Mechanism transformation of cyclohexene-thiophene competitive adsorption in FAU zeolite

Competition of hydrocarbon compounds with sulfides in gasoline has caused a not very high selectivity of sulfides in adsorption desulfurization so far,resulting in a reduction of catalyst lifetime as well as more sulfur oxide emissions.Tostudy the whole competitive process changing with the increase of the loading,the dynamic competition adsorption mechanism of cyclohexene and thiophene in siliceous faujasite(FAU)zeolite was analyzed by the Monte Carlo simulation.The results showed that with the increase of the loading,thiophene and cyclohexene had different performances before and after the inflection point of 40 molecule/UC.The adsorbates were distributed ideally at optimal sites during the stage that occurred before the inflection point,which is called the“optimal-displacement adsorption”stage.When approaching the inflection point,the competition became apparent and the displacement appeared accordingly,some thiophene molecules at S sites(refers to the sites inside the supercages)were displaced by cyclohexene.After the inflection point,the concentration of adsorbates at W sites(refers to the 12-membered ring connecting the supercages)was significantly reduced,whereas the adsorbates at S sites got more concentrated.The stage some cyclohexene molecules displaced by thiophene and inserted into the center of the supercage can be named as the“insertion-displacement adsorption”stage,and both the adsorption behavior and the competitive relationship became localized when the adsorption amount became saturated.This shift in the competitive adsorption mechanism was due to the sharp increase of interaction energy between the adsorbates.Besides,the increase in temperature and ratio of Si/Al will allow the adsorbates,especially thiophene molecules to occupy more adsorption sites,and it is beneficial to improve the desulfurization selectivity.

Preparation of Fe3O4-octadecyltrichlorosilane for Removal of Methyl Orange and Methylene Blue:Influence of p H and Ionic Strength on Competitive Adsorption

Fe3O4-octadecyltrichlorosilane（Fe3O4-OTS）was synthesized and used to remove dyes in a competitive system.Fe3O4-OTS was prepared by slow hydrolysis of OTS in cyclohexane on the surface of Fe3O4obtained through coprecipitation method.Scanning electron microscope（SEM）,energy dispersive spectrometer（EDS）,and contact angle analyzer（CA）were used to analyze the properties of Fe3O4-OTS.Methyl orange（MO）and methylene blue（MB）were selected as model molecules to study the influence mechanism of p H and ionic strength on competitive adsorption.The results of EDS and CA indicated that Fe3O4 was modified successfully with OTS on the surface.Silicon appeared and carbon content increased obviously on the surface of adsorbent.Contact angle of adsorbent increased from 0~o to 107~o after being modified by OTS.Fe3O4-OTS showed good separation for MO and MB in competitive system,which has potential to separate dyes in sewage.Separation factor（β~OB）changed from 18.724 to 0.017,when p H changed from 7 to 12,revealing that MO and MB could be separated almost thoroughly by Fe3O4-OTS.p H could change the surface charge of Fe3O4-OTS and structure of dyes,and thus change the interactions of competitive system indirectly.Even though hydrophobic interaction was enhanced,ionic strength reduced the difference of electrostatic interaction between dyes and Fe3O4-OTS.So it is unfavorable to separate dyes with opposite charges when ionic strength increases.These findings may provide theoretical guidances to separate two-component dye pollutants.