Department of Chemical & Biomolecular Engineering, Graduate School of EEWS (WCU), Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea.
ChemSusChem. 2012 Aug;5(8):1513-22. doi: 10.1002/cssc.201100821. Epub 2012 Jun 29.
The production of syngas was investigated by steam reforming glycerol over Ni/Al(2)O(3), Ni/CeO(2), and Ni/SiC (which have acidic, basic, and neutral properties) at temperatures below 773 K. The complete and stable conversion of glycerol with a yield (higher than 90 %) of gaseous products (mainly syngas) was achieved over Ni/SiC during a 60 h reaction, whereas the conversion of glycerol continually decreases over Ni/Al(2)O(3) (by 49.8 %) and Ni/CeO(2) (by 77.1 %). The deactivation of Ni/Al(2)O(3) and Ni/CeO(2) is mainly caused by coke deposition because of the C-C cleavage of the byproducts produced by dehydration over acidic sites and condensation over basic sites. Gaseous products with a 1.0-1.9 syngas ratio (H(2)/CO) are produced over Ni/SiC. This ratio is required for the Fischer-Tropsch synthesis. However, a syngas ratio of more than 3.0 was observed over Ni/Al(2)O(3) and Ni/CeO(2) because of the high activity of the water-gas-shift reaction. Any dissociative or associative adsorption of water on Al(2)O(3) and CeO(2) promotes a water-gas-shift reaction and produces a higher syngas ratio. H(2) and CO were mainly produced by decomposition of glycerol through dehydrogenation and decarbonylation over Ni sites. Thus, SiC promotes an intrinsic contribution of nickel (dehydrogenation, and decarbonylation) without any byproducts from the dehydration and condensation.
在低于 773 K 的温度下,通过蒸汽重整甘油研究了 Ni/Al(2)O(3)、Ni/CeO(2) 和 Ni/SiC(分别具有酸性、碱性和中性性质)上的合成气生产。在 60 小时的反应中,Ni/SiC 上甘油完全且稳定转化,气态产物(主要是合成气)收率(高于 90%)高,而 Ni/Al(2)O(3)(降低 49.8%)和 Ni/CeO(2)(降低 77.1%)上的甘油转化率持续下降。Ni/Al(2)O(3) 和 Ni/CeO(2) 的失活主要是由于酸性位上脱水副产物的 C-C 断裂和碱性位上缩合导致积碳造成的。在 Ni/SiC 上产生了 H2/CO 比为 1.0-1.9 的气态产物。这一比值是费托合成所需要的。然而,在 Ni/Al(2)O(3) 和 Ni/CeO(2) 上观察到超过 3.0 的合成气比值,这是由于水煤气变换反应的高活性所致。在 Al(2)O(3) 和 CeO(2) 上,水的任何离解或缔合吸附都会促进水煤气变换反应并产生更高的合成气比值。H2 和 CO 主要是通过 Ni 位上甘油的脱氢和脱羰分解产生的。因此,SiC 促进了镍的内在贡献(脱氢和脱羰),而没有来自脱水和缩合的任何副产物。