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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.

Data availability

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

References

  1. Chang, C. D. & Silvestri, A. J. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts. J. Catal. 47, 249–259 (1977).

    Article  CAS  Google Scholar 

  2. Haw, J. F., Song, W., Marcus, D. M. & Nicholas, J. B. The mechanism of methanol to hydrocarbon catalysis. Acc. Chem. Res. 36, 317–326 (2003).

    Article  CAS  Google Scholar 

  3. Yarulina, I., Chowdhury, A. D., Meirer, F., Weckhuysen, B. M. & Gascon, J. Recent trends and fundamental insights in the methanol-to-hydrocarbons process. Nat. Catal. 1, 398–411 (2018).

    Article  CAS  Google Scholar 

  4. Yarulina, I. et al. Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process. Nat. Chem. 10, 804–812 (2018).

    Article  CAS  Google Scholar 

  5. Tian, P., Wei, Y., Ye, M. & Liu, Z. Methanol to olefins (MTO): from fundamentals to commercialization. ACS Catal. 5, 1922–1938 (2015).

    Article  CAS  Google Scholar 

  6. Ilias, S. & Bhan, A. Mechanism of the catalytic conversion of methanol to hydrocarbons. ACS Catal. 3, 18–31 (2013).

    Article  CAS  Google Scholar 

  7. Hazari, N., Iglesia, E., Labinger, J. A. & Simonetti, D. A. Selective homogeneous and heterogeneous catalytic conversion of methanol/dimethyl ether to triptane. Acc. Chem. Res. 45, 653–662 (2012).

    Article  CAS  Google Scholar 

  8. Teketal, S., Svelle, S., Lillerud, K. P. & Olsbye, U. Shape-selective conversion of methanol to hydrocarbons over 10-ring unidirectional-channel acidic H-ZSM-22. ChemCatChem 1, 78–81 (2009).

    Article  Google Scholar 

  9. Teketel, S. et al. Shape selectivity in the conversion of methanol to hydrocarbons: the catalytic performance of one-dimensional 10-ring zeolites: ZSM-22, ZSM-23, ZSM-48 and EU-1. ACS Catal. 2, 26–37 (2012).

    Article  CAS  Google Scholar 

  10. Stocker, M. Methanol-to-hydrocarbons: catalytic materials and their behaviour. Microporous Mesoporous Mater. 29, 3–48 (1999).

    Article  CAS  Google Scholar 

  11. Keil, F. Methanol-to-hydrocarbons: process technology. Microporous Mesoporous Mater. 29, 49–66 (1999).

    Article  CAS  Google Scholar 

  12. Mokrani, T. & Scurrell, M. Gas conversion to liquid fuels and chemicals: the methanol route-catalysis and processes development. Catal. Rev. 51, 1–145 (2009).

    Article  CAS  Google Scholar 

  13. Phillips, S. D., Tarud, J. K., Biddy, M. J. & Dutta, A. Gasoline from Wood via Integrated Gasification, Synthesis, and Methanol-to-Gasoline Technologies. Report No. NREL/TP-5100-47594 (National Renewable Energy Laboratory, 2011).

  14. Lange, J.-P. Lignocellulose conversion: an introduction to chemistry, process and economics. Biofuel. Bioprod. Biorefin. 1, 39–48 (2007).

    Article  CAS  Google Scholar 

  15. Ruddy, D. A. et al. Recent advances in heterogeneous catalysts for bio-oil upgrading via ‘ex situ catalytic fast pyrolysis’: catalyst development through the study of model compounds. Green Chem. 16, 454–490 (2014).

    Article  CAS  Google Scholar 

  16. Griffin, M. B. et al. Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration. Energy Environ. Sci. 11, 2904–2918 (2018).

    Article  CAS  Google Scholar 

  17. Grim, R. G. et al. Growing the bioeconomy through catalysis: a review of recent advancements in the production of fuels and chemicals from syngas-derived oxygenates. ACS Catal. 9, 4145–4172 (2019).

    Article  CAS  Google Scholar 

  18. Ahn, J. H., Temel, B. & Iglesia, E. Selective homologation routes to 2,3,3-trimethylbutane on solid acids. Angew. Chem. Int. Ed. 48, 3814–3816 (2009).

    Article  CAS  Google Scholar 

  19. Simonetti, D. A., Ahn, J. H. & Iglesia, E. Mechanistic details of acid-catalyzed reactions and their role in the selective synthesis of triptane and isobutane from dimethyl ether. J. Catal. 277, 173–195 (2011).

    Article  CAS  Google Scholar 

  20. Simonetti, D. A., Ahn, J. H. & Iglesia, E. Catalytic co-homologation of alkanes and dimethyl ether and promotion by adamantane as a hydride transfer co-catalyst. ChemCatChem 3, 704–718 (2011).

    Article  CAS  Google Scholar 

  21. Tan, E. C. D. et al. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates. Biofuel. Bioprod. Bioref. 10, 17–35 (2016).

    Article  CAS  Google Scholar 

  22. Higgins, T.J. The New Economics of Octane: What Drives the Cost of Octane and Why Octane Costs have Risen since 2012 (OPIS, 2017); https://www.opisnet.com/wp-content/uploads/2017/08/OctaneReport_TOC_Exhibits.pdf

  23. Dutta, A. et al. Techno-economics for conversion of lignocellulosic biomass to ethanol by indirect gasification and mixed alcohol synthesis. Environ. Prog. Sustain. Energy 31, 182–190 (2012).

