多级孔硅铝酸盐纳米球的合成及其吸附分离多环芳烃

doi:10.16085/j.issn.1000-6613.2023-0176

摘要/Abstract

摘要：

以阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）和阴离子聚电解质聚丙烯酸（PAA）形成的介观复合物为动态模板，以异丙醇铝为铝源，原位合成了不同硅铝比的多级孔硅铝酸盐纳米球（NKM-5-Al-x）。采用X射线衍射仪（XRD）、氮气吸附脱附、程序升温（NH₃-TPD）、核磁（²⁷Al NMR）、扫描电镜（SEM）、透射电镜（TEM）等表征方法对多级孔硅铝酸盐纳米球进行了表征分析，并对比孔径结构相对均一的SBA-15和MCM-41氧化硅材料，考察材料的多级孔结构和酸性质对多环芳烃吸附分离性能的影响。结果表明，孔分布和酸性质对多环芳烃分离性能影响显著，多级孔结构有利于多环芳烃的扩散，酸性增强有利于提高多环芳烃分离效率，具有较强酸量和多级孔结构的NKM-5-Al-5呈现出最优的多环芳烃分离效果，分离度R_{多环芳烃/非芳烃}>1.2，且脱吸附速率较快，脱/吸附速率比接近1。

关键词: 多级孔纳米球, 孔分布, 酸性质, 多环芳烃, 吸附分离

Abstract:

Hierarchically porous aluminosilicate nanospheres (NKM-5-Al-x) with different Si/Al ratios were synthesized by employing organic mesomorphous complexes of cationic surfactant cetyltrimethylammonium bromide (CTAB) and anionic polyelectrolyte polyacrylic acid (PAA) as the dynamic template and aluminum isopropoxide as the aluminum source. The hierarchically porous aluminosilicate nanospheres were characterized by X-ray diffraction (XRD), nitrogen adsorption desorption, temperature programmed (NH₃-TPD), nuclear magnetic resonance (²⁷Al NMR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The SBA-15 and MCM-41 silica materials with relatively uniform pore structure were compared. The effects of the hierarchically porous structure and acid properties of the materials on the adsorption and separation performance of polycyclic aromatic hydrocarbons (PAHs) were investigated. The results showed that the pore distribution and acid properties had a significant impact on the separation performance of PAHs. The hierarchically porous structure was profit for the diffusion of PAHs. The increase of acid content was beneficial to improve the separation efficiency of PAHs. NKM-5-Al-5 with strong acid content and hierarchically porous structure indicated the best PAHs separation effect. The separation degree of R_{PAHs/non-aromatics} was above 1.2 and the desorption/adsorption rate was fast with the desorption/adsorption rate ratio close to 1.

Key words: hierarchically porous nanospheres, pore distribution, acidic properties, polycyclic aromatic hydrocarbons, adsorption separation

中图分类号:

TQ21

武鲁明, 于海斌, 臧甲忠, 王亚权, 李滨, 孙振海. 多级孔硅铝酸盐纳米球的合成及其吸附分离多环芳烃[J]. 化工进展, 2023, 42(12): 6452-6460.

WU Luming, YU Haibin, ZANG Jiazhong, WANG Yaquan, LI Bin, SUN Zhenhai. Synthesis of hierarchically porous aluminosilicate nanospheres and their adsorption and separation of polycyclic aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6452-6460.

图/表 17

参考文献 19

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吸附剂	SiO₂质量分数/%	Al₂O₃质量分数/%
NKM-5	99.8	—
NKM-5-Al-1	99.1	0.9
NKM-5-Al-2	97.9	1.9
NKM-5-Al-3	95.6	4.2
NKM-5-Al-4	92.0	7.9
NKM-5-Al-5	85.3	14.7

吸附剂	SiO₂质量分数/%	Al₂O₃质量分数/%
NKM-5	99.8	—
NKM-5-Al-1	99.1	0.9
NKM-5-Al-2	97.9	1.9
NKM-5-Al-3	95.6	4.2
NKM-5-Al-4	92.0	7.9
NKM-5-Al-5	85.3	14.7

样品名称	比表面积 /m²·g^-1	一次孔孔径 /nm	二次孔孔径 /nm	孔体积 /cm³·g^-1
NKM-5	336	2.7	20~90	0.85
NMK-5-Al-1	586	2.8	20~90	1.02
NMK-5-Al-2	615	2.7	20~90	1.06
NMK-5-Al-3	578	2.7	20~90	1.02
NMK-5-Al-4	562	2.6	20~90	0.96
NMK-5-Al-5	597	2.6	20~90	1.00
MCM-41	1375	2.6	—	0.79
SBA-15	774	6.6	—	0.97

样品名称	比表面积 /m²·g^-1	一次孔孔径 /nm	二次孔孔径 /nm	孔体积 /cm³·g^-1
NKM-5	336	2.7	20~90	0.85
NMK-5-Al-1	586	2.8	20~90	1.02
NMK-5-Al-2	615	2.7	20~90	1.06
NMK-5-Al-3	578	2.7	20~90	1.02
NMK-5-Al-4	562	2.6	20~90	0.96
NMK-5-Al-5	597	2.6	20~90	1.00
MCM-41	1375	2.6	—	0.79
SBA-15	774	6.6	—	0.97

编号	总酸酸量 /mmol·g^-1	弱酸酸量 /mmol·g^-1	中强酸酸量 /mmol·g^-1
NKM-1	0.23	0.23	0.00
NKM-Al-1	0.39	0.27	0.12
NKM-Al-2	0.47	0.31	0.16
NKM-Al-3	0.51	0.33	0.18
NKM-Al-4	0.54	0.34	0.19
NKM-Al-5	0.56	0.32	0.24