New insights for the valorisation of glycerol over MgO catalysts in the gas-phase

作者: Louise R. Smith , Paul J. Smith , Karl S. Mugford , Mark Douthwaite , Nicholas F. Dummer

DOI: 10.1039/C8CY02214C

关键词:

摘要: Aqueous glycerol solutions of up to 50 wt% were reacted over magnesium oxide catalysts at temperatures greater than 300 °C, the reactivity which was compared catalyst-free reactions. Under conditions, modest levels dehydration hydroxyacetone observed >400 °C in a steel reactor tube and >320 silicon carbide. For reactions MgO, product distribution becomes more diverse, resulting formation methanol, acetaldehyde, ethylene glycol, 1,2-propanediol acetic acid. The methanol space–time–yield MgO catalyst samples (0.5 g) found be highest 400 (205 g h−1 kgcat−1) with solution glycerol, or concentration 10 wt%; 255 kgcat−1 0.1 catalyst. Despite high conversion achieved, stable 48 h, following decrease during initial 2 h reaction. Post-reaction characterisation revealed that level coking conversions (>90%) ≥120 mg gcat−1. carbon mass balance determined by GC analysis for typical reaction 75% so lost from only represents quantity missing carbon; typically <10%. also promote molecular weight products via condensation reactions, responsible remainder ca. 15%. Therefore, total organic content post-reaction mixture coke calculated 94% starting solution. We conclude surface directs however, results indicate conditions are crucial obtain optimum yields.

参考文章(52)
C. Montassier, D. Giraud, J. Barbier, Polyol Conversion by Liquid Phase Heterogeneous Catalysis Over Metals Studies in Surface Science and Catalysis. ,vol. 41, pp. 165- 170 ,(1988) , 10.1016/S0167-2991(09)60811-9
Chang Liu, Rong Liu, Tiefeng Wang, Glycerol dehydration to acrolein: Selectivity control over CsPW/Nb2O5 catalyst Canadian Journal of Chemical Engineering. ,vol. 93, pp. 2177- 2183 ,(2015) , 10.1002/CJCE.22339
Rajeesh Kumar Pazhavelikkakath Purushothaman, J. van Haveren, D. S. van Es, I. Melián-Cabrera, H. J. Heeres, The oxidative esterification of glycerol to methyl glycerate in methanol using gold on oxidic supports: an insight in product selectivity Green Chemistry. ,vol. 14, pp. 2031- 2037 ,(2012) , 10.1039/C2GC35226E
J. S. Francisco, A comprehensive theoretical examination of primary dissociation pathways of formic acid Journal of Chemical Physics. ,vol. 96, pp. 1167- 1175 ,(1992) , 10.1063/1.462204
Benjamin Katryniok, Sébastien Paul, Virginie Bellière-Baca, Patrick Rey, Franck Dumeignil, Glycerol dehydration to acrolein in the context of new uses of glycerol Green Chemistry. ,vol. 12, pp. 2079- 2098 ,(2010) , 10.1039/C0GC00307G
JA Melero, G Vicente, G Morales, M Paniagua, JM Moreno, R Roldán, A Ezquerro, CJACAG Pérez, None, Acid-catalyzed etherification of bio-glycerol and isobutylene over sulfonic mesostructured silicas Applied Catalysis A-general. ,vol. 346, pp. 44- 51 ,(2008) , 10.1016/J.APCATA.2008.04.041
Takafumi Shido, Kiyotaka Asakura, Yasuhiro Iwasawa, Reactant-promoted reaction mechanism for catalytic water-gas shift reaction on MgO Journal of Catalysis. ,vol. 122, pp. 55- 67 ,(1990) , 10.1016/0021-9517(90)90261-H
Graham J. Hutchings, Chunli Xu, Jonathan K. Bartley, Dan I. Enache, David W. Knight, High Surface Area MgO as a Highly Effective Heterogeneous Base Catalyst for Michael Addition and Knoevenagel Condensation Reactions Synthesis. ,vol. 2005, pp. 3468- 3476 ,(2005) , 10.1055/S-2005-918467
Wei Yan, Galen J. Suppes, Low-Pressure Packed-Bed Gas-Phase Dehydration of Glycerol to Acrolein Industrial & Engineering Chemistry Research. ,vol. 48, pp. 3279- 3283 ,(2009) , 10.1021/IE801200P
André O. Menezes, Priscila S. Silva, Eduardo Padrón Hernández, Luiz E. P. Borges, Marco A. Fraga, Tuning surface basic properties of nanocrystalline MgO by controlling the preparation conditions. Langmuir. ,vol. 26, pp. 3382- 3387 ,(2010) , 10.1021/LA903149Y