Submitted to: Industrial and Engineering Chemistry Research
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 6/30/2015
Publication Date: 6/30/2015
Citation: Jackson, M.A., Appell, M., Blackburn, J.A. 2015. Hydrodeoxygenation of fructose to 2,5-dimethyltetrahydrofuran using a sulfur poisoned Pt/C catalyst. Industrial and Engineering Chemistry Research. 54(28):7059-7066. doi: 10.1021/acs.iecr.5b00766.
Interpretive Summary: In this work we demonstrated a simple conversion of sugar to the fuel component DMTHF. A second generation biofuel, 2,5-dimethyltetrahydrofuran (DMTHF) has properties that are better than ethanol, such as being insoluble in water, that make it attractive. What we found in this work is that if the proper catalyst is used for the conversion of the sugar fructose, yields of DMTHF can be quite high. The commercialization of this technology will lead to greater use of crop residues or energy crops for production of a renewable chemical with uses as a solvent or fuel additive.
Technical Abstract: In order to expand the number of biobased chemicals available, fructose has been hydrogenated to 2,5-dimethyltetrahydrofuran using a sulfided Pt/C catalyst. The reaction was carried out in a stirred reactor at 10.3 MPa H2 and 175°C which allowed a 10% fructose solution to be converted in about 2 h. The selectivity was greatly enhanced by using ethanol as solvent with 95% ethanol giving 50% DMTHF versus 9% in water. The only intermediate found along the reaction pathway was 2,5-hexanedione. This is presumed to be hydrogenated to 2,5-hexanediol which then ring closes to DMTHF. Molecular simulation at the B3LYP/6-31+G* level was used to propose a reaction pathway to 2,5-hexanedione. The catalyst loses sulfur during the reaction and so cannot be reused, and it cannot even be repoisoned.