磁性水滑石复合材料的制备及其对曙红Y的吸附性能

陈杰; 李明明; 王超; 姜海峰; 刘治刚; 金华

doi:10.13801/j.cnki.fhclxb.20210813.001

磁性水滑石复合材料的制备及其对曙红Y的吸附性能

doi: 10.13801/j.cnki.fhclxb.20210813.001

陈杰^1, ,,
李明明¹,
王超¹,
姜海峰²,
刘治刚¹,
金华¹

1.
吉林化工学院　分析测试中心，吉林 132022
2.
东北电力大学　能源与动力工程学院，吉林 132012

基金项目: 国家自然科学基金 (51902125)；吉林省自然科学基金-联合基金项目(YDZJ202101ZYTS029)；吉林市科技创新发展计划项目-杰出青年人才培养专项(20210103092)；吉林省发改委项目(2020C036-4)；吉林省教育厅科学技术研究项目(JJKH20210236KJ)

详细信息

通讯作者:
陈杰，博士，副教授，硕士生导师，研究方向为功能复合材料的制备与应用　E-mail：jiechendr@163.com

中图分类号: X703
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出版历程
- 收稿日期: 2021-04-30
- 修回日期: 2021-07-26
- 录用日期: 2021-07-31
- 网络出版日期: 2021-08-13
- 刊出日期: 2022-03-23

Preparation of magnetic hydrotalcite composite and its Eosin Y adsorption performance

1.
Analysis and Test Center, Jilin Institute of Chemical Technology, Jilin 132022, China
2.
School of Energy and Power Engineering, Northeast Electric Power University, Jilin 132012, China

摘要

摘要: 为了解决水滑石型(LDH)吸附剂在污水处理中难回收的问题，采用双滴沉淀法将磁性Fe₃O₄颗粒与具有吸附性能的Ni-Mg-Al-LDH水滑石相结合，合成了Fe₃O₄@Ni-Mg-Al-LDH磁性水滑石复合吸附材料，利用SEM、XRD、FT-IR和氮气吸附脱附等表征对Fe₃O₄@Ni-Mg-Al-LDH材料的形貌和结构进行测试，并将其用于曙红Y染料废水处理。结果表明，Fe₃O₄@Ni-Mg-Al-LDH对曙红Y染料的吸附在20 min内较为迅速，120 min后吸附趋于平衡，且随着曙红Y初始浓度的升高，Fe₃O₄@Ni-Mg-Al-LDH对曙红Y染料的吸附量也逐渐增加，最大吸附量达到108.6 mg·g⁻¹。同时，Fe₃O₄@Ni-Mg-Al-LDH对曙红Y的吸附过程符合Langmuir等温吸附模型和伪二级动力学方程，表明该吸附过程以单分子层化学吸附为主，且表面扩散和颗粒内扩散共同控制吸附速率。经五次循环后，吸附剂对曙红Y染料的去除率仍能保持80%以上，且吸附后易于磁分离，说明所制备的Fe₃O₄@Ni-Mg-Al-LDH磁性水滑石材料是一种良好的染料废水吸附剂。
- 吸附 /
- 水滑石 /
- 磁性 /
- 去除率 /
- 曙红Y /
- 废水
Abstract: In order to solve the problem of difficult recovery of hydrotalcite (LDH) adsorbent in sewage treatment, Fe₃O₄@Ni-Mg-Al-LDH magnetic hydrotalcite composite adsorption material was synthesized by combining magnetic Fe₃O₄ particles with Ni-Mg-Al-LDH hydrotalcite via double-drop precipitation method. The morphology and structure of the as-prepared Fe₃O₄@Ni-Mg-Al-LDH samples were characterized by SEM, XRD, FT-IR and N₂ adsorption-desorption technologies. And it was used as adsorbent to simulate the wastewater treatment performance of Eosin Y dye. The results show that the adsorption of Eosin Y dye on Fe₃O₄@Ni-Mg-Al-LDH is very quickly within 20 min, while the adsorption tends to balance after 120 min. In addition, with the increase of the initial concentration of Eosin Y dye, the adsorption capacity of Fe₃O₄@Ni-Mg-Al-LDH sample for Eosin Y dye increases gradually and the maximum adsorption capacity is 108.6 mg·g⁻¹. Meanwhile, the adsorption process of Eosin Y dye on Fe₃O₄@Ni-Mg-Al-LDH conforms to the Langmuir isothermal model and pseudo second-order kinetic equation, indicating that the adsorption process is dominated by the chemisorption of molecular layer, and the adsorption rate is controlled by surface diffusion and intra particle diffusion. After five cycles, the removal rate of Eosin Y dye still keeps above 80%, and the adsorbent is easy to be separated by magnetic field, implying that Fe₃O₄@Ni-Mg-Al-LDH magnetic hydrotalcite composite is a good adsorbent for dye wastewater.
- adsorption /
- hydrotalcite /
- magnetism /
- removal rate /
- Eosin Y /
- wastewater

