Zn-Fe-S<sub>2</sub>O<sub>8</sub><sup style="margin-left:-6px;">-2</sup>/ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> 超酸催化剂:活性、表面分析以及失活和再生研究

Huapeng Cui, Shengnan Li
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摘要

制备了Zn和Fe改性的S2O8-2/ZrO2-Al2O3催化剂(Zn-Fe- sza),并以正戊烷异构化为探针反应,探讨了催化剂的失活机理和再生方法。结果表明,新鲜Zn-Fe-SZA-F催化剂的异戊烷产率在运行初期约为57%,在1500 min内逐渐下降至50%,在1500 ~ 2500 min间由50%迅速下降至40%。Zn-Fe-SZA催化剂的失活可能是由于催化剂表面形成碳、氢还原导致硫酸盐基的衰减、硫种的去除和强酸位的损失。结果表明,Zn-Fe-SZA-T催化剂的初始催化活性为48%,比新鲜催化剂(57%)提高了84.3%。但在1500分钟内异戊烷收率由48%急剧下降到29%,稳定性较差。这与去除硫化物导致的酸度损失有关,通过热处理基本上无法恢复硫化物。结果表明,与煅烧样品相比,煅烧后的催化剂能显著提高催化剂的酸性,尤其是强酸位点。所制催化剂稳定性的提高可以解释为:1)煅烧过程在一定程度上消除了碳沉积;2)通过再硫化形成改善的酸性,有利于酸性位点的异构化;3)通过煅烧-再硫化过程对酸和金属位点进行了重组。
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Hydroisomerization of <i>n</i>-Pentane over Zn-Fe-S<sub>2</sub>O<sub>8</sub><sup style="margin-left:-6px;">-2</sup>/ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> Superacid Catalyst: Activity, Surface Analysis and the Investigation of Deactivation and Regeneration
The Zn and Fe modified S2O8-2/ZrO2-Al2O3 catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.
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Hydroisomerization of <i>n</i>-Pentane over Zn-Fe-S<sub>2</sub>O<sub>8</sub><sup style="margin-left:-6px;">-2</sup>/ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> Superacid Catalyst: Activity, Surface Analysis and the Investigation of Deactivation and Regeneration Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands.
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