the acrylic group	pH=4.0, magnetization saturation value of 20.0 emu·g⁻¹, low adsorption efficiency	pH=4.0, maximum adsorption efficiency of 42.3 mg·g⁻¹, and magnetization saturation value of 38.0 emu·g⁻¹	[36]
Deep eutectic solvent	Glutaraldehyde	Increased specific surface area for efficient selective identification and binding to cavities	20-60℃, the average adsorption capacity is about 15.0 mg·g⁻¹, which is about 1.9 times that of MgO	20-60℃, the average adsorption capacity is 80.8 mg·g⁻¹, which is about 11.0 times that of MgO	[31]

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表 5 MCM的接枝改性

Table 5. Graft modification of MCM

Grafting material	Product preparation	Removal of ions	Control experiment	Experimental result	Ref.
Glutamine	Glutamine-modified magnetic chitosan microspheres	Acid green 25 (AG25), Mercury ions	Maximum adsorption of G25 at pH=2.0 was 460.0 mg·g⁻¹ and the maximum adsorption of Hg²⁺ at pH=6.0 was 80.0 mg·g⁻¹	Maximum adsorption of G25 was 900.0 mg·g⁻¹ at pH=2.0 and 140.0 mg·g⁻¹ for Hg²⁺ at pH=6.0	[42]
Ammonium persulfate (NH4)	Aminated magnetic chitosan microspheres	Methylene blue (MB), Brilliant red (RBR)	Adsorption amount for MB was 105.0 mg·g⁻¹ at pH=12.0 and 450.0 mg·g⁻¹ for RBR at pH=10.0	Maximum adsorption amounts for MB and RBR were 210.9 and 638.7 mg·g⁻¹ at pH=12.0, respectively	[43]
1,6-hexanediamine	1, 1,6-hexanediamine-functionalized magnetic chitosan microspheres (AF-MCTS)	Cr(Ⅵ)	Maximum adsorption capacity was 110.0 mg·g⁻¹	Maximum adsorption capacity was 208.3 mg·g⁻¹	[44]

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表 6 壳聚糖烷基化改性的不同位置优缺点

Table 6. Advantages and disadvantages of different positions of chitosan alkylation modification

Route	Modification position	Advantage	Disadvantage
O-site alkylation	Hydroxyl groups at C3 and C6 positions	Amino group has a polycationic character, decreases crystallinity, weakens intermolecular hydrogen bonds, and interacts with negative charges to inhibit bacteria and sterilization	Amino group is more active than the hydroxyl group, and the reaction starts with the amino group at the C2 position, which is not easy to prepare
N-position alkylation	Amino in the C2 position	Intermolecular hydrogen bonds are broken, regularity is reduced, crystallinity of the molecule is decreased, new functional groups are introduced, and the complex has new properties	Special nature of arsenate, solution alkaline good, the removal of metal ions when the solution pH plays an important role, the two need to coordinate
O, N-position alkylation	Amino group at C2 position, hydroxyl group at C3 and C6 positions	Adding substances with different biocompatibility differences, hydrophobicity changes, and simpler preparation process	Introduction of large substituents reduces intermolecular hydrogen bonds and changes hydrolysis ability

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表 7 MCM做吸附剂处理印染废水

Table 7. Treatment of printing and dyeing wastewater with MCM as adsorbent

Adsorbent	Dye	Principle of action	Experimental result	Repeat regeneration experiment	Ref.
β-cyclodextrin modified magnetic chitosan microspheres	Methylene blue dye	Electrostatic adsorption between -OH and methylene blue	Maximum adsorption capacity was 123.7 mg·g⁻¹ and the maximum adsorption capacity was positively correlated with pH and negatively correlated with temperature	Adsorption amounts of the first and third experiments were 123.7 mg·g⁻¹ and 115.9 mg·g⁻¹, and the decolorization rates were 93.7% and 92.7%, respectively	[54]
Silver particle-modified magnetic chitosan microspheres	Composite dye system	The —NH₂ and —OH of the shell layer are protonated and deprotonated significantly at different acid and alkaline levels, and are easily bound to anionic and cationic dyes	At 35℃ and pH=4.0, the maximum dye adsorption was 271.2 mg·g⁻¹; the maximum removal rate of dye was 99.5%.	Adsorption rates of dyes were 99.0%, 95.0% and 91.0% for the three repeated regeneration experiments, respectively	[55]
Polyacryloyloxyethyl trimethyl ammonium chloride grafted magnetic chitosan microspheres	Sunset yellow dye	Quaternary ammonium group has increased hydrophilicity, and the quaternary ammonium group can be electrostatically attracted to sunset yellow with or without -NH2 protonation	Maximum adsorption capacity at 25℃ and pH=2.0 was 787.1 mg·g⁻¹	Adsorption rate was 96.2% after five adsorption elution cycles	[56]
Sr_3.8Fe_25.7O_70.4 Chitosan magnetic particles	Crystalline Violet (CV) Alkaline Red (BR9)	Initial concentration difference provides resistance to two-phase mass transfer and promotes dye adsorption through hydrogen bonding, electrostatic adsorption	Maximum removal rates of CV and BR9 at 30-40℃ and pH>7 are 94.5% and 97.5%, respectively, and are highly efficient and environmentally friendly.	Dye removal rate remains above 90.0% after five cycles	[57]

