Abstract
The reaction of aqueous glycerol over a series of ceria catalysts is investigated, to produce bio-renewable methanol. Product distributions were greatly influenced by the reaction temperature and catalyst contact time. Glycerol conversion of 21% was achieved for a 50 wt.% glycerol solution, over CeO2 (8 m2 g−1) at 320 °C. The carbon mass balance was >99 % and the main product was hydroxyacetone. In contrast, at 440 °C the conversion and carbon mass balance were >99.9 % and 76 % respectively. Acetaldehyde and methanol were the major products at this higher temperature, as both can be formed from hydroxyacetone. The space-time yield (STY) of methanol at 320 °C and 440 °C was 15.2 and 145 gMeOH kgcat−1 h−1 respectively. Fresh CeO2 was prepared and calcined at different temperatures, the textural properties were determined and their influence on the product distribution at iso-conversion and constant bed surface area was investigated. No obvious differences to the glycerol conversion or product selectivity were noted. Hence, we conclude that the surface area of the CeO2 does not appear to influence the reaction selectivity to methanol and other products formed from the conversion of glycerol.
Highlights
The increased availability of glycerol; a by-product of first generation biodiesel production, has provided researchers with an opportunity to identify new routes to important platform chemicals and fuels from glycerol [1,2]
The results presented here should form the basis for future development work with ceria catalysts in order to achieve greater product yields to methanol, for example, through catalyst design
[28,29], we reported that a number of the products, including; including; methanol, acetaldehyde and 2,3-butanedione, originate from secondary reactions, which methanol, acetaldehyde originate from secondary reactions, we we proposed were formed and from 2,3-butanedione, hydroxyacetone
Summary
The increased availability of glycerol; a by-product of first generation biodiesel production, has provided researchers with an opportunity to identify new routes to important platform chemicals and fuels from glycerol [1,2]. Production of biodiesel produces impure glycerol at approximately one tenth the mass of biodiesel [3] and consumes methanol derived from fossil fuels [4,5,6]. For this reason, it would be advantageous to develop a means of producing methanol directly from glycerol in a sustainable and economic manner. Acrolein is a valuable intermediate for the production of acrylic acid [12], which is used in the manufacture of many plastics
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