Katryniok Benjamin, Meléndez Roger, Bellière-Baca Virginie, Rey Patrick, Dumeignil Franck, Fatah Nouria, Paul Sébastien
CNRS, Centrale Lille, ENSCL, Univ. Lille, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, Lille, France.
ADISSEO France SAS, Antony, France.
Front Chem. 2019 Mar 14;7:127. doi: 10.3389/fchem.2019.00127. eCollection 2019.
The gas-phase catalytic dehydration of glycerol to acrolein was carried out in a Two-Zone Fluidized-Bed Reactor (TZFBR) using a 20 wt. % phosphotungstic acid (HPWO) catalyst supported on CARIACT-Q10 commercial silica. In the first step, a hydrodynamic study of the reactor was performed. A quality of fluidization of more than 80% was obtained. In the second step, the mechanical stability of the catalyst was studied. It was found that only the external layer of active phase is eliminated under the conditions of operation whereas the global composition of the catalyst was not significantly affected after 44 h of fluidization. Finally, in a third step, the influence of the main operating parameters on the overall catalytic performances (glycerol/oxygen molar ratio and relative volumes of the reaction and regeneration zones) was investigated, showing notably the importance of the O/glycerol ratio, resulting in an inverse trend between conversion and selectivity. Increasing O/glycerol ratio led to higher conversion (lower coke deposit as shown by TGA analysis), but to the detriment of the selectivity to acrolein, supposedly due to the presence of O in the reaction zone causing the degradation of glycerol and acrolein.
在两段式流化床反应器（TZFBR）中，以负载于CARIACT-Q10商用硅胶上的20 wt.%磷钨酸（HPWO）为催化剂，进行甘油气相催化脱水制丙烯醛的反应。第一步，对反应器进行了流体动力学研究，获得了超过80%的流化质量。第二步，研究了催化剂的机械稳定性，发现在操作条件下仅活性相的外层被消除，而流化44小时后催化剂的整体组成未受到显著影响。最后，第三步，研究了主要操作参数对整体催化性能（甘油/氧气摩尔比以及反应区和再生区的相对体积）的影响，特别表明了氧气/甘油比的重要性，导致转化率和选择性呈相反趋势。增加氧气/甘油比导致更高的转化率（热重分析表明焦炭沉积减少），但不利于丙烯醛的选择性，推测是由于反应区中氧气的存在导致甘油和丙烯醛降解。
