Preparation of quaternary ammonium-modified silica and its adsorption of vanadium(V)

doi:10.19965/j.cnki.iwt.2023-1266

Abstract

Abstract:

Vanadium(Ⅴ) is an emerging contaminant reported in wastewater along with the increasing of alloy manufacturing, chemicals, new energy fields as a significant national strategy resource. In this study, a quaternary ammonium modified silica(SiO₂@DMOA) material was synthesized for the adsorption of vanadium(Ⅴ) in aqueous solution. The results of TGA, FT-IR, SEM, and EDS confirmed the successful synthesis of SiO₂@DMOA composite. Under the conditions of solution volume of 20 mL, vanadium(Ⅴ) concentration of 2 mmol/L, solution pH of 3.3, contact time of 15 minutes, and temperature of 298 K, the adsorption capacity for vanadium(Ⅴ) by SiO₂@DMOA was 38.97 mg/g. The pseudo-second-order reaction kinetics and Langmuir adsorption isotherm model indicated that the process of adsorbing vanadium(Ⅴ) by SiO₂@DMOA was a surface monolayer chemical adsorption process, and the intra-particle diffusion model and Boyd model demonstrated that liquid film diffusion was the main limiting rate of this adsorption process. Thermodynamic studies demonstrated the feasibility and spontaneity of vanadium(Ⅴ) adsorption by SiO₂@DMOA, with ΔH ⁰>0, ΔS ⁰>0 and ΔG ⁰<0. The influence of ionic strength (NaCl) on adsorption was found to be negligible at concentrations of less than 0.1 mol/L. Furthermore, within pH range of 3-5, the maximum separation factor(β _V/Cr) between vanadium(Ⅴ) and chromium(Ⅵ) was 135.42. The adsorption efficiency of SiO₂@DMOA did not show any significant attenuation after five cycles of adsorption-desorption experiments.

Key words: adsorption, quaternary ammonium salts, modified silica, vanadium(Ⅴ)

摘要：

钒（Ⅴ）是一种重要的战略金属资源，在合金制造、化工和新能源等领域被广泛应用，逐渐成为废水中的新兴污染物之一。合成了一种季铵盐改性二氧化硅（SiO₂@DMOA）材料用于吸附水溶液中的钒（Ⅴ）。热重分析、FT-IR、SEM以及EDS结果证明了SiO₂@DMOA复合材料的成功合成。在20 mL 2 mmol/L钒（Ⅴ）溶液中加入50 mg SiO₂@DMOA，调节溶液pH为3.3，在接触时间为15 min和温度为298 K条件下，SiO₂@DMOA对钒（Ⅴ）的吸附容量为38.97 mg/g。准二级反应动力学和Langmuir吸附等温模型结果表明SiO₂@DMOA吸附钒（Ⅴ）的过程为表面单层的化学吸附，颗粒内扩散模型和Boyd模型证明了液膜扩散是该吸附过程的主要限速步骤。热力学结果显示SiO₂@DMOA吸附钒（Ⅴ）的ΔH ⁰>0、ΔS ⁰>0、ΔG ⁰<0，表明吸附过程是可行的和自发的。在离子强度（NaCl）<0.1 mol/L时，共存离子对SiO₂@DMOA吸附钒（Ⅴ）效果的影响几乎可以忽略。此外，在pH为3~5时，钒（Ⅴ）与铬（Ⅵ）两者的最大分离系数（β _V/Cr）为135.42。经过5个循环的吸附-解吸实验，SiO₂@DMOA的吸附效能无明显衰减。

关键词: 吸附, 季铵盐, 改性二氧化硅, 钒（Ⅴ）

CLC Number:

TQ424

Cuihong ZHANG, Jing WANG, Jie WANG, Wenjiao YUAN. Preparation of quaternary ammonium-modified silica and its adsorption of vanadium(V)[J]. Industrial Water Treatment, 2025, 45(1): 104-114.