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表 8 MCM作吸附剂处理重金属离子

Table 8. Treatment of heavy metal ions with MCM as adsorbent

Adsorbent	Heavy Metal	Principle of action	Experimental result	Repeat Regeneration Experiment	Ref.
Magnetic chitosan microspheres	P	Adsorption of porous carbon films depends mainly on electrostatic effect	Maximum adsorption amount was 4.8 mg·g⁻¹ at pH=7.0	After treatment and reuse, the adsorption effect is almost unaffected	[62]
Quaternary ammonium magnetic chitosan microspheres	Cr，P	Adsorption mechanism of chromium and phosphorus is mainly electrostatic interactions	At 25°C and pH=6.0, the saturation adsorption amounts of P and Cr were 416.0 and 419.0 mg·g⁻¹, respectively	After performing four adsorption-desorption cycles, the adsorption effect was not affected by	[63]
Novel cross-linked chitosan magnetic beads modified with cysteinyl urea Schiff base	Cu、Cr	Acidic environment -NH₂ and -C=N- have high nitrogen content to facilitate chelation, and both protonate and electrostatically adsorb with CRO₄^2- and HCrO₄⁻	The maximum adsorption amounts of most Cr at pH=2.0 and pH=5.0 were 156.5 and 138.5 mg·g⁻¹, respectively	After three adsorption-desorption cycles, the adsorption efficiency of metal ions was still higher than 91.0%	[64]
Magnetic carboxymethyl chitosan composite microspheres	Mn²⁺	pH=6.5-7.5 to prevent the generation of manganese hydroxide precipitation; electrostatic adsorption of surface adsorption sites with Mn²⁺	At 25°C and pH=7.0, the adsorption capacity of Mn²⁺ was 75.7 mg·g⁻¹ and the adsorption rate was higher than 90.0%	After five elution tests, the adsorption efficiency for Mn²⁺ was still 77.9%	[65]
Nanoporous magnetic cellulose-chitosan composite microspheres	Cu	Hydrogen bonding and miscibility between the two effectively suppress the crystal structure; copper and nitrogen atoms are chemically bonded	Adsorption amount was 65.8 mg·g⁻¹ at pH=5.0	Five cycles of experiments, the adsorption capacity of Cu, no significant decline	[47]
Magnetic Fe₃O₄ chitosan microspheres	Ag	Electrostatic interaction causes surface cations to form complexes with electron-rich organic ligands	Extraction efficiency of lakes and wastewater ranged from about 84.9% to 98.8%	Average extraction efficiency was still 77.2% after multiple repetitions of the experiment	[66]

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表 9 在不同领域作吸附剂的应用实例

Table 9. Application examples of adsorbent in different fields

Adsorbent	Adsorbed material	Mechanism of action	Experimental result	Ref.
PEI-modified magnetic chitosan microspheres	Ibuprofen	Regular spherical shape, narrow particle size distribution, successful introduction of a large number of amino	Maximum adsorption capacities of the three composites with different ratios were 89.3, 100.0 and 138.6 mg·g⁻¹, respectively	[67]
Magnetic chitosan microspheres	Apple juice organic acid	Acid ions form ionic bonds with protonated amino groups	At 25℃, the average adsorption capacity was 112.4 mg·g⁻¹ and the saturation capacity was 188.7 mg·g⁻¹	[68]
Molecularly imprinted polymer modified magnetic group microspheres	Chloramphenicol	Hydrogen bonds, ionic bonds make strong interactions between molecules	30-40℃, the maximum adsorption capacity is 32.5 mg·g⁻¹	[69]
Quaternary ammonium-functionalized magnetic chitosan microspheres	Beet juice coloring agent	Electrostatic adsorption of quaternary ammonium groups and impurities, ion exchange reaction between Cl⁻ and quaternary ammonium cations	Maximum adsorption efficiency was 99.4% and the maximum adsorption capacity was 127.2 mg·g⁻¹	[70]
Novel magnetic chitosan microspheres	Lysozyme	Cavity-specific recognition of lysozyme	25℃, the maximum adsorption capacity is 130.0 mg·g⁻¹	[71]

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