<i>β</i>-CD/羧基修饰PAMSMs交联共聚物微球吸附水中亚甲基蓝

doi:10.19965/j.cnki.iwt.2024-0360

摘要/Abstract

摘要：

采用自稳定沉淀聚合法制备α-甲基苯乙烯马来酸酐交联共聚物微球（PAMSMs），再以PAMSMs为载体固载β-环糊精（β-CD），得到β-CD修饰的PAMSMs-CD微球，将PAMSMs-CD水解后得到表面羧基功能化的交联共聚物微球H-PAMSMs-CD，并对微球形貌及表面官能团进行表征。以H-PAMSMs-CD微球为吸附剂去除水中亚甲基蓝（MB），研究了吸附剂投加量、吸附时间、MB初始浓度、温度、pH等因素对H-PAMSMs-CD微球吸附MB效果的影响。SEM分析表明，H-PAMSMs-CD微球具有良好的球形度，且粒径均一。H-PAMSMs-CD微球对MB具有优异的吸附性能，在吸附剂投加量0.25 g/L、温度40 ℃、pH=7、吸附时间4 h、MB初始质量浓度120 mg/L条件下，H-PAMSMs-CD微球对MB的最大吸附量为318 mg/g。Langmuir模型和准二阶反应动力学模型能更好地描述H-PAMSMs-CD微球吸附MB的过程，且H-PAMSMs-CD微球对MB的吸附是自发进行的吸热过程。5次脱附循环使用后，H-PAMSMs-CD微球对MB的去除率仍保持在85.0%以上。

关键词: 共聚物微球, β-环糊精, 羧基功能化, 亚甲基蓝, 吸附

Abstract:

α-methylstyrene-maleic anhydride crosslinked copolymer microspheres(PAMSMs) were prepared via self-stable precipitation polymerization, and then β-cyclodextrin(β-CD) functionalized microspheres PAMSMs-CD were obtained by immobilizing β-CD on the PAMSMs. Carboxyl-functionalized crosslinked copolymer microspheres of H-PAMSMs-CD were achieved by the hydrolysis of PAMSMs-CD. The morphology and surface functional groups of the microspheres were characterized. H-PAMSMs-CD microspheres were used as adsorbents to remove methylene blue(MB) from water. The effects of adsorbent dosage, adsorption time, initial concentration of MB, temperature, pH, and other factors on the adsorption efficiency of H-PAMSMs-CD microspheres for MB were studied. SEM analysis showed that H-PAMSMs-CD with spherical morphology and narrow size distribution were obtained. It was found that microspheres had good removal ability on MB. The maximum adsorption capacity of H-PAMSMs-CD for MB was up to 381 mg/g when the initial concentration of MB was 120 mg/L, the dosage of adsorbent was 0.25 g/L, pH of solution was 7, the adsorption temperature was 40 ℃, and the reaction time was 4 h. The adsorption process of H-PAMSMs-CD on MB could be better described by the Langmuir model and quasi second-order kinetic model, which was a spontaneous endothermic process. Furthermore, the removal rate of MB by H-PAMSMs-CD could be maintained more than 85.0% after 5 times of desorption and recycling.

Key words: copolymer microspheres, β-cyclodextrin, carboxyl functionalization, methylene blue, adsorption

中图分类号:

罗菊香, 赖槐东, 杨雨晴, 程德书. β-CD/羧基修饰PAMSMs交联共聚物微球吸附水中亚甲基蓝[J]. 工业水处理, 2025, 45(5): 120-126.

Juxiang LUO, Huaidong LAI, Yuqing YANG, Deshu CHENG. β-CD/carboxyl functionalized PAMSMs crosslinked copolymer microspheres for adsorption of methylene blue in water[J]. Industrial Water Treatment, 2025, 45(5): 120-126.

https://www.iwt.cn/CN/Y2025/V45/I5/120

图/表 14

图1 微球的SEM

Fig.1 SEM images of microspheres

图2 微球的FT-IR光谱

Fig.2 FT-IR spectra of microspheres

图3 PAMSMs-CD和H-PAMSMs-CD的N₂吸附-脱附等温曲线

Fig.3 N₂ adsorption-desorption isotherms of PAMSMs-CD and H-PAMSMs-CD

图4 吸附剂投加量对微球吸附性能的影响

Fig.4 Effects of adsorbent dosage on the adsorption performance of microspheres

图5 吸附时间对微球吸附性能的影响

Fig.5 Effects of adsorption time on the adsorption performance of microspheres

图6 MB初始浓度及温度对微球吸附性能的影响

Fig.6 Effects of initial MB concentration and temperature on the adsorption performance of microspheres

图7 MB溶液初始pH对微球吸附性能的影响

Fig.7 Effects of initial pH of MB solution on the adsorption performance of microspheres

图8 H-PAMSMs-CD微球吸附MB的Langmuir（a）和Freundlich（b）等温模型

Fig.8 The Langmuir（a） and Freundlich（b） isotherm models of MB adsorbed by H-PAMSMs-CD microspheres

表1 H-PAMSMs-CD微球吸附MB的Langmuir和Freundlich等温模型拟合参数

Table 1 Langmuir and Freundlich isotherm fitting parameters of MB adsorbed by H-PAMSMs-CD microspheres

T/K	Langmuir			Freundlich
T/K	Q _max/（mg·g^-1）	K _L/（L·mg^-1）	R ²	K _F	1/n	R ²
298	279	0.398	0.992	143	0.168	0.859
303	299	0.449	0.997	150	0.184	0.802
313	318	0.501	0.995	162	0.185	0.973

图9 H-PAMSMs-CD微球吸附MB行为的准一阶（a）和准二阶（b）动力学模型

Fig.9 The pseudo-first-order（a） and pseudo-second-order（b） kinetic models of MB adsorption on H-PAMSMs-CD microspheres

表2 H-PAMSMs-CD微球吸附MB的动力学模型拟合参数

Table 2 The kinetic model fitting parameters of MB adsorption on H-PAMSMs-CD microspheres

准一阶反应动力学模型			准二阶反应动力学模型
k ₁/min^-1	Q _e，1/（mg·g^-1）	R ²	k ₂/（g·mg^-1·min^-1）	Q _e，2/（mg·g^-1）	R ²
8.15×10^-3	207	0.915	1.06×10^-3	307	0.994

图10 H-PAMSMs-CD微球吸附MB的热力学模型

Fig.10 The thermodynamic model of MB adsorption on H-PAMSMs-CD microspheres

表3 H-PAMSMs-CD吸附MB的热力学拟合参数

Table 3 The thermodynamic fitting parameters of MB adsorption on H-PAMSMs-CD

T/K	ΔG/（kJ·mol^-1）	ΔH/（kJ·mol^-1）	ΔS/（J·mol^-1·K^-1）
298	-2.14	31.3	51.9
303	-2.40
313	-2.80
323	-3.51
333	-3.92

图11 H-PAMSMs-CD微球吸附再生性能

Fig.11 The adsorption and regeneration performance of H-PAMSMs-CD microspheres

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β-CD/羧基修饰PAMSMs交联共聚物微球吸附水中亚甲基蓝

β-CD/carboxyl functionalized PAMSMs crosslinked copolymer microspheres for adsorption of methylene blue in water

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β-CD/羧基修饰PAMSMs交联共聚物微球吸附水中亚甲基蓝

β-CD/carboxyl functionalized PAMSMs crosslinked copolymer microspheres for adsorption of methylene blue in water

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