HTML全文

图 1 Fe₃O₄ (a)和 Fe₃O₄@Ni-Mg-Al-水滑石 (Fe₃O₄@Ni-Mg-Al-LDH) (b)的SEM图像

Figure 1. SEM images of Fe₃O₄ (a) and Fe₃O₄@Ni-Mg-Al-hydrotalcite (Fe₃O₄@Ni-Mg-Al-LDH) (b)

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图 2 Fe₃O₄@Ni-Mg-Al-LDH样品的EDS图谱

Figure 2. EDS spectrum of Fe₃O₄@Ni-Mg-Al-LDH

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图 3 Fe₃O₄, Ni-Mg-Al-LDH和Fe₃O₄@Ni-Mg-Al-LDH样品的XRD图谱

Figure 3. XRD patterns of Fe₃O₄, Ni-Mg-Al-LDH and Fe₃O₄@Ni-Mg-Al-LDH samples

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图 4 Fe₃O₄@Ni-Mg-Al-LDH样品的N₂吸附-脱附等温曲线及孔径分布图

Figure 4. N₂ adsorption-desorption isotherm curve and pore diameter distribution of Fe₃O₄@Ni-Mg-Al-LDH

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图 5 Fe₃O₄和Fe₃O₄@Ni-Mg-Al-LDH样品的室温磁滞曲线

Figure 5. Room-temperature magnetization curves of Fe₃O₄ and Fe₃O₄@Ni-Mg-Al-LDH

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图 6 Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y染料前(a)和吸附后(b)的FTIR图谱

Figure 6. FTIR spectra of Fe₃O₄@Ni-Mg-Al-LDH before (a) and after (b) adsorption of Eosin Y

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图 7 不同组成Fe₃O₄@Ni-Mg-Al-LDH对曙红Y的去除率

Figure 7. Removal efficiency of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH with different composition

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图 8 溶液pH值对曙红Y吸附效果的影响

Figure 8. Effect of solution pH value on the Eosin Y adsorption

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图 9 不同时间下Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y曲线

Figure 9. Adsorption curve of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH under different time

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图 10 不同初始浓度下Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y曲线

Figure 10. Adsorption curve of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH under different Eosin Y initial concentration

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图 11 Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y的Langmuir (a)、Freundlich (b)、Temkin (c) 吸附等温线模型和Langmuir的R_L参数变化曲线 (d)

Figure 11. Langmuir (a), Freundlich (b), Temkin (c) adsorption isotherm models and Langmuir parameter (R_L) curve (d) of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH

Q_e—Equilibrium adsorption capacity; c_e—Equilibrium concentration; R_L—Separation factor; c₀—Initial concentration; R₁², R₂², R₃²—Correlation coefficient of Langmuir, Freundlich and Temkin models

