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Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis

Abstract

Biofuels production from lignocellulosic biomass is hindered by high conversion costs in the generation of high-quality fuels, driving research towards the development of new pathways with less severe conditions, higher yields and higher-quality products. Here, we present a market-responsive biorefinery concept based on methanol as the key intermediate, which generates high-octane gasoline (HOG) and jet fuel blendstocks from biomass. Process models and techno-economic analysis are linked with both fundamental and applied catalyst development research to quantify the impact of catalyst advancements on process economics. By facilitating reincorporation of C4 by-products during dimethyl ether homologation, a Cu-modified beta zeolite catalyst enabled a 38% increase in yield of the HOG product and a 35% reduction in conversion cost compared to the benchmark beta zeolite catalyst. Alternatively, C4 by-products were directed to a synthetic kerosene that met five specifications for a typical jet fuel, with a minor increase in the fuel synthesis cost versus the HOG-only case.

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Fig. 1: Schematic flow diagram of a market-responsive biorefinery concept.
Fig. 2: Sensitivity analysis of catalyst parameters in the HOG synthesis reactor.
Fig. 3: Block flow diagram with TEA metrics for the target and benchmark BEA cases.
Fig. 4: Comparison of catalytic performance for Cu/BEA and benchmark BEA.
Fig. 5: Mass spectra of products from DME homologation with co-fed 13C-labelled isobutane.
Fig. 6: Kinetic and mechanistic considerations for isobutane activation.

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Data availability

Data that support the plots and other findings in this Article are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was authored by the Alliance for Sustainable Energy, the manager and operator of the National Renewable Energy Laboratory for the US Department of Energy (DOE) under contract no. DE-AC36-08GO28308. Funding was provided by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office in collaboration with the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Energy Materials Network (EMN). The views expressed in this Article do not necessarily represent the views of the DOE or the US Government. The authors thank M. Behl for assistance with the olefin coupling experiments, A. Dutta for helpful discussions about the process model and TEA, and J. Super for assistance with the CatCost analysis.

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Contributions

D.A.R., J.E.H. and J.A.S. conceptualized the research effort and designed the experimental outline. D.A.R. prepared the catalysts. D.A.R. and F.G.B. characterized the catalysts. C.P.N. performed the catalysis experiments. E.C. performed the fuel property analyses. E.C.D.T. performed technoeconomic analyses. D.A.R., J.E.H., J.A.S., C.P.N. and C.A.F. analysed the catalysis data. C.A.F. performed reaction energy computations. K.M.V.A. and F.G.B. performed the CatCost analysis. All authors contributed to data interpretation. D.A.R. drafted the initial manuscript. All authors reviewed and edited the manuscript and Supplementary Information.

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Correspondence to Daniel A. Ruddy.

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Supplementary Tables 1–11 and Supplementary Figs. 1–8

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Ruddy, D.A., Hensley, J.E., Nash, C.P. et al. Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis. Nat Catal 2, 632–640 (2019). https://doi.org/10.1038/s41929-019-0319-2

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