Properties and mechanism of V(Ⅴ) removal by mussel shells loaded with nano zero-valent iron

doi:10.19965/j.cnki.iwt.2023-0919

Abstract

Abstract:

Aiming at the environmental pollution problems caused by vanadium-containing wastewater produced by mining, metallurgy, petroleum refining, and other industries, this study prepared mussel shells loaded nano-zero-valent iron composites(nZVI@CMS) by liquid-phase reduction method using pyrolyzed mussel shell powder(CMS) as the carrier. The morphology and structure of nZVI@CMS were characterized by SEM, TEM, XRD, BET, FT-IR and XPS. The adsorption performance of V(Ⅴ) on nZVI@CMS was investigated by batch adsorption experiments, and the adsorption mechanism of V(Ⅴ) on nZVI@CMS was analyzed using adsorption kinetics, adsorption isotherm, and adsorption thermodynamics. The results showed that nZVI@CMS was a loose and porous chain sphere-like structure containing a variety of oxygen-containing functional groups. The maximum adsorption of V(Ⅴ) by nZVI@CMS was 149.33 mg/g under the conditions of nZVI@CMS dosage of 0.05 g/L, initial pH=7, V(Ⅴ) concentration of 20 mg/L, solution volume of 100 mL, and temperature of 25 ℃. The adsorption of V(Ⅴ) by nZVI@CMS could be fitted by Langmuir adsorption isotherm equation and pseudo second-order reaction kinetic equation, and it was a spontaneous heat adsorption process. The main mechanisms of V(Ⅴ) removal by nZVI@CMS included adsorption, reduction, and co-precipitation. This study turned the mussel shells into treasure, and provided a new idea for the efficient treatment of V(Ⅴ) in wastewater.

Key words: mussel shell, liquid-phase synthesis, nano zero-valent iron, vanadium, reduction

摘要：

针对采矿、冶金、石油炼制等行业产生的含钒废水导致的环境污染难题，以热解后的贻贝壳粉（CMS）为载体，通过液相还原法制备了贻贝壳负载纳米零价铁复合材料（nZVI@CMS），采用SEM、TEM、XRD、BET、FT-IR和XPS等对其进行了表征，通过批量吸附实验考察了nZVI@CMS对V（Ⅴ）的吸附性能，利用吸附动力学、吸附等温线和吸附热力学分析了nZVI@CMS对V（Ⅴ）的吸附机制。结果表明：nZVI@CMS具有疏松多孔的链球状结构，含有多种含氧官能团；在nZVI@CMS投加量0.05 g/L、初始pH=7、V（Ⅴ）初始质量浓度20 mg/L、溶液体积100 mL、温度25 ℃的条件下，nZVI@CMS在600 min内对V（Ⅴ）的最大吸附量为149.33 mg/g。nZVI@CMS对V（Ⅴ）的吸附过程可通过Langmuir吸附等温模型与准二级反应动力学方程拟合，且该过程是自发的吸热过程。nZVI@CMS对V（Ⅴ）的去除机制主要包括吸附、还原和共沉淀作用。本研究将贻贝壳变废为宝，同时为废水中V（Ⅴ）的高效治理提供了新思路。

关键词: 贻贝壳, 液相合成, 纳米零价铁, 钒, 还原

CLC Number:

X703
TQ424

Ran LI, Lili JI, Qianrui HE, Xiaoyue XIA, Yaning WANG. Properties and mechanism of V(Ⅴ) removal by mussel shells loaded with nano zero-valent iron[J]. Industrial Water Treatment, 2024, 44(9): 127-135.

李然, 纪丽丽, 何前锐, 夏晓月, 王亚宁. 贻贝壳负载纳米零价铁去除钒（Ⅴ）的性能与机制[J]. 工业水处理, 2024, 44(9): 127-135.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0919

https://www.iwt.cn/EN/Y2024/V44/I9/127

Figures/Tables 17

Fig.1 Preparation route of nZVI@CMS

Fig.2 SEM（a-b），TEM（c） and HRTEM（d） of CMS and nZVI@CMS

Fig.3 XRD of CMS and nZVI@CMS

Fig.4 N₂ adsorption-desorption isotherms（a） and pore size distributions（b） of CMS and nZVI@CMS

Table 1 Pore structure parameters of CMS and nZVI@CMS

材料	比表面积/（m²∙g^-1）	孔径/nm	孔容/（cm³∙g^-1）
CMS	1.820 6	17.398 5	0.000 561
nZVI@CMS	4.776 3	29.696 3	0.001 424

Fig.5 FT-IR spectra of CMS and nZVI@CMS

Fig.6 The adsorption capacity of V（Ⅴ） by CMS and nZVI@CMS

Fig.7 Effects of nZVI@CMS dosage on removal of V（Ⅴ） by nZVI@CMS

Fig.8 Effects of initial pH on removal of V（Ⅴ） by nZVI@CMS

Fig.9 Effects of initial V（Ⅴ） concentration on removal of V（Ⅴ） by nZVI@CMS

Fig.10 Kinetic model fitting curves for adsorption of V（Ⅴ） on nZVI@CMS

Table 2 Kinetic parameters for adsorption of V（Ⅴ） on nZVI@CMS

动力学模型	动力学参数
准一级反应动力学	Q _e1/（mg∙g^-1）	k ₁/min^-1	R ²
准一级反应动力学	97.805	0.115	0.939
准二级反应动力学	Q _e2/（mg∙g^-1）	k ₂/（g·mg^-1·min^-1）	R ²
准二级反应动力学	113.506	0.000 17	0.978
颗粒内扩散模型	k _d1/（mg∙g^-1∙min^-0.5）	C ₁/（mg∙g^-1）	R²
	9.068	-9.789	0.984
	k _d2/（mg∙g^-1∙min^-0.5）	C ₂/（mg∙g^-1）	R²
	1.517	65.805	0.891
	k _d3/（mg∙g^-1∙min^-0.5）	C ₃/（mg∙g^-1）	R²
	0.232	96.636	0.586

Table 3 Fitting parameters of the isotherm adsorption models

Langmuir模型			Freundlich模型
Q _m/（mg∙g^-1）	K _L	R²	n	K _F	R²
133.51	0.151	0.923	0.325	27.3	0.879

Table 4 Thermodynamic fitting parameters for adsorption of V（Ⅴ） on nZVI@CMS

T/K	ΔG/（kJ∙mol^-1）	ΔH/（kJ∙mol^-1）	ΔS/（J∙mol^-1∙K^-1）
298	-14.11	2.481	0.055 69
308	-14.67
318	-15.23

Fig.11 SEM（a） and XRD（b） of nZVI@CMS after treatment of V（Ⅴ）

Fig.12 XPS spectras of nZVI@CMS before and after the reaction

Fig.13 Schematic diagram of V（Ⅴ） removal mechanisms by nZVI@CMS

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