Facile Fabrication of Fe3O4⁃Based β⁃Cyclodextrin Polymers and Its Adsorption Performances

doi:10.3969/j.issn.1672-6952.2022.06.005

Abstract

Abstract:

β?cyclodextrin polymers modified with Fe₃O₄ (β?CDP@Fe₃O₄) was synthesized in alkaline medium using β?cyclodextrin (β?CD) as monomer and epichlorohydrin as crosslinker. The adsorption performances of β?CDP@Fe₃O₄ on bisphenol A (BPA) under static and dynamic conditions were investigated. The results of static experiment show that the adsorption performance of 100 mg/L BPA (pH=5.6) is best at 0.10 g β?CDP@Fe₃O₄. At this point, the equilibrium adsorption capacity, adsorption rate and the maximum adsorption capacity are 45.600 mg/g, 91.3%, and 113.600 mg/g, respectively. The results of dynamic experiment show that the smaller the liquid hourly space velocity, the higher the adsorbent utilization rate, and with the increase of BPA concentration, the adsorption breakthrough time and saturation time are declined. At the same time, the synthesis and adsorption mechanism of β?CDP@Fe₃O₄ were discussed. A rapid adsorption rate for the removal of BPA onto β?CDP@Fe₃O₄ from water solution was achieved, and the adsorption process was mainly due to hydrogen bond and hydrophobic interaction. β?CDP@Fe₃O₄has good regenerative performance, through 6 cycles of static adsorption?desorption, and 3 cycles of dynamic adsorption?desorption without significant changes in adsorption performance.

Key words: β?cyclodextrin crossing resins, Fe₃O₄ modification, Bisphenol A, Adsorption, Regeneration

摘要：

以β?环糊精(β?CD)为单体、环氧氯丙烷为交联剂，在碱性介质中合成了Fe₃O₄改性的β?环糊精聚合物(β?CDP@Fe₃O₄)。在静态和动态条件下，研究了β?CDP@Fe₃O₄对双酚A (BPA)的吸附性能。静态实验结果表明，采用0.10 g β?CDP@Fe₃O₄对100 mg/L BPA（pH=5.6）吸附，其平衡吸附量为45.600 mg/g，吸附率为91.3%，饱和吸附量为113.600 mg/g。动态实验结果表明，液时空速越小，吸附剂利用率越高，且随着BPA质量浓度的增加，吸附穿透时间和饱和时间均呈下降趋势。同时，探讨了β?CDP@Fe₃O₄的合成及吸附机理。β?CDP@Fe₃O₄对BPA的快速吸附是通过氢键和疏水作用实现的。β?CDP@Fe₃O₄具有良好的再生性能，经过6次静态吸附?解吸循环和3次动态吸附?解吸循环后，吸附性能均无明显变化。

关键词: β?环糊精交联树脂, Fe₃O₄改性, 双酚A, 吸附, 再生

CLC Number:

TQ324.8

Yushi Wei, Rui Wang, Zhuang Lin, Heng Jiang, Mingren Huo, Xinyue Chen, Xiaoyan Liang, Chongyang Zhang. Facile Fabrication of Fe₃O₄⁃Based β⁃Cyclodextrin Polymers and Its Adsorption Performances[J]. Journal of Liaoning Petrochemical University, 2022, 42(6): 28-35.

魏雨诗, 王锐, 林壮, 姜恒, 霍明仁, 陈欣悦, 梁晓艳, 张重阳. Fe₃O₄ 基β⁃环糊精聚合物的制备及吸附性能[J]. 辽宁石油化工大学学报, 2022, 42(6): 28-35.

Figures/Tables 11

References 42

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C₀/ (mg·L^-1)	q_e,exp/ (mg·g^-1)	准一级动力学模型			准二级动力学模型			粒子内扩散模型
C₀/ (mg·L^-1)	q_e,exp/ (mg·g^-1)	k₁×10²/ min^-1	q_e,cal/ (mg·g^-1)	R²	k₂×10³/ (g∙mg^-1∙min^-1)	q_e,cal/ (mg·g^-1)	R²	k₃/ (mg∙g^-1∙min^-1/2)	R²
50	22.500	2.5	6.400	0.688 4	50.0	22.300	0.999 8	1.7	0.678 3
100	45.700	4.0	29.300	0.899 9	11.1	45.900	0.999 3	3.6	0.729 5
150	67.200	3.0	31.900	0.894 3	6.4	67.400	0.999 1	5.3	0.749 0

