Comparison and Analysis of Toluene Adsorption Properties of ZSM-5 Molecular Sieve Treated by Different Modification Methods: Adsorption Kinetic and Mechanism Studies

MFI molecular sieve with high specific surface area,adjustable pore size and low production cost have been recognized as an effective adsorbent for VOCs removal.In this paper,NaOH solution was used to etch ZSM-5 to increase specific surface area and micro-mesoporous content.Graphene oxide(GO)was loaded on ZSM-5 by ultrasonic-assisted heating immersion method,and largeπ-bond structure and oxygen-containing functional groups were added to ZSM-5 for improving the composite adsorption performance.In addition,the properties of OH-ZSM-5 and ZSM-5@GO composites for toluene adsorption under different factors were also studied.It was positively correlated with initial concentration and adsorbent mass,but was negatively correlated with temperature.Meanwhile,the results showed that the saturated adsorption capacity of OH-ZSM-5(107.3 mg/g)was 1.34 times higher than that of ZG-15%(80.2 mg/g).The pseudo-first-order and pseudo-second-order kinetic model can well describe the adsorption behavior of toluene on the OH-ZSM-5 and ZG-15%,respectively.The adsorption mechanism of OH-ZSM-5 was mainly pore-filled adsorption.However,the adsorption mechanisms of ZSM-5@GO composite were pore-filled adsorption,π-πinteraction,and H-bond interaction.This study will help to design a new strategy for enhancing the performance of traditional adsorbent ZSM-5 in VOCs removal.

Facile fabrication of nanoscale hierarchical porous zeolitic imidazolate frameworks for enhanced toluene adsorption capacity

The development of a simple and facile synthesis route is a highly desirable but challenging process in the fabrication of nanoscale hierarchical porous zeolitic imidazolate frameworks(ZIFs).Herein we describe a facile method for rapidly synthesizing hierarchically porous ZIF-90 nanocrystals(particle sizes of~300 nm)using hydroxyl double salts as intermediates at room temperature.The as-synthesized ZIF-90 contained hierarchical porous structures developed using a crystalline interior and a random stack of multiple nanoparticles.Both the morphology and particle size of ZIF-90 nanocrystals could be tuned by controlling the molar ratio of ICA/Zn^(2+).Note that the as-synthesized hierarchically porous ZIF-90 nanocrystals exhibited higher thermal stability compared with the conventional ZIF-90.Because of the introduction of hierarchical porous structures,the resultant hierarchically porous ZIF-90 nanocrystals showed enhanced toluene adsorption capacity than those of conventional metal organic frameworks and zeolites.

Preparation of Solid Waste-Based Activated Carbon and Its Adsorption Mechanism for Toluene

Regenerated activated carbon(RAC)samples were prepared by carbon activation using waste activated carbon from solid waste resources as the carbon source precursor coupled with adding alkaline additives,and then were further modified by potassium ferrate to finally prepare high-performance carbon for VOCs adsorption.At the same time,the samples before and after modification were systematically studied through characterization techniques such as SEM,Raman spectrometry,FT-IR,XPS,and dynamic/static adsorption.The results showed that the specific surface area and pore volume of the RAC after modification by the strong oxidant potassium ferrate increased by 1.4 times;the degree of defects was enhanced and the content of oxygen-containing functional groups on the surface increased significantly.Among them,the sample modified with potassium ferrate for 24 h had the best dynamic toluene adsorption performance(375.5 mg/g),and the dynamic adsorption capacity was twice that of the original sample(192.8 mg/g).The static adsorption test found that the maximum adsorption capacity of RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h was 796 mg/g,which indicated that the potassium ferrate modification treatment could significantly increase the VOCs adsorption performance of RAC.In addition,through consecutive toluene adsorption-desorption cycle tests,it was found that the RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h sample still retained 91%of adsorption activity after the fifth regeneration cycle.This indicates that RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h has good cycle stability and great application value for the efficient purification of industrial waste VOCs gas.

