ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究

doi:10.11949/0438-1157.20240042

摘要/Abstract

摘要：

通过水热法成功合成了一系列宽硅铝比（50、100、150、300、500、800、1500、3000）的ZSM-5分子筛，旨在研究其对涂装行业典型挥发性有机物（volatile organic compounds， VOCs）的吸附规律。同时，结合分子筛表面的酸性位点，以解析硅铝比对分子筛吸附性能的影响机制。实验结果表明，丙酮的吸附能力主要受自身极性、支链结构和分子筛表面酸位点的影响。而乙酸丁酯、苯乙烯、对二甲苯、苯、甲苯的吸附性能会同时受到自身的分子量、分子直径、极性、分子结构和官能团的影响，分子量和分子直径大、极性强且具有支链结构的VOCs更容易被ZSM-5分子筛吸附。这6种VOCs中，ZSM-5分子筛对丙酮的吸附效果最好，硅铝比对其吸附性能的影响也最大，这是因为丙酮比其他VOCs更容易吸附在路易斯酸位点上，硅铝比的改变会影响酸位点的数量。低硅铝比的分子筛由于具有较多的酸位点，更适用于丙酮的吸附。

关键词: ZSM-5分子筛, 吸附剂, 硅铝比, 吸附, 涂装挥发性有机物, 路易斯酸位点

Abstract:

A series of ZSM-5 molecular sieves with wide silica-to-aluminium ratios (50, 100, 150, 300, 500, 800, 1500, 3000) were successfully synthesized by hydrothermal method with the aim of investigating their adsorption patterns of volatile organic compounds (VOCs) typical of the coating industry. Meanwhile, the acidic sites on the surface of the molecular sieves were combined in order to resolve the mechanism of the influence of the silica-aluminium ratio on the adsorption performance of the molecular sieves. The experimental results showed that the adsorption capacity of acetone was mainly affected by its own polarity, branched structure and acid sites on the surface of molecular sieves. The adsorption performance of butyl acetate, styrene, p-xylene, benzene and toluene would be affected by their own molecular weight, molecular diameter, polarity, molecular structure and functional groups at the same time, and VOCs with large molecular weights and molecular diameters, high polarity and branched structures were more likely to be adsorbed by ZSM-5 molecular sieves. Among these six VOCs, ZSM-5 molecular sieve showed the best adsorption effect on acetone, the silica-aluminium ratio had the greatest effect on its adsorption performance, because acetone is more easily adsorbed on Lewis acid sites than the others, the change of silica-aluminium ratio will affect the number of acid sites. The molecular sieves with low silica-aluminium ratio are suitable for acetone adsorption due to their higher number of acid sites.

Key words: ZSM-5 molecular sieves, adsorbents, silicon-aluminum ratio, adsorption, volatile organic compounds in coatings, Lewis acid sites

中图分类号:

TQ 630.9

冀钟, 赵彦玲, 陈雨濛, 高林霞, 王翼鹏, 刘欢. ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240042.

Zhong JI, Yanling ZHAO, Yumeng CHEN, Linxia GAO, Yipeng WANG, Huan LIU. Adsorption performance and mechanism of ZSM-5 molecular sieves on typical coating VOCs[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240042.

图/表 13

图1 华中地区某著名汽车涂装厂VOCs检测结果

Fig.1 VOCs test results of a famous automobile coating plant in central China

图2 不同硅铝比ZSM-5分子筛的合成

Fig.2 Synthesis of ZSM-5 molecular sieves with different silicon-aluminum ratios

图3 吸附性能测试装置图

Fig.3 Diagram of adsorption performance test device

图 4 不同硅铝比分子筛的XRD图谱

Fig. 4 XRD patterns of molecular sieves with different silicon-aluminum ratios

图 5 不同硅铝比分子筛的氮气脱附曲线（a）和孔径分布图（b）

Fig. 5 Nitrogen desorption curves (a) and pore size distribution (b) of molecular sieves with different silicon-aluminum ratios

表1 合成不同硅铝比分子筛的基本参数

Table 1 Basic parameters for the synthesis of molecular sieves with different Si/Al ratios

样品	理论Si/Al	实际Si/Al	总比表面积(m²/g)^①	微孔表面积(m²/g)^②	外比表面积(m²/g)	总孔容(m³/g)^③	平均孔径(nm)^④
1	50	48.49	420.59	360.74	59.85	0.36	3.47
2	100	91.84	471.92	396.42	75.50	0.54	4.54
3	150	129.88	468.11	407.82	60.29	0.62	5.32
4	300	245.05	402.45	335.09	67.36	0.24	2.43
5	500	350.98	416.94	369.04	47.90	0.26	2.46
6	800	547.63	438.67	391.86	46.81	0.24	2.42
7	1500	730.17	465.56	373.01	92.43	0.38	3.23
8	3000	933.74	437.19	372.81	64.37	0.33	3.01

图6 不同分子量VOCs在ZSM-5分子筛上吸附的饱和吸附量（a）和穿透时间(b)

Fig.6 Saturation adsorption (a) and penetration time (b) of different molecular weight VOCs adsorbed on ZSM-5 molecular sieves

图7 不同分子直径VOCs在ZSM-5分子筛上吸附的饱和吸附量（a）和穿透时间(b)

Fig. 7 Saturation adsorption (a) and penetration time (b) of VOCs with different molecular diameters adsorbed on ZSM-5 molecular sieves

图8 不同结构VOCs在ZSM-5分子筛上吸附的饱和吸附量（a）和穿透时间(b)

Fig.8 Saturation adsorption (a) and penetration time (b) of VOCs with different structures adsorbed on ZSM-5 molecular sieves

图 9 不同偶极矩VOCs在ZSM-5分子筛上吸附的饱和吸附量（a）和穿透时间（b）

Fig. 9 Saturation adsorption (a) and penetration time (b) of VOCs with different dipole moments adsorbed on ZSM-5 molecular sieves

图10 不同硅铝比ZSM-5分子筛吸附丙酮和乙酸丁酯的饱和吸附量（a）和穿透时间（b）

Fig. 10 Saturation adsorption (a) and penetration time (b) of acetone and butyl acetate adsorbed on ZSM-5 molecular sieves with different silica-to-aluminum ratios

图11 硅铝比100、500分子筛原样NH3-TPD测试图

Fig. 11 Silica-aluminum ratio of 100, 500 molecular sieves samples NH3-TPD test charts

图12 硅铝比100、500分子筛对丙酮、乙酸丁酯吸附前后NH3-TPD测试图（a~d）和质谱测试图（e~h）注:(Ⅰ、Ⅱ、Ⅲ 分别为分子筛吸附VOCs前后弱、中、强酸变化量)

Fig. 12 NH3-TPD test graphs (a~d) and mass spectrometry test graphs (e~h) before and after adsorption of acetone and butyl acetate on silica-aluminium ratios of 100 and 500 molecular sieves

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