第315回触媒化学研究センターコロキウム
Glycerol Dehydration to Acrolein, from Catalyst
Development to Process
Professor Franck Dumeignil (Univ. Lille Nord deFrance)
2012年12月10日（月）13：30—14：10（創成科学研究棟4階セミナー室B・C）
http://www.cat.hokudai.ac.jp/access.html
Due to the increasing amount of glycerol by-produced with biodiesel, its upgrading by dehydration toacrolein is driving much attention. This reaction can be catalyzed by various solid acid catalysts, whichhave all in common that they deactivate by coking. We studied the possibility of in situ regeneration ofspent catalysts based on Keggin-type silicotungstic acid (STA - H4SiW12O40). Two samples wereprepared with 20 wt.% STA, the first one supported on bare SBA-15, and the second one supported on
SBA-15 in which 20 wt.% of ZrO2 nanoparticles were dispersed. The acidity of the catalysts wasdetermined by NH3-TPD and the thermal stability of the active phase was studied by TGA. The catalytic
performances were determined at 275 °C in a fixed bed down flow reactor. The STA/ZrO2/SBA-15
catalyst showed significantly increased long-term performance (69 % vs. 24 % yield in acrolein after 24 hof reaction). Grafting with zirconia led to a decrease in the acid strength of the STA, which was assigned
to a modified electronic interaction between the active phase and the support, with further an increased
thermal stability of the active phase. Thanks to this latter property, STA decomposition during one-shot
regeneration of the catalyst by coke burning under air was suppressed, and the initial catalytic
performance could be essentially recovered. In contrast, over the ZrO2-free catalyst, the regeneration
step led to a significant loss in acrolein yield (30 %) due to thermal destruction of STA. As thisdecomposition proceeds via the loss of constitutional water from the Keggin-structure, addition of waterin the regeneration feed enabled recovering a slightly higher yield in acrolein (42 %), due to equilibrium
displacement. Finally, cyclic regeneration of the catalyst was performed using iso-chronical cycles of 10
min for reaction and coke burning. The STA/ZrO2/SBA-15 catalyst exhibited then poor performances(35 % yield in acrolein), which was explained by the longer activation period needed by this catalyst. On
the other hand, the non-grafted catalyst exhibited rather stable performances (74 % yield in acrolein),
without STA destruction. This was attributed to the shortness of the cycles, with thus only small amounts
cokes to be burnt, then preventing the formation of harmful hotspots during regeneration. At last, wedeveloped an integrated process for simultaneous reaction and regeneration, based on a Two-Zone
Fluidized Bed Reactor (TZFBR) technology we patented.
問合せ先： 触媒化学研究センター・福岡淳（fukuoka@cat.hokudai.ac.jp/011-706-9140）
Franck Dumeignil is Professor at the University of Lille North of France, and the Deputy Director of UCCS. After hisPhD at the University of Lille (1998), he spent 6.5 years in Japan. After a 2 years post-doctoral stay at NIMC inTsukuba, he was subsequently employed at the Tokyo University of Agriculture and Technology (TUAT), first with a
2 years post-doctoral position, and then as an associate professor, within the frame of a Centre of Excellence(Scientific Cluster). In January 2010, he was nominated vice-director of UCCS, UMR CNRS 8181, France, which
comprises more than 200 persons. Franck Dumeignil has further been nominated as a Junior Member of theprestigious IUF academy from the 1st of October 2010. He is co-author of more than 50 scientific articles, 6 patents,and more than 200 communications (oral and poster) in national and international congress.

315th Catalysis Research Center (CRC) Colloquium