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

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

Abstract

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

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

CLC Number:

TE869

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.

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.

Figures/Tables 23

References 19

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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

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

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

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

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

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

Fe₃O₄@PGMA-Arg磁性吸附剂的制备及对亚铁离子的吸附性能

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Figures/Tables 23

References 19

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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

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