C₀/ (mg·L^-1)	q_e,exp/ (mg·g^-1)	准一级动力学模型			准二级动力学模型			粒子内扩散模型
C₀/ (mg·L^-1)	q_e,exp/ (mg·g^-1)	k₁×10²/ min^-1	q_e,cal/ (mg·g^-1)	R²	k₂×10³/ (g∙mg^-1∙min^-1)	q_e,cal/ (mg·g^-1)	R²	k₃/ (mg∙g^-1∙min^-1/2)	R²
50	22.500	2.5	6.400	0.688 4	50.0	22.300	0.999 8	1.7	0.678 3
100	45.700	4.0	29.300	0.899 9	11.1	45.900	0.999 3	3.6	0.729 5
150	67.200	3.0	31.900	0.894 3	6.4	67.400	0.999 1	5.3	0.749 0

材料	吸附剂	q_max/(mg·g^-1)	循环次数	仪器	文献
β⁃CD基材料	β⁃CDP@Fe₃O₄	113.600	6	紫外可见光谱仪	本文
	CDP⁃MNPs	74.630	3	荧光光谱仪	[34]
	MMIP	105.500	6	紫外可见光谱仪	[35]
	G⁃Fe₃O₄⁃BCD	59.600	6	紫外可见光谱仪	[12]
	CD/CA	79.000	5	紫外可见光谱仪	[14]
	P⁃CDPs	84.000	5	紫外可见光谱仪	[28]
磁性材料	IPDA@MGO	41.200	5	高效液相色谱仪	[22]
	Fe₃O₄@PANI	23.100	-	紫外可见光谱仪	[21]
	Fe₃O₄/GO	72.800	8	高效液相色谱仪	[36]
	C₁₆⁃SiO₂/磁性⁃MMT	59.170	-	高效液相色谱仪	[37]
其他材料	磁性固定化漆酶	100.000	5	紫外可见光谱仪	[38]
	TPC	91.300	-	紫外可见光谱仪	[39]
	GO	49.260	-	高效液相色谱仪	[40]
	Ag₃PO₄/rGH	15.000	5	高效液相色谱仪	[41]
	PP⁃g⁃DMAEMA/PM	44.430	7	高效液相色谱仪	[42]
	MAlOr⁃NaBt	5.000	1	高效液相色谱仪	[20]
	PES⁃SiO₂	0.053	-	高效液相色谱仪	[19]

材料	吸附剂	q_max/(mg·g^-1)	循环次数	仪器	文献
β⁃CD基材料	β⁃CDP@Fe₃O₄	113.600	6	紫外可见光谱仪	本文
	CDP⁃MNPs	74.630	3	荧光光谱仪	[34]
	MMIP	105.500	6	紫外可见光谱仪	[35]
	G⁃Fe₃O₄⁃BCD	59.600	6	紫外可见光谱仪	[12]
	CD/CA	79.000	5	紫外可见光谱仪	[14]
	P⁃CDPs	84.000	5	紫外可见光谱仪	[28]
磁性材料	IPDA@MGO	41.200	5	高效液相色谱仪	[22]
	Fe₃O₄@PANI	23.100	-	紫外可见光谱仪	[21]
	Fe₃O₄/GO	72.800	8	高效液相色谱仪	[36]
	C₁₆⁃SiO₂/磁性⁃MMT	59.170	-	高效液相色谱仪	[37]
其他材料	磁性固定化漆酶	100.000	5	紫外可见光谱仪	[38]
	TPC	91.300	-	紫外可见光谱仪	[39]
	GO	49.260	-	高效液相色谱仪	[40]
	Ag₃PO₄/rGH	15.000	5	高效液相色谱仪	[41]
	PP⁃g⁃DMAEMA/PM	44.430	7	高效液相色谱仪	[42]
	MAlOr⁃NaBt	5.000	1	高效液相色谱仪	[20]
	PES⁃SiO₂	0.053	-	高效液相色谱仪	[19]

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Facile Fabrication of Fe₃O₄⁃Based β⁃Cyclodextrin Polymers and Its Adsorption Performances

Fe₃O₄ 基β⁃环糊精聚合物的制备及吸附性能

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