Glycerol for renewable acrolein production by catalytic dehydration Amin Talebian-Kiakalaieh, Nor Aishah Saidina Amin n , Hadi Hezaveh Chemical Reaction Engineering Group (CREG), Faculty of Chemical Engineering, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor, Malaysia article info Article history: Received 7 September 2013 Received in revised form 1 July 2014 Accepted 19 July 2014 Keywords: Acrolein Glycerol Catalytic dehydration Bio-based Techno-economical Value-added chemical abstract The significant surge in biodiesel production by transesterification of edible or non-edible oils have caused surplus of glycerol in the market. With its characteristics, unique structure, renewability, and bio- availability, glycerol has tremendous potential to be transformed to higher value-added chemicals. This article provides a comprehensive and critical review of glycerol dehydration to acrolein in both petroleum-and bio-based processes. Acrolein has enormous industrial applications as a significant chemical intermediate for acrylic acid, DL-Methionine and superabsorbent polymer production. The current development of several precursors on suitable support such as heteropoly acids, zeolites, mixed metal oxides, and pyrophosphates in creating superior catalytic properties for both liquid- and gas-phase processes has been discussed. The acidity and textural properties of various catalysts, as significant variables affecting acrolein yield and selectivity, are evaluated separately. Techno-economical evaluation on dehydration of petroleum- and bio-based glycerol to acrolein proved that the bio-based processes are more feasible compared to the conventional petroleum-based process. In addition, various proposed mechanisms for catalytic dehydration of glycerol to acrolein have been examined. Particularly, catalyst coking and few crude glycerol applications have been identified as the main drawbacks for immediate industrialization and commercialization of glycerol dehydration to acrolein. & 2014 Elsevier Ltd. All rights reserved. Contents 1. Introduction ......................................................................................................... 29 1.1. Glycerol ...................................................................................................... 29 1.2. Acrolein ...................................................................................................... 31 2. Petroleum-based acrolein production..................................................................................... 32 2.1. Partial oxidation of propylene to acrolein ........................................................................... 32 3. Bio-based acrolein production .......................................................................................... 33 3.1. Gas-phase dehydration of glycerol to acrolein ........................................................................ 33 3.1.1. Application of supported heteropoly acid catalysts ............................................................. 35 3.1.2. Application of supported zeolite catalysts .................................................................... 36 3.1.3. Application of mixed metal oxides, phosphates, and pyrophosphates catalysts ....................................... 38 3.2. Liquid phase dehydration of glycerol to acrolein ...................................................................... 41 3.3. Physico-chemical effect of catalyst on acrolein yield ................................................................... 43 3.3.1. Catalyst acidity.......................................................................................... 43 3.3.2. Textural properties (pore size) ............................................................................. 44 3.4. Catalyst deactivation and regeneration.............................................................................. 44 3.5. Reaction mechanism ............................................................................................ 46 3.6. Application of crude glycerol for acrolein production .................................................................. 48 4. Techno-economical evaluation of bio-based acrolein production ............................................................... 49 Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/rser Renewable and Sustainable Energy Reviews http://dx.doi.org/10.1016/j.rser.2014.07.168 1364-0321/& 2014 Elsevier Ltd. All rights reserved. n Corresponding author. Tel.: þ60 7 553 5579; fax: þ60 7 558 8166. E-mail addresses: talebian_amin@yahoo.com (A. Talebian-Kiakalaieh), noraishah@cheme.utm.my (N.A.S. Amin). Renewable and Sustainable Energy Reviews 40 (2014) 28–59