13X@SiO2合成及其甲苯吸附性能

doi:10.15541/jim20220449

无机材料学报 ›› 2023, Vol. 38 ›› Issue (5): 537-543.DOI: 10.15541/jim20220449

13X@SiO₂合成及其甲苯吸附性能

马晓森(), 张丽晨, 刘砚超, 汪全华, 郑家军(), 李瑞丰

太原理工大学化学化工学院, 省部共建煤基能源清洁高效利用国家重点实验室, 太原 030024

收稿日期:2022-08-01 修回日期:2022-11-02 出版日期:2022-11-16 网络出版日期:2022-11-16
通讯作者: 郑家军, 教授. E-mail: zhengjiajun@tyut.edu.cn
作者简介:马晓森(1998-), 男, 硕士研究生. E-mail: 294945674@qq.com
基金资助:
国家自然科学基金(U19B2003);中国石油化工股份有限公司(121014-2)

13X@SiO₂: Synthesis and Toluene Adsorption

MA Xiaosen(), ZHANG Lichen, LIU Yanchao, WANG Quanhua, ZHENG Jiajun(), LI Ruifeng

State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Received:2022-08-01 Revised:2022-11-02 Published:2022-11-16 Online:2022-11-16
Contact: ZHENG Jiajun, professor. E-mail: zhengjiajun@tyut.edu.cn
About author:MA Xiaosen (1998-), male, Master candidate. E-mail: 294945674@qq.com
Supported by:
National Natural Science Foundation of China(U19B2003);China Petroleum & Chemical Corporation(121014-2)

摘要/Abstract

摘要：

常见的吸附剂如13X等的硅铝比较低, 具有较强的亲水性, 但水和有机挥发份(VOCs)之间的竞争吸附, 常常会影响吸附剂对VOCs实际脱除效果。本研究利用CTABr为模板剂, 正硅酸乙酯为硅源, 对13X进行表面修饰, 制备了以13X为核, 介孔硅为壳的核壳复合材料13X@SiO₂, 并以甲苯作为探针分子在穿透实验装置对改性前后沸石分别进行干/湿条件下的吸附性能测试。结果表明: 在干燥条件下, 13X@SiO₂-2.6样品(制备中添加了2.6 mL正硅酸乙酯)相比13X原样的吸附量提升了18%左右。在30%和50%相对湿度下, 13X@SiO₂的最优吸附容量分别提高了约53%和90%; 循环再生实验表明13X@SiO₂-2.6样品经2次再生后仍保持初始样品90%的甲苯吸附量。

关键词: 核壳结构, 复合材料, 疏水改性, 有机物挥发性, 吸附

Abstract:

In practice, adsorbents such as 13X have strong hydrophilicity due to their low Si/Al ratio, whose competitive adsorption between vapour and volatile organic compounds (VOCs) often impairs the actual removal effect of VOCs on the adsorbents. Here, 13X was modified using CTABr as a templating agent and tetraethoxysilane (TEOS) as a silica source.Based on this modified 13X, a core-shell composites with 13X core and a mesoporous silica shell, named as 13X@SiO₂, was therefore synthesized. Its adsorption performance was tested by using toluene as a probe molecule under different humidity conditions on a penetration experimental device, compared with that of the pristine 13X. The results show that the adsorption capacity of sample 13X@SiO₂-2.6 (2.6 mL TEOS added in the preparation) was about 18% higher than that of 13X original sample under dry conditions. At 30% and 50% relative humidity, the optimum adsorption capacity of 13X@SiO₂ was increased by about 53% and 90%, respectively. In order to test the stability and reusability of the adsorbents, twice regeneration of sample 13X@SiO₂-2.6, treated for 2 h in situ desorption at 350 ℃, were performed, and the result showed that the regenerated sample 13X@SiO₂-2.6 still retained 90% of the original toluene adsorption capacity.

