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Efficient green methanol synthesis from glycerol

Nature Chemistry volume 7, pages 1028–1032 (2015)Cite this article

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Abstract

The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry.

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Figure 1: Catalytic activity of the metal-oxide and mixed metal-oxide materials.
Figure 2: Catalytic conversion of glycerol over cerium oxide and selectivity to methanol.
Figure 3: The influence of reaction temperature on the conversion and product selectivities (mol%) over MgO (A) with different feed concentrations of 1,3-propanediol.
Figure 4: Proposed mechanism for the formation of methanol from glycerol (1).
Figure 5: Catalytic activity of CeO2 increases the glycerol feed concentration for both pure and crude glycerol.

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Acknowledgements

The authors acknowledge the financial support of Cardiff University, the Engineering and Physical Sciences Research Council (Grant No. EP/J013420/1), the European Research Council (ERC-2011-ADG, Grant Agreement No. 291319: ‘After The Gold Rush’) and the Technology Strategy Board. This work initially formed part of the Glycerol Challenge and was cofunded by the Technology Strategy Board's Collaborative Research and Development programme after an open competition. The Technology Strategy Board is an executive body established by the UK Government to drive innovation. The authors also thank Biodiesel Amsterdam BV for supplying crude glycerol.

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  1. Muhammad H. Haider

    Present address: Present address: Sabic Technology & Innovation Center (STC), PO Box 42503, Riyadh 11551, Kingdom of Saudi Arabia,

Authors and Affiliations

  1. Cardiff Catalysis Institute, School of Chemistry. Cardiff University, Cardiff, CF10 3AT, UK

    Muhammad H. Haider, Nicholas F. Dummer, David W. Knight, Robert L. Jenkins, Jacob Moulijn, Stuart H. Taylor & Graham J. Hutchings

  2. Hull Research & Technology Centre, Saltend, HU12 8DS, Hull, UK

    Mark Howard

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Contributions

M.H.H. prepared and tested the catalysts and designed the initial experiments, N.F.D designed the reactor and provided assistance with experimental design and D.W.K. provided mechanistic insights into the chemistry. Detailed analysis was provided by R.L.J. S.H.T provided expertise on catalyst preparation. G.J.H. directed the overall research and all the authors contributed to the analysis of the data and the writing of the manuscript.

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Correspondence to Muhammad H. Haider or Graham J. Hutchings.

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The authors declare no competing financial interests.

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Haider, M., Dummer, N., Knight, D. et al. Efficient green methanol synthesis from glycerol. Nature Chem 7, 1028–1032 (2015). https://doi.org/10.1038/nchem.2345

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