金属有机骨架材料Fe/Cu-BTC的制备及其脱硫性能

Preparation and Desulfurization Performance of Metal-OrganicFramework Material Fe/Cu-BTC

采用FeCl_(2)对金属有机骨架材料Cu-BTC改性制备了Fe/Cu-BTC,并通过X射线粉末衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、电感耦合等离子体原子发射光谱(ICP)、氮气物理吸附及X射线光电子能谱(XPS)对样品进行了表征。考察了Fe/Cu-BTC对丙硫醇和乙硫醚的静态吸附性能、脱除率、动态吸附性能以及再生性能。结果表明:经FeCl_(2)改性后,Cu-BTC中部分Cu(Ⅱ)被还原为Cu(Ⅰ),由于过度还原导致FeCl_(2)改性后其结晶度降低。此外,随着Fe与Cu物质的量比(Fe/Cu比)增加,吸附剂Fe/Cu-BTC对丙硫醇和乙硫醚的吸附硫容呈先增加后减小的趋势。Fe/Cu比为0.15时的材料Fe/Cu-BTC-0.15的硫容最高,其对丙硫醇和乙硫醚的吸附硫容比Cu-BTC的吸附硫容分别提升了32.3%和46.3%,穿透硫容提升了58.0%和65.9%。Fe/Cu-BTC-0.15对高硫含量模拟油中丙硫醇和乙硫醚的吸附率达90.5%和88.5%。再生Fe/Cu-BTC-0.15对乙硫醚的硫容仍能保持新鲜材料的91.3%。

The metal-organic framework material Fe/Cu-BTC was prepared by modification of Cu-BTC with FeCl_(2).The obtained materials were characterized by X ray diffraction(XRD),scanning electron microscope(SEM),X ray energy dispersive spectroscopy(EDS),inductively coupled plasma(ICP),N2 adsorption and X ray photoelectron spectroscopy(XPS).The static adsorption property,removal ratio of sulfide,dynamic adsorption and regeneration property of Fe/Cu-BTC were investigated.The results showed that the reduction of Cu(II)to Cu(I)happened in the Cu-BTC during the modification process of FeCl_(2) and the corresponding crystallinity decreased after modification with FeCl_(2) because of over reduction.Besides,with the increase of Fe/Cu molar ratio,the adsorption capacity of the adsorbents Fe/Cu-BTC for 1-propanethiol and ethyl sulfide increased first and then decreased.The sulfur capacity of Fe/Cu-BTC-0.15 with 0.15 molar ratio of Fe to Cu reached the highest level.It’s adsorption capacities for 1-propanethiol and ethyl sulfide were 32.3%and 46.3%higher than those of Cu-BTC respectively,the dynamic adsorption capacities of Fe/Cu-BTC-0.15 for 1-propanethiol and ethyl sulfide were 58.0%and 65.9%higher than those of Cu-BTC.The ratio of adsorption for 1-propanethiol and ethyl sulfide by Fe/Cu-BTC-0.15 were high up to 90.5%and 88.5%in the simulated oil with high sulfur content.The adsorption capacity of the regenerated Fe/Cu-BTC-0.15 for ethyl sulfide reached 91.3%of the fresh one.