磁性复合凝胶球对Pb(Ⅱ)的吸附特性与机制

包炳钦; 张军; 宋卫锋; 刘建国; 冯嘉颖; 胡志成

doi:10.13801/j.cnki.fhclxb.20200924.001

磁性复合凝胶球对Pb(Ⅱ)的吸附特性与机制

doi: 10.13801/j.cnki.fhclxb.20200924.001

包炳钦^{1, 2, 3, 4,},
张军^{2, 3, 4,},
宋卫锋^1, ,,
刘建国^{2, 3, 4,},
冯嘉颖^{1, 2, 3, 4},
胡志成^{2, 3, 4,}

1.
广东工业大学　环境科学与工程学院，广州 510006
2.
广东省资源综合利用研究所，广州 510000
3.
稀有金属分离与综合利用国家重点实验室，广州 510000
4.
广东省矿产资源开发与综合利用重点实验室，广州 510000

基金项目: 广州市科技计划项目(201904020021)；广东省科学院科技专项项目(2018GDASCX-0109)

详细信息

通讯作者:
宋卫锋，博士，教授，研究方向为水污染治理　E-mail：842663012@qq.com

中图分类号: X52；X703；TQ424
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- 文章访问数: 982
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- 被引次数: 0
出版历程
- 收稿日期: 2020-07-30
- 录用日期: 2020-09-09
- 网络出版日期: 2020-09-24
- 刊出日期: 2021-06-23

Adsorption characteristics and mechanism of Pb(Ⅱ) on magnetic composite gel spheres

BAO Bingqin^{1, 2, 3, 4
,},
ZHANG Jun^{2, 3, 4
,},
SONG Weifeng^{1
, ,},
LIU Jianguo^{2, 3, 4
,},
FENG Jiaying^{1, 2, 3, 4},
HU Zhicheng^{2, 3, 4
,}

1.
School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China
2.
Guangdong Institute of Resources Comprehensive Utilization, Guangzhou 510000, China
3.
State Key Laboratory of Rare Metal Separation and Comprehensive Utilization, Guangzhou 510000, China
4.
Guangdong Provincial Key Laboratory of Mineral Resources Development and Comprehensive Utilization, Guangzhou 510000, China

摘要

摘要: 以海藻酸钠(SA)作为基体前驱材料，通过离子交联法包埋固化L-甲硫氨酸(L-met)和纳米Fe₃O₄形成磁性复合凝胶球SA@Fe₃O₄/L-met。实验探究了SA@Fe₃O₄/L-met在不同pH、投加量和初始离子浓度条件下对Pb(Ⅱ)吸附能力的影响。结果表明，在pH=5、投加量为0.5 g·L⁻¹、初始浓度为20 mg·L⁻¹时，SA@Fe₃O₄/L-met对Pb(Ⅱ)能达到较好的吸附效率，最大吸附量可达到328.02 mg·g⁻¹，远大于Fe₃O₄@SA与SA的吸附量142.5 mg·g⁻¹和152.8 mg·g⁻¹。吸附动力学和热力学研究表明该吸附过程分别对准二级动力学方程和Langmuir方程的拟合程度更大，且反应过程是一个熵增吸热的过程。最后采用SEM、XPS、VSM等对SA@Fe₃O₄/L-met的结构与性能进行表征分析，发现SA@Fe₃O₄/L-met中的氨基和羧基通过配位反应与Pb(Ⅱ)结合，同时还存在着离子交换作用。经过5次解吸后SA@Fe₃O₄/L-met的吸附量仍能达到210.5 mg·g⁻¹，是一种较理想的环保吸附剂。
- Pb(Ⅱ) /
- L-甲硫氨酸(L-met) /
- 海藻酸钠 /
- 吸附 /
- 磁性
Abstract: In this paper, SA@Fe₃O₄/L-met used sodium alginate (SA) as matrix precursor material, with magnetic composite gel balls obtained by immobilizing iron trioxide (Fe₃O₄) and L-methionine (L-met) by ion cross-linking. The influence of pH, dosage and initial concentration on Pb(Ⅱ) adsorption was explored. The results show that at pH=5, the dosage is 0.5 g·L⁻¹, the initial concentration is 20 mg·L⁻¹, SA@Fe₃O₄/L-met can achieve better adsorption efficiency for Pb(Ⅱ), and the maximum adsorption amount can reach 328.02 mg·g⁻¹, much larger than the adsorption capacity of SA@Fe₃O₄ and SA, 142.5 mg·g⁻¹ and 152.8 mg·g⁻¹. Studies on adsorption kinetics and thermodynamics show that the adsorption process is aligned with the second-order kinetic equation and Langmuir equation to a greater degree of fit, and the reaction process is a process of entropy increase and heat absorption. The structure and performance of the gel sphere were characterized by using SEM, XPS and VSM. It was found that the amino groups, carboxyl groups and hydroxyl groups in the gel ball participating in the reaction process, combining with Pb(Ⅱ), and there also exists ion exchange. After 5 times of desorption, the adsorption capacity of the material can still reach 210.5 mg·g⁻¹, which is an ideal environmentally friendly adsorbent.
- Pb(Ⅱ) /
- L-methionine (L-met) /
- sodium alginate /
- adsorption /
- magnetic

HTML全文

图 1 pH对海藻酸钠(SA)@Fe₃O₄/L-甲硫氨酸(L-met)吸附Pb(Ⅱ)的影响

Figure 1. Effect of pH on the adsorption capacity of Pb(Ⅱ) by the sodium alginate (SA)@Fe₃O₄/L-methionine (L-met)