张翠红, 王靖, 王洁, 袁文蛟. 季铵盐改性二氧化硅的制备及其吸附钒（Ⅴ）的性能[J]. 工业水处理, 2025, 45(1): 104-114.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-1266

https://www.iwt.cn/EN/Y2025/V45/I1/104

Figures/Tables 21

Fig.1 Synthesis route of SiO₂@DMOA

Fig.2 Thermogravimetric variation of SiO₂@HCl and SiO₂@DMOA

Fig.3 FT-IR spectra of SiO₂@HCl，SiO₂@DMOA and SiO₂@DMOA-loaded vanadium（V）

Fig.4 SEM images of the prepared materials

Table 1 The atomic fractions of the main elements in different materials

SiO₂种类	元素原子数分数/%
SiO₂种类	Si	O	C	N	Cl	V
SiO₂@HCl	48.25	51.75	—	—	—	—
SiO₂@CPTES	21.89	40.82	35.12	—	2.16	—
SiO₂@DMOA	20.41	39.94	33.16	4.96	1.52	—
SiO₂@DMOA（V）	21.02	43.30	34.23	—	—	1.45

Fig.5 Time-of-flight mass spectra of vanadium（Ⅴ） in solution pH=3

Fig.6 Effect of solution pH on adsorption of vanadium（Ⅴ） by SiO₂@DMOA（a） and pH_pzc of SiO₂@DMOA（b）

Fig.7 Effect of SiO₂@DMOA dosage on adsorption of vanadium（Ⅴ）

Fig.8 Effect of contact time on adsorption of vanadium（Ⅴ） by SiO₂@DMOA

Fig.9 Quasi-first- and second-order reaction kinetics equations and Elovich model fitting curves for vanadium（Ⅴ） adsorption by SiO₂@DMOA

Table 2 Kinetic models parameters for vanadium（Ⅴ） adsorption by SiO₂@DMOA

模型	准一级反应动力学				准二级反应动力学模型				Elovich模型
模型	q _e	k ₁	R ²	RMSE	q _e	k ₂	R ²	RMSE	α	β	R ²	RMSE
拟合参数数值	37.63	0.847	0.709	2.701	40.33	0.036 9	0.938	1.259	2 599.13	0.236 8	0.887	1.686

Fig.10 Fitting curves of intra-particle diffusion model（a） and Boyd model（b）

Table 3 Parameters of intra-particle diffusion model for vanadium（V） adsorption by SiO₂@DMOA

动力学模型	颗粒内扩散模型
动力学模型	K ₁/（mg·g^-1·min^-1）	K ₂/（mg·g^-1·min^-1）	C ₁/（mg·g^-1）	C ₂/（mg·g^-1）
数值	0.943	0.490	19.91	38.08

Fig.11 Fitting curves of Freundlich and Langmuir models for vanadium（Ⅴ） adsorption by SiO₂@DMOA

Table 4 Fitting parameters of Langmuir and Freundlich models for vanadium（Ⅴ） adsorption by SiO₂@DMOA

等温吸附模型	Langmuir模型				Freundlich模型
等温吸附模型	q _m	K _L	R ²	RMSE	K _F	1/n	R ²	RMSE
参数数值	71.30	0.092 7	0.982	2.313	20.470	0.238	0.764	8.278

Fig.12 Langmuir model related dimensionless separation factor R _L

Fig.13 Adsorption capacity at temperatures corresponding to 288-318 K（a） and fitting curve of lnK _c to 1/T（b）

Table 4 Thermodynamic parameters of vanadium（Ⅴ） adsorption by SiO₂@DMOA

温度/K	热力学参数
温度/K	lnK _c	ΔG ⁰/（kJ·mol^-1）	ΔH ⁰/（kJ·mol^-1）	ΔS ⁰/（J·mol^-1·K^-1）
288	3.184	-7.624	27.08	120.47
298	3.597	-8.914
303	3.749	-9.446
308	3.799	-9.728
318	4.305	-11.381

Fig.14 Effect of ionic strength（NaCl） on vanadium（Ⅴ） adsorption by SiO₂@DMOA

Fig.15 Effect of solution pH on adsorption of vanadium（Ⅴ） and chromium（Ⅵ） by SiO₂@DMOA

Fig.16 Effect of different desorbents on the desorption of SiO₂@DMOA loaded with vanadium（Ⅴ） and regeneration of SiO₂@DMOA on the adsorption capacity of vanadium（Ⅴ）

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