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图 12 Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y的伪一级动力学 (a)、伪二级动力学 (b) 和颗粒内扩散 (c) 模型

Figure 12. Pseudo-first-order (a), pseudo-second-order (b) and intra-particle diffusion kinetics model (c) for the adsorption of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH

R_3i², R_3j², R_3k²—Correlation coefficient of the first, second and third stage of intra-particle diffusion model

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图 13 Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y的循环实验

Figure 13. Cycle test for the adsorption of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH

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表 1 Fe₃O₄@Ni-Mg-Al-LDH对曙红Y的吸附等温线参数

Table 1. Adsorption isotherm parameters of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH

Isotherm models	Parameters	Fe₃O₄@Ni-Mg-Al-LDH
Langmuir	R₁²	0.9741
	Q_max/(mg·g⁻¹)	116.01
	K_L/(L·mg⁻¹)	0.0606
Freundlich	R₂²	0.8741
	K_F/(mg·g⁻¹)	21.28
	n	3.184
Temkin	R₃²	0.8909
	B/(J·mol⁻¹)	17.07
	K_T/(L·mg⁻¹)	2.291
Notes: R₁², R₂² and R₃²—Correlation coefficient of Langmuir, Freundlich and Temkin models; Q_max—Maximum adsorption capacity; K_L, K_F and K_T—Adsorption equilibrium constant of Langmuir, Freundlich and Temkin models; n—Constant related to adsorption strength; B—Constant related to heat of adsorption.

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表 2 Fe₃O₄@Ni-Mg-Al-LDH吸附曙红Y的动力学参数

Table 2. Kinetics parameters for the adsorption of Eosin Y on Fe₃O₄@Ni-Mg-Al-LDH

Kinetic models	Parameters	Fe₃O₄@Ni-Mg-Al-LDH
Pseudo-first-order dynamic model	R₁²	0.9428
	K₁/(min⁻¹)	0.0293
	Q₁/(mg·g⁻¹)	5.590
Pseudo-second-order dynamic model	R₂²	0.9987
	K₂/(g·mg⁻¹·min⁻¹)	0.0169
	Q₂/(mg·g⁻¹)	9.785
Intra-particle diffusion model	R_3i²	0.9741
	K_3i/(mg·g⁻¹·min^−0.5)	1.802
	b_i/(mg·g⁻¹)	−0.0321
	R_3j²	0.9978
	K_3j/(mg·g⁻¹·min^−0.5)	0.5015
	b_j/(mg·g⁻¹)	4.671
	R_3k²	0.7288
	K_3k/(mg·g⁻¹·min^−0.5)	0.0168
	b_k/(mg·g⁻¹)	9.266
Notes: R₁², R₂² —Correlation coefficient of pseudo-first-order and pseudo-second-order dynamic models; R_3i², R_3j² and R_3k²—Correlation coefficient of the first, second and third stage of intra-particle diffusion model; K₁, K₂—Rate constant of pseudo-first-order and pseudo-second-order dynamic models; K_3i, K_3j and K_3k—Rate constant of the first, second and third stage of intra-particle diffusion model; Q₁, Q₂—Adsorption capacity of pseudo-first-order and pseudo-second-order dynamic models; b_i, b_j and b_k—Constant related to the thickness of the boundary layer of the first, second and third stage of intra-particle diffusion model.

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表 3 Fe₃O₄@Ni-Mg-Al-LDH吸附剂使用后金属离子浸出量

Table 3. Metal ion leaching amount after the use of Fe₃O₄@Ni-Mg-Al-LDH adsorbent

Cycle number	Metal ion leaching amount/(mg·L⁻¹)
Cycle number	Fe	Ni	Mg	Al
1	0.21	0.11	0.06	0.07
2	0.17	0.09	0.04	0.03
3	0.12	0.05	0.02	0.02
4	0.09	0.02	0.01	0.02
5	0.07	0.01	−	−

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