Fe3O4@PGMA-Arg磁性吸附剂的制备及对亚铁离子的吸附性能

doi:10.16085/j.issn.1000-6613.2021-0109

摘要/Abstract

摘要：

为脱除油田采出水中的Fe(Ⅱ)合成磁性吸附剂，本文以溶剂热法制得亲水性Fe₃O₄纳米颗粒，使用盐酸多巴胺（DA）进行包覆得到Fe₃O₄@PDA，再以甲基丙烯酸缩水甘油酯（GMA）在其表面聚合接枝得到Fe₃O₄@PGMA，后经精氨酸（Arg）修饰后得到功能化的Fe₃O₄@PGMA-Arg。通过红外光谱、X射线光电子能谱、X射线衍射和磁化强度对制备的纳米颗粒进行表征，结果表明Fe₃O₄@PGMA-Arg中具有伯胺、亚胺双键、羟基和羧基官能团，其中伯胺基团和亚胺双键上的N可与Fe(Ⅱ)形成配位键，羟基和羧基的O可与Fe(Ⅱ)形成配位键，从而达到吸附Fe(Ⅱ)的目的。合成产物仍保持了Fe₃O₄的反尖晶石结构，具有好的磁响应性能。通过静态吸附实验探究吸附条件对Fe₃O₄@PGMA-Arg吸附Fe(Ⅱ)的影响因素，结果表明，Fe(Ⅱ)的吸附量随着温度和初始浓度的增加而增加，适宜的pH为4。动力学和热力学研究表明，吸附Fe(Ⅱ)过程符合准二级反应动力学模型，吸附等温线符合Langmuir模型，吸附过程活化能为45.60kJ/mol，为化学吸附。Fe₃O₄@PGMA-Arg经5次再生后，对亚铁离子仍保持较高的脱除率。

关键词: 亚铁离子, 磁性, 吸附, 聚合物接枝

Abstract:

Magnetic adsorbents were synthesized to remove the ferrous ion form oilfield. The hydrophilic Fe₃O₄ nanoparticles were prepared by solvothermal method and Fe₃O₄@PDA was obtained by coating with dopamine hydrochloride. Glycidyl methacrylate was also grafted onto Fe₃O₄@PDA to obtain Fe₃O₄@PGMA. Fe₃O₄@PGMA-Arg was obtained by modifying Fe₃O₄@PGMA with arginine. Infrared spectrometer, X-ray photoelectron spectrometer, X-ray diffractometer and vibrating sample magnetometer were used to characterize these adsorbents. Fe₃O₄@PGMA-Arg had primary amine, imine double bond, hydroxyl and carboxyl functional groups. The N on the primary amine group and imine double bond could form coordination bonds with Fe(Ⅱ), and the O on the hydroxyl and carboxyl groups could also form coordination bond with Fe(Ⅱ), which made Fe₃O₄@PGMA-Arg could adsorb Fe(Ⅱ). These synthesized adsorbents maintained the inverse spinel structure of Fe₃O₄ and the magnetic response properties were good. The static adsorption experiment was carried out to explore the influencing factors of adsorption conditions on Fe(Ⅱ) adsorption by Fe₃O₄@PGMA-Arg. The results indicated that the adsorption capacity of Fe(Ⅱ) increased with the increase of temperature and initial concentration, and the suitable pH was 4. Kinetic and thermodynamic studies showed that the process of Fe(Ⅱ) adsorption conformed to the quasi-second-order reaction kinetic model. The adsorption isotherms conformed to the Langmuir model. The activation energy was 45.60kJ/mol, which was chemical adsorption. Fe₃O₄@PGMA-Arg maintained a high removal rate of ferrous ions after 5 times regeneration.

Key words: ferrous ion, magnetic, adsorption, polymer grafting

中图分类号:

TE869

田忠宇, 杨敬一, 王怿兴, 徐心茹. Fe₃O₄@PGMA-Arg磁性吸附剂的制备及对亚铁离子的吸附性能[J]. 化工进展, 2022, 41(2): 881-891.

TIAN Zhongyu, YANG Jingyi, WANG Yixing, XU Xinru. Preparation of Fe₃O₄@PGMA-Arg magnetic adsorbents and its adsorption performance for ferrous ion[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 881-891.

