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Biomass has emerged as a potential stable source of carbon in response to concerns about the depletion of fossil resources and global warming. Consequently, processes using biomass as a renewable energy feedstock1)~5) are being developed to produce biodiesel fuel as a potential replacement for fossil fuels. Biodiesel is usually produced by trans-esterification of triglycerides, e.g., vegetable oils and animal fats, with methanol, in which three moles of methanol per mole of triglyceride are stoichiometrically required to yield three moles of fatty acid alkyl ester, i.e., biodiesel, and one mole of glycerol. Accordingly, development of an efficient utilization method for the glycerol byproduct is needed. Glycerol is one of the major platform chemicals in a biorefinery and conversion of glycerol into useful chemicals has much investigation6)~16). Most studies have concentrated on converting glycerol into acrolein6)~8), hydroxyacetone (acetol)9), or 1,2and 1,3-propanediol10)~12). Acrolein and acetol are produced through gas-phase dehydration of glycerol over acidic catalysts including heteropolyacids and zeolites, and copper metal catalysts, respectively. 1,2and 1,3-Propanediol are obtained through hydrogenolysis of glycerol over supported Ru, Rh, and Pt catalysts. Additionally, allyl alcohol has been synthesized from glycerol13)~16) over an iron oxide (hematite, α-Fe2O3) catalyst. We have developed a zirconia_iron oxide catalyst, ZrO2FeOx, for the catalytic conversion of biomass resources, and succeeded in producing phenol and ketones from tar derived from plant biomass17)~21), sewage sludge22), and fermentation residue23),24), in which ZrO2 loaded on FeOx is important for the high catalytic performance and stability. Moreover, we have succeeded in producing useful chemicals, including propylene, allyl alcohol, carboxylic acids, and ketones, from glycerol using ZrO2FeOx catalyst25)~27). Allyl alcohol and propylene are useful and valuable chemicals obtained from glycerol through a characteristic reaction using iron oxide catalyst. The ZrO2FeOx catalyst is very active for reactions involving organic compounds with hydroxyl and carboxyl groups, so this catalyst may also be applicable to the catalytic conversion of glycerol into useful chemicals through two main pathways, formation of allyl alcohol14),25)~27) and propylene (Pathway I), and dehydration of glycerol to form hydroxyacetone and acrolein (Pathway II)28)~32). Hydroxyacetone (acetol) is easily converted into carboxylic acids (acetic and propionic acids), which are then further reacted to form ketones (acetone, methyl ethyl ketone and pentanone) via ketonization24),33). The present study describes the production of useful chemicals from glycerol (crude glycerol and reagent 197 Journal of the Japan Petroleum Institute, 57, (5), 197-207 (2014)

Conversion of Glycerol into Useful Chemicals over Iron Oxide-based Catalyst