Abstract: 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 weredistributed ideally at optimal sites during the stage that occurredbefore the inflection point, which is called the "optimal-displacement adsorption" stage. When approachingthe 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.

Key words: Competitive adsorption mechanism, Cyclohexene, Thiophene, FAU zeolite, Molecular simulation, Selectivity

摘要： 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 weredistributed ideally at optimal sites during the stage that occurredbefore the inflection point, which is called the "optimal-displacement adsorption" stage. When approachingthe 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.

关键词: Competitive adsorption mechanism, Cyclohexene, Thiophene, FAU zeolite, Molecular simulation, Selectivity