    Article  CAS  Google Scholar 

  24. Schaidle, J. A. et al. Conversion of dimethyl ether to 2,2,3-trimethylbutane over a Cu/BEA catalyst: role of Cu sites in hydrogen incorporation. ACS Catal. 5, 1794–1803 (2015).

    Article  CAS  Google Scholar 

  25. Farberow, C. A. et al. Exploring low-temperature dehydrogenation at ionic Cu sites in beta zeolite to enable alkane recycle in eimethyl ether homologation. ACS Catal. 7, 3662–3667 (2017).

    Article  CAS  Google Scholar 

  26. Behl, M., Schaidle, J. A., Christensen, E. & Hensley, J. E. Synthetic middle-distillate-range hydrocarbons via catalytic dimerization of branched C6−C8 olefins derived from renewable dimethyl ether. Energy Fuels 29, 6078–6087 (2015).

    Article  CAS  Google Scholar 

  27. Baddour, F. G., Snowden-Swan, L., Super, J. D. & Van Allsburg, K. M. Estimating precommercial heterogeneous catalyst price: a simple step-based method. Org. Process Res. Dev. 22, 1599–1605 (2018).

    Article  CAS  Google Scholar 

  28. Ilias, S., Khare, R., Malek, A. & Bhan, A. A descriptor for the relative propagation of the aromatic- and olefin-based cycles in methanol-to-hydrocarbons conversion on H-ZSM-5. J. Catal. 303, 135–140 (2013).

    Article  CAS  Google Scholar 

  29. Khare, R., Millar, D. & Bhan, A. A mechanistic basis for the effects of crystallite size on light olefin selectivity in methanol-to-hydrocarbons conversion on MFI. J. Catal. 321, 23–31 (2015).

    Article  CAS  Google Scholar 

  30. Khare, R., Liu, Z., Han, Y. & Bhan, A. A mechanistic basis for the effect of aluminum content on ethene selectivity in methanol-to-hydrocarbons conversion on HZSM-5. J. Catal. 348, 300–305 (2017).

    Article  CAS  Google Scholar 

  31. Hwang, A., Prieto-Centurion, D. & A. Bhan, A. Isotopic tracer studies of methanol-to-olefins conversion over HSAPO-34: the role of the olefins-based catalytic cycle. J. Catal. 337, 52–56 (2016).

    Article  CAS  Google Scholar 

  32. Arora, S. S., Nieskens, D. L. S., Malek, A. & Bhan, A. Lifetime improvement in methanol-to-olefins catalysis over chabazite materials by high-pressure H2 co-feeds. Nat. Catal. 1, 666–672 (2018).

    Article  CAS  Google Scholar 

  33. Hu, J. Z. et al. 27Al MAS NMR studies of HBEA zeolite at low and high magnetic fields. J. Phys. Chem. C 121, 12849–12854 (2017).

    Article  CAS  Google Scholar 

  34. Hill, I. M., Ng, Y. S. & Bhan, A. Kinetics of butene isomer methylation with dimethyl ether over zeolite catalysts. ACS Catal. 2, 1742–1748 (2012).

    Article  CAS  Google Scholar 

  35. Svelle, S., Ronning, P. O. & Kolboe, S. Kinetic studies of zeolite-catalyzed methylation reactions 1. Coreaction of [12C]ethene and [13C]methanol. J. Catal. 224, 115–213 (2004).

    Article  CAS  Google Scholar 

  36. Svelle, S., Ronning, P. O., Olsbye, U. & Kolboe, S. Kinetic studies of zeolite-catalyzed methylation reactions. Part 2. Co-reaction of [12C]propene or [12C]n-butene and [13C]methanol. J. Catal. 234, 385–400 (2005).

    Article  CAS  Google Scholar 

  37. Yamazaki, H. et al. Evidence for a ‘carbene-like’ intermediate during the reaction of methoxy species with light alkenes on H-ZSM-5. Angew. Chem. Int. Ed. 50, 1853–1856 (2011).

    Article  CAS  Google Scholar 

  38. Wang, W. & Hunger, M. Reactivity of surface alkoxy species on acidic zeolite catalysts. Acc. Chem. Res. 41, 895–904 (2008).

    Article  CAS  Google Scholar 

  39. Svelle, S., Visur, M., Olsbye, U., Saepurahman & Bjorgen, M. Mechanistic aspects of the zeolite catalysed methylation of alkenes and aromatics with methanol: a review. Top. Catal. 54, 897–906 (2011).

    Article  CAS  Google Scholar 

  40. Tan, E. C. D. et al. Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading. Biofuel. Bioprod. Bioref. 11, 41–66 (2017).

    Article  CAS  Google Scholar 

  41. Tao, L., Markham, J. N., Haq, Z. & Biddy, M. Techno-economic analysis for upgrading the biomass-derived ethanol-to-jet blendstocks. Green Chem. 19, 1082–1101 (2017).

    Article  CAS  Google Scholar 

  42. Olah, G. A. Beyond oil and gas: the methanol economy. Angew. Chem. Int. Ed. 44, 2636–2639 (2005).

    Article  CAS  Google Scholar 

  43. Olah, G. A., Goeppert, A. & Prakash, G. K. S. Beyond Oil and Gas: The Methanol Economy 2nd edn (Wiley, 2009).

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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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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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