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图 2 初始浓度对SA@Fe₃O₄/L-met吸附Pb(Ⅱ)的影响

Figure 2. Effect of initial concentration on the adsorption capacity of Pb(Ⅱ)by the SA@Fe₃O₄/L-met

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图 3 投加量对SA@Fe₃O₄/L-met吸附Pb(Ⅱ)的影响

Figure 3. Influence of dosage on the adsorption capacity of Pb(Ⅱ) by SA@Fe₃O₄/L-met

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图 4 不同初始浓度下时间对SA@Fe₃O₄/L-met吸附Pb(Ⅱ)的影响

Figure 4. Effect of time at different initial concentrations on the adsorption of Pb(Ⅱ) by SA@Fe₃O₄/L-met

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图 5 不同循环次数下SA@Fe₃O₄/L-met吸附量的变化

Figure 5. Changes in the adsorption capacity of SA@Fe₃O₄/L-met under different cycle times

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图 6 SA@Fe₃O₄/L-met的表面形貌 (a)、Fe (b) 和N (c) 的表面元素分布和EDS能谱 (d)

Figure 6. Surface morphology (a) of SA@Fe₃O₄/L-met, element distribution diagram of Fe (b) and N (c) and EDS spectrum (d)

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图 7 SA@Fe₃O₄/L-met凝胶球吸附Pb(Ⅱ)的XPS能谱

Figure 7. XPS spectra of SA@Fe₃O₄/L-met adsorption of Pb(Ⅱ)

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图 8 Fe₃O₄和SA@Fe₃O₄/L-met磁滞回线

Figure 8. Hysteresis loop of Fe₃O₄andSA@Fe₃O₄/L-met

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图 9 SA@Fe₃O₄/L-met磁场固液分离现象

Figure 9. Magnetic field solid-liquid separation phenomenon of SA@Fe₃O₄/L-met

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表 1 SA@Fe₃O₄/L-met吸附Pb(Ⅱ)的准一级动力学与准二级动力学拟合

Table 1. Calculated kinetic parameters for adsorption of Pb(II) by the SA@Fe₃O₄/L-met

C_o/(mg·L⁻¹)	Pseudo-first-order kineticmodel			Pseudo-second-order kineticmodel
C_o/(mg·L⁻¹)	Q_e/(mg·g⁻¹)	k₁	R²	Q_e/(mg·g⁻¹)	k₂	R²
50	95.116	0.04111	0.97535	94.6073	0.00281	0.99922
100	161.851	0.02371	0.91516	164.8347	0.00194	0.99966
200	325.131	0.02286	0.92226	323.8061	0.00129	0.99996
Notes: C_o—Initial concentration of Pb(Ⅱ); Q_e—Adsorption capacity at adsorption equilibrium; k₁, k₂—Adsorption constant; R²—Goodness.

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表 2 SA@Fe₃O₄/L-met吸附Pb(Ⅱ)的吸附等温线模型拟合

Table 2. Isotherm model constants and correlation for adsorption of Pb(II) by the SA@Fe₃O₄/L-met

Temperature/℃	Langmuir				Freundich
Temperature/℃	Q_max/(mg·g⁻¹)	k_L/(L·mg⁻¹)	R²	R_L	k_F/(L·mg⁻¹)	n	R²
25	330.430	0.032810	0.99977	0.03685	115.329	4.857	0.82080
35	333.011	0.042134	0.99982	0.02925	121.857	5.0457	0.83013
45	337.240	0.049391	0.99983	0.02521	129.423	5.2625	0.81762
55	342.271	0.057546	0.99986	0.02182	138.023	5.5236	0.81789
Notes: Q_max—Maximum adsorption capacity; k_L—Langmuir equilibrium constant; k_F—Freundich equilibrium constant; n-Adsorption intensity characteristic constant; R_L—Determine the adsorption properties.

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表 3 SA@Fe₃O₄/L-met的吸附热力学参数

Table 3. Thermodynamic parameters for adsorption of Pb(II) by the SA@Fe₃O₄/L-met

Temperature/℃	k_F	∆G/(kJ·mol⁻¹)	∆H/(kJ·mol⁻¹)	∆S/(J·mol⁻¹)
25	115.329	−11.76210	4.8667	55.8043
35	121.857	−12.29872		55.7319
45	129.423	−12.85728		55.7015
55	138.027	−13.43712		55.6541
Notes: k_F—Freundich equilibrium constant; ∆G—Gibbs Free Energy; ∆H—Adsorption enthalpy change; ∆S—Adsorption entropy change.

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表 4 SA@Fe₃O₄/L-met吸附量与其他吸附材的吸附量比较

Table 4. Adsorption results of Pb(II) onto different absorbents by the SA@Fe₃O₄/L-met

Adsorbent	pH	Reaction time/h	Maximum adsorption capacity/(mg·g⁻¹)	References
Silica modified calcium alginate–xanthan gum hybrid bead	5	3.3	18.9	ZHANG S, et al^[21]
Iron-oxide modified sericite alginate beads	5	15	133.73	LALHMUNSIAMARADHESHYAM R,et al^[22]
Sodium alginate/graphene oxide aerogel	5.5	4	267.4	JIAO C,et al^[23]
Hydrocolloid liquid-core capsules	5.5	3	300	NUSSINOVITCH A, et al^[24]
SA@Fe₃O₄/L-met	5	0.5	328.02	This paper
Carboxylated cellulose nanocrystal/sodium alginate hydrogel beads	5	2	338.98	HU Z, et al^[19]
Magnetic carboxyl-functionalized attapulgite/calcium alginate beads	5	2	471.20	ZOU M F,et al^[25]

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