Adsorption performance and mechanism of ZSM-5 molecular sieves on typical coating VOCs

doi:10.11949/0438-1157.20240042

Abstract

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, aiming to study their effects on typical volatile organic compounds (volatile organic compounds, VOCs) in 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

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Lewis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, Lewis酸位点

CLC Number:

TQ 630.9

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, 2024, 75(6): 2332-2343.

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, 2024, 75(6): 2332-2343.

Figures/Tables 13

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

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

Fig.3 Diagram of adsorption performance test device

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

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

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

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

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

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

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

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

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

Fig.12 NH3-TPD test graphs and mass spectrometry test graphs before and after adsorption of acetone and butyl acetate on silica-aluminium ratios of 100 and 500 molecular sieves（Ⅰ,Ⅱ,Ⅲ indicate the change of weak, medium and strong acids before and after VOCs adsorption)

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