图/表 23

图1 Fe3O4@PGMA-Arg的制备

图2 Fe3O4、Fe3O4@PDA、Fe3O4@PGMA和Fe3O4@PGMA-Arg的红外光谱图

a—Fe3O4；b—Fe3O4@PDA；c—Fe3O4@PGMA；d—Fe3O4@PGMA-Arg

图3 Fe3O4@PDA、Fe3O4@PGMA和Fe3O4@PGMA-Arg XPS扫描能谱

a—Fe3O4@PDA；b—Fe3O4@PGMA；c—Fe3O4@PGMA-Arg

表1 Fe3O4@PDA、Fe3O4@PGMA和Fe3O4@PGMA-Arg表面元素含量

样品	C 1s（摩尔分数）/%	N 1s（摩尔分数）/%	O 1s（摩尔分数）/%	Br 3d（摩尔分数）/%
Fe₃O₄@PDA	73.97	7.73	18.66	—
Fe₃O₄@PGMA	72.04	0.42	24.48	1.06
Fe₃O₄@PGMA-Arg	70.99	4.10	24.73	0.18

图4 Fe3O4@PGMA-Arg的C 1s XPS分析图谱

图5 Fe3O4@PGMA-Arg的N 1s XPS分析图谱

图6 Fe3O4@PGMA-Arg的O 1s XPS分析图谱

图7 Fe3O4与Fe3O4@PGMA-Arg的XRD图

图8 Fe3O4、Fe3O4@PDA、Fe3O4@PGMA和Fe3O4@PGMA-Arg的TEM图

图9 Fe3O4、Fe3O4@PDA、Fe3O4@PGMA和Fe3O4@PGMA-Arg的磁滞回归线

a—Fe3O4；b—Fe3O4@PDA；c—Fe3O4@PGMA；d—Fe3O4@PGMA-Arg

图10 Fe3O4、Fe3O4@PDA和Fe3O4@PGMA-Arg对Fe(Ⅱ)吸附效果比较

图11 吸附时间对Fe3O4@PGMA-Arg吸附Fe(Ⅱ)的影响

图12 pH对Fe3O4@PGMA-Arg吸附Fe(Ⅱ)的影响

图13 不同pH下Fe3O4@PGMA-Arg的zeta电位

图14 温度和时间对Fe3O4@PGMA-Arg吸附Fe(Ⅱ)的影响

图15 不同初始浓度下温度对Fe3O4@PGMA-Arg吸附Fe(Ⅱ)的影响

图16 Fe3O4@PGMA-Arg用量对不同初始浓度Fe(Ⅱ)吸附效果的影响

表2 Fe3O4@PGMA-Arg不同起始浓度下吸附动力学模型拟合参数

浓度 /mg·L^-1	准一级动力学模型			准二级动力学模型
浓度 /mg·L^-1	k₁/min^-1	Q_e/mg·g^-1	R²	k₂/g·mg^-1·min^-1	Q_e/mg·g^-1	R²
25	0.7465	22.5	0.8833	0.05338	22.8	0.9999
50	1.9614	42.8	0.8601	0.01167	43.8	0.9994
100	1.8076	70.5	0.8520	0.00030	79.0	0.9990

表3 Fe3O4@PGMA-Arg吸附等温线模型拟合参数

温度 /℃	Langmuir模型			Freundlich模型
温度 /℃	K_L/L·mg^-1	Q_m/mg·g^-1	R²	K_F/mg^1-1/ⁿ·L^1/ⁿ·g^-1	n	R²
20	0.08276	121.2	0.9931	16.05	2.05	0.9704
30	0.13181	123.3	0.9924	22.37	2.28	0.9803
40	0.39558	127.2	0.9921	42.24	3.04	0.9783
50	0.67623	136.8	0.9877	54.51	3.15	0.9325

表4 Fe3O4@PGMA-Arg热力学曲线拟合参数

温度/℃	ΔG^?/kJ·mol^-1	ΔH^?/kJ·mol^-1	ΔS^?/J·mol^-1·K^-1
20	-13.55	67.34	298.39
30	-22.44
40	-26.04
50	-28.32

图17 Fe3O4@PGMA-Arg对50mg/L Fe(Ⅱ)吸附再生效果的影响

图18 Fe3O4@PGMA-Arg对20mg/L Fe(Ⅱ)吸附再生效果的影响

图19 Fe3O4@PGMA-Arg对10mg/L Fe(Ⅱ)吸附再生效果的影响

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Fe₃O₄@PGMA-Arg磁性吸附剂的制备及对亚铁离子的吸附性能

Preparation of Fe₃O₄@PGMA-Arg magnetic adsorbents and its adsorption performance for ferrous ion

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