Univ. Lille Nord de France, Ecole Centrale de Lille, Unité de Catalyse et de Chimie du Solide (UMR8181), Cité Scientifique, F-59655 Villeneuve d'Ascq, France.
ChemSusChem. 2012 Jul;5(7):1298-306. doi: 10.1002/cssc.201100635. Epub 2012 Apr 13.
The dehydration reaction of glycerol to acrolein is catalyzed by acid catalysts. These catalysts tend to suffer from the formation of carbonaceous species on their surface (coking), which leads to substantial degradation of their performances (deactivation). To regenerate the as-deactivated catalysts, various techniques have been proposed so far, such as the co-feeding of oxygen, continuous regeneration by using a moving catalytic bed, or alternating between reaction and regeneration. Herein, we study the regeneration of supported heteropolyacid catalysts. We show that the support has a strong impact on the thermal stability of the active phase. In particular, zirconia has been found to stabilize silicotungstic acid, thus enabling the nondestructive regeneration of the catalyst. Furthermore, the addition of steam to the regeneration feed has a positive impact by hindering the degradation reaction by equilibrium displacement. The catalysts are further used in a periodic reaction/regeneration process, whereby the possibility of maintaining long-term catalytic performances is evidenced.
甘油脱水生成丙烯醛的反应由酸催化剂催化。这些催化剂往往容易在表面形成碳质物种(结焦),从而导致其性能严重下降(失活)。为了使失活的催化剂再生,迄今为止已经提出了各种技术,例如共进料氧气、使用移动催化床连续再生或在反应和再生之间交替进行。在此,我们研究了负载杂多酸催化剂的再生。我们表明,载体对活性相的热稳定性有很大的影响。特别是,发现氧化锆能稳定硅钨酸,从而能够实现催化剂的无损再生。此外,在再生进料中添加蒸汽通过平衡取代反应阻碍降解反应,从而产生积极影响。这些催化剂进一步用于周期性的反应/再生过程,证明了保持长期催化性能的可能性。