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负载于多孔硅铝磷酸盐沸石上的锌基尖晶石吸附剂的晶格取代与脱硫动力学分析

Lattice substitution and desulfurization kinetic analysis of Zn-based spinel sorbents loading onto porous silicoaluminophosphate zeolites.

作者信息

Liu Qiang, Liu Bingsi, Liu Qinze, Xu Rongnian, Xia Hong

机构信息

Department of Chemistry, Tianjin University, and The National Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, People's Republic of China.

Department of Chemistry, Tianjin University, and The National Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, People's Republic of China.

出版信息

J Hazard Mater. 2020 Feb 5;383:121151. doi: 10.1016/j.jhazmat.2019.121151. Epub 2019 Sep 4.

Abstract

Green Zn-based spinel sorbents for hot coal gas desulfurization have been developed with the assistance of optimization procedures. The pilot study highlights an outstanding ordered mesoporous support (S = 323 m g, Da = 4.3 nm) of SAPO-34@as-prepared SBA-15 (SS) for loading active metal oxides. ZnCoO spinel loaded onto SS (ZnCo/SS) exhibits a prominent desulfurization performance compared to other sorbents whose partial Co is substituted by Mn or Fe in spinel B-site, owing to the slight effect of PO in SS. After systematic evaluation on role of sulfidation condition, 50 wt% ZnCo/SS sorbent possesses the sulfur storage capacity of 138.08  mg gat550 °C and little loss of active species in 5 desulfurization-regeneration cycles. Results of high resolution transmission electron microscopy (HRTEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS) etc. demonstrate that 70.42% of initial sulfur capacity of ZnCo/SS presented in the 2nd utilization is associated with zinc evaporation, existence of high stable sulfides and partial sintering. The improved deactivation kinetic model suitably describes that the HS concentration distribution relates with the spatial position of fixed-bed reactor and desulfurization time.

摘要

在优化程序的辅助下,已开发出用于热煤气脱硫的绿色锌基尖晶石吸附剂。中试研究突出了一种出色的有序介孔载体(S = 323 m²/g,Da = 4.3 nm),即SAPO-34@制备态SBA-15(SS),用于负载活性金属氧化物。负载在SS上的ZnCoO尖晶石(ZnCo/SS)与其他在尖晶石B位部分Co被Mn或Fe取代的吸附剂相比,表现出显著的脱硫性能,这归因于SS中PO的轻微影响。在对硫化条件的作用进行系统评估后,50 wt%的ZnCo/SS吸附剂在550°C时具有138.08 mg/g的硫储存容量,并且在5次脱硫-再生循环中活性物种损失很少。高分辨率透射电子显微镜(HRTEM)、布鲁诺尔-埃米特-泰勒(BET)、X射线光电子能谱(XPS)等结果表明,ZnCo/SS在第二次使用时初始硫容量的70.42%与锌蒸发、高稳定性硫化物的存在和部分烧结有关。改进的失活动力学模型适当地描述了HS浓度分布与固定床反应器的空间位置和脱硫时间的关系。

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