Key words: core-shell structure, composite material, hydrophobic modification, volatile organic compounds, adsorption

中图分类号:

TQ174

马晓森, 张丽晨, 刘砚超, 汪全华, 郑家军, 李瑞丰. 13X@SiO₂合成及其甲苯吸附性能[J]. 无机材料学报, 2023, 38(5): 537-543.

MA Xiaosen, ZHANG Lichen, LIU Yanchao, WANG Quanhua, ZHENG Jiajun, LI Ruifeng. 13X@SiO₂: Synthesis and Toluene Adsorption[J]. Journal of Inorganic Materials, 2023, 38(5): 537-543.

图/表 14

图S1 穿透实验装置

Fig. S1 Diagram of the penetration experimental apparatus

图1 样品(a)13X、(b, e)13X@SiO2-2.2、(c, f)13X@SiO2-2.6和(d, g)13X@SiO2-3.5的XRD图谱

Fig. 1 XRD patterns of the samples of (a) 13X, (b, e) 13X@SiO2-2.2,(c, f) 13X@SiO2-2.6, and (d, g) 13X@SiO2-3.5 (A) Large angle XRD patterns; (B) Small angle XRD patterns

图2 样品的SEM照片

Fig. 2 SEM images of the samples (A) 13X; (B, E, F) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

图S2 样品的扫描电镜照片及相应的EDS结果

Fig. S2 SEM images and the corresponding EDS results of samples (A) 13X; (B) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

图3 样品的TEM照片

Fig. 3 TEM images of the samples (A, B, E) 13X@SiO2-2.2; (C, D) 13X@SiO2-2.6

图S3 样品的(A)氮气吸附脱附等温曲线与(B)DFT模型孔径分布图

Fig. S3 (A) Nitrogen adsorption-desorption isothermal curves and (B) the corresponding pore size distributions decided by a DFT model of samples

表1 样品的比表面积及孔结构参数

Table 1 Textural properties of the samples

Sample	S_BET/(m²·g^-1)	S_ext/(m²·g^-1)	S_mic/(m²·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)
13X	314	14	299	0.11	0.02
13X@SiO₂-2.2	324	95	229	0.09	0.07
13X@SiO₂-2.6	337	130	207	0.08	0.09
13X@SiO₂-3.5	444	259	184	0.07	0.18

图S4 样品的红外光谱

Fig. S4 FT-IR spectra of the sample (a) 13X; (b) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

图S5 不同改性沸石的水接触角测量照片

Fig. S5 Images of water droplets on the surfaces of different samples

图4 干条件下不同吸附剂对甲苯的吸附实验

Fig. 4 Adsorption of toluene on the different adsorbents under dry condition (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough times; (D) Cumulative adsorption capacity of different adsorbents

图S6 SiO2在干条件下对甲苯的(A)吸附穿透曲线和(B)累积吸附量

Fig. S6 (A) Toluene adsorption breakthrough curves and (B) cumulative toluene adsorption capacity of SiO2 under dry condition

图5 不同吸附剂在相对湿度30%条件下对甲苯的吸附实验

Fig. 5 Adsorption of toluene on the different adsorbents under 30% relative humid conditions (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough time; (D) Cumulative adsorption capacities of different adsorbents of toluene

图6 不同吸附剂在相对湿度50%条件下对甲苯的吸附实验

Fig. 6 Adsorption of toluene on the different adsorbents under 50% relative humid conditions (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough time; (D) Cumulative adsorption capacity of different adsorbents of toluene

图S7 50% RH下, 13X和13X@SiO2-2.6的(A)三次吸附-脱附循环吸附穿透曲线与(B)饱和吸附量变化曲线

Fig. S7 (A) Adsorption of toluene on different adsorbents with triple adsorption-desorption cycle. Adsorption penetration curve and (B) saturated adsorption capacity under 50% relative humid conditions

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13X@SiO₂合成及其甲苯吸附性能

13X@SiO₂: Synthesis and Toluene Adsorption

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