Heteroatomic Modification of Solid-Waste-Based Mesoporous Carbon for Volatile Organic Compound Adsorption

Solid-waste-based activated carbon(AC)was utilized as a carbon source to synthesize a series of carbon-based functional material RAC-X(X=P and S,where P and S denote phosphoric and sulfuric acids,respectively).The toluene adsorption capacities of the regeneration AC(RAC)samples can be significantly improved by adopting the heteroatomic modification strategy.RAC-P and RAC-S have the same specific surface area(1156 m^(2)/g)and similar porous structures.However,they have different toluene adsorption capacities,with 316.22 mg/g for RAC-P and 460.12 mg/g for RAC-S,which are 1.6 and 2.4 times greater than that for RAC.The X-ray photoelectron spectroscopy measurements showed that the increase in the amount ofπ–π^(2)chemical bond over the AC surface results in the improvement of the toluene adsorption performance.The density functional theory results showed that the S-containing functional groups loaded near the defect sites of RAC-S promote toluene adsorption.Moreover,reusability tests showed that RAC-S still retains 86%of its adsorption activity after four consecutive adsorption–desorption experiments.This indicates that the heteroatomic modification method affords excellent toluene adsorption performance and recycling practicability,which not only is beneficial for achieving the rational utilization of solid waste resources but also provides a practical method for the efficient elimination of volatile organic compounds.

Synthesis of porous carbon from orange peel waste for effective volatile organic compounds adsorption: role of typical components

Volatile organic compounds have posed a serious threat to the environment and human health,which require urgent and effective removal.In recent years,the preparation of porous carbon from biomass waste for volatile organic compounds adsorption has attracted increasing attention as a very cost-effective and promising technology.In this study,porous carbon was synthesized from orange peel by urea-assisted hydrothermal carbonization and KOH activation.The role of typical components(cellulose,hemicellulose,and lignin)in pore development and volatile organic compounds adsorption was investigated.Among the three components,hemicellulose was the major contributor to high porosity and abundant micropores in porous carbon.Higher hemicellulose content led to more abundant–COOR,amine-N,and pyrrolic/pyridonic-N in the derived hydrochar,which were favorable for porosity formation during activation.In this case,the toluene adsorption capacity of the porous carbon improved from 382.8 to 485.3 mg·g^(–1).Unlike hemicellulose,cellulose reduced the>C=O,amine-N,and pyrrolic/pyridonic-N content of the hydrochar,which caused porosity deterioration and worse toluene adsorption performance.Lignin bestowed the hydrochar with slightly increased–COOR,pyrrolic/pyridonic-N,and graphitic-N,and reduced>C=O,resulting in comparatively poor porosity and more abundant micropores.In general,the obtained porous carbon possessed abundant micropores and high specific surface area,with the highest up to 2882 m^(2)·g^(–1).This study can provide guidance for selecting suitable biomass waste to synthesize porous carbon with better porosity for efficient volatile organic compounds adsorption.

Comparison of dynamic adsorption/desorption characteristics of toluene on different porous materials

Four different types of adsorbents, SBA-15, MCM-41, NaY and SiO2, were used to study the dynamic adsorption/desorption of toluene. To further investigate the influence of pore structure on its adsorption performance, two SBA-15 samples with different microspores were also selected. It is shown that microporous material NaY has the largest adsorption capacity of 0.2873 mL/g, and the amorphous SiO2 exhibits the least capacity of 0.1003 mL/g. MCM-41 also shows a lower break through capacity in spite of the relatively small pore diameter, because it can not provide the necessary small geometric confinement for the tiny adsorbates. However, the mesoporous SBA-15 silica with certain micropore volume shows relatively higher adsorption capacity than that of MCM-41 silica. The presence of micropores directly leads to an increase in the dynamic adsorption capacity of toluene. Although NaY has the highest adsorption capacity for toluene, its complete desorption temperature for toluene is high （〉 350°C）, which limits its wide application. On the contrary, mesoporous silica materials exhibits a good desorption performance for volatile organic compounds at lower temperatures. Among these materials mesoporous SBA-15 samples, with a larger amount micropores and a lower desorption temperature, are a potentially interesting adsorbent for the removal of volatile organic compounds. This behavior should been related with the best synergetic effect of mesopores and micropores.

Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination

In this study,a hydrophobic synthetic zeolite,namely ZSM-5 is chosen as an adsorbent/catalyst for toluene removal.Experimental results showed that toluene adsorption onto ZSM-5 was favourable,following a Langmuir adsorption isotherm model.ZSM-5 zeolite was regenerated using gaseous ozone at low temperature.Adsorbed toluene was oxidised,releasing mainly CO_2 and H_2O.Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone.After four successive cycles of adsorption/ozonation,the adsorption efficiency was not affected（92%-99%）.These results showed that volatile organic compound（VOC）removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.