Article

Discovery of optimal zeolites for challenging separations and chemical transformations using predictive materials modeling

  • Nature Communications 6, Article number: 5912 (2015)
  • doi:10.1038/ncomms6912
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Abstract

Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure. To date, 213 framework types have been synthesized and >330,000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol from fermentation broths and the hydroisomerization of alkanes with 18–30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modelling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds.

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References

  1. 1.

    Handbook of Petroleum Refining Processes McGraw-Hill (2003).

  2. 2.

    Catalytic isomerization process using a silicoaluminophosphate molecular sieve containing an occluded group VIII metal therein, U.S. Patent 4689138 (1987).

  3. 3.

    & Method for producing a plurality of lubricant base oils from paraffinic feedstock, U.S. Patent 6962651 (2005).

  4. 4.

    & Selective hydroisomerization of long chain normal paraffins. Appl. Catal. A 119, 121–138 (1994).

  5. 5.

    , , & Fischer-Tropsch waxes upgrading via hydrocracking and selective hydroisomerization. Oil Gas Sci. Technol. Rev. IFP 64, 91–112 (2009).

  6. 6.

    , & Anhydrous ethanol: a renewable source of energy. Renew. Sust. Energ. Rev. 14, 1830–1844 (2010).

  7. 7.

    , , & inStudies in Surface Science and catalysis eds Aiello R., Giordano G., Testa F. Vol. 1421595–1602Elsevier (2002).

  8. 8.

    et al. Adsorption of water and ethanol in MFI-type zeolites. Langmuir 28, 8664–8673 (2012).

  9. 9.

    , & Multicomponent adsorption of alcohols onto silicalite-1 from aqueous solution: Isotherms, structural analysis, and assessment of ideal adsorbed solution theory. Langmuir 28, 15566–15576 (2012).

  10. 10.

    , & A database of new zeolite-like materials. Phys. Chem. Chem. Phys. 13, 12407–12412 (2011).

  11. 11.

    et al. Large-scale screening of hypothetical metal-organic frameworks. Nat. Chem. 4, 83–89 (2012).

  12. 12.

    et al. Large-scale computational screening of zeolites for ethane/ethene separation. Langmuir 28, 11914–11919 (2012).

  13. 13.

    , & Predictive framework for shape-selective separations in three-dimensional zeolites and metal-organic frameworks. Langmuir 29, 5599–5608 (2013).

  14. 14.

    , , , & Exploring the limits of methane storage and delivery in nanoporous materials. J. Phys. Chem. C 118, 6941–6951 (2014).

  15. 15.

    , , & In silico design of porous polymer networks: high-throughput screening for methane storage materials. J. Am. Chem. Soc. 136, 5006–5022 (2014).

  16. 16.

    et al. In silico screening of carbon-capture materials. Nat. Mater. 11, 633–641 (2012).

  17. 17.

    & Accelerating applications of metal-organic frameworks for gas adsorption and separation by computational screening of materials. Langmuir 28, 14114–14128 (2012).

  18. 18.

    , , & Large-scale screening of zeolite structures for CO2 membrane separations. J. Am. Chem. Soc. 135, 7545–7552 (2013).

  19. 19.

    et al. Optimizing nanoporous materials for gas storage. Phys. Chem. Chem. Phys. 16, 5499–5513 (2014).

  20. 20.

    , , & High-throughput screening of porous crystalline materials for hydrogen storage capacity near room temperature. J. Phys. Chem. C 118, 5383–5389 (2014).

  21. 21.

    & Ethanol fermentation from biomass resources: current state and prospects. Appl. Microbiol. Biotechnol. 69, 627–642 (2006).

  22. 22.

    & Trends in biotechnological production of fuel ethanol from different feedstocks. Bioresour. Technol. 99, 5270–5295 (2008).

  23. 23.

    & Database of zeolite structures (2014).

  24. 24.

    et al. Diffusion of water and ethanol in silicalite crystals synthesized in fluoride media. Microporous Mesoporous Mater. 170, 259–265 (2013).

  25. 25.

    , , & Computer-assisted screening of ordered crystalline nanoporous adsorbents for separation of alkane isomers. Angew. Chem. Int. Ed. 51, 11867–11871 (2012).

  26. 26.

    , , , & Algorithms and tools for high-throughput geometry- based analysis of crystalline porous materials. Microporous Mesoporous Mater. 149, 134–141 (2012).

  27. 27.

    et al. Separation of hexane isomers in a metal-organic framework with triangular channels. Science 340, 960–964 (2013).

  28. 28.

    , & Cost-effective CO2 capture based on in silico screening of zeolites and process optimization. Phys. Chem. Chem. Phys. 15, 17601–17618 (2013).

  29. 29.

    , & Discovery of novel zeolites for natural gas purification through combined material screening and process optimization. AlChE J. 60, 1767–1785 (2014).

  30. 30.

    , , , & Flexibility as an indicator of feasibility of zeolite frameworks. J. Phys. Chem. C 116, 16175–16181 (2012).

  31. 31.

    , & Synthesis of a specified, silica molecular sieve by using computationally predicted organic structure-directing agents. Angew. Chem. Int. Ed. 53, 8372–8374 (2014).

  32. 32.

    et al. Computational design of metal-organic frameworks based on stable zirconium building units for storage and delivery of methane. Chem. Mater. 26, 5632–5639 (2014).

  33. 33.

    , & TraPPE-zeo: transferable potentials for phase equilibria force field for all-silica zeolites. J. Phys. Chem. C 117, 24375–24387 (2013).

  34. 34.

    & Transferable potentials for phase equilibria. 1. United-atom description of n-alkanes. J. Phys. Chem. B 102, 2569–2577 (1998).

  35. 35.

    & Novel configurational-bias Monte Carlo method for branched molecules. Transferable potentials for phase equilibria. 2. United-atom description of branched alkanes. J. Phys. Chem. B 103, 4508–4517 (1999).

  36. 36.

    , & Monte Carlo calculations for alcohols and their mixtures with alkanes. Transferable potentials for phase equilibria. 5. United-atom description of primary, secondary, and tertiary alcohols. J. Phys. Chem. B 105, 3093–3104 (2001).

  37. 37.

    , , , & Comparison of simple potential functions for simulating liquid water. J. Chem. Phys. 79, 926–935 (1983).

  38. 38.

    et al. A computational study of the adsorption of n-perfluorohexane in zeolite BCR-704. Fluid Phase Equil. 366, 146–151 (2014).

  39. 39.

    , , & Understanding the unusual adsorption behavior in hierarchical zeolite nanosheets. ChemPhysChem 15, 2225–2229 (2014).

  40. 40.

    & Computer Simulation of Liquids Clarendon (1987).

  41. 41.

    , & Prediction of low occupancy sorption of alkanes in silicalite. J. Phys. Chem. 94, 1508–1516 (1990).

  42. 42.

    & Computer simulations of the energetics and siting of n-alkanes in zeolites. J. Phys. Chem. 98, 8442–8452 (1994).

  43. 43.

    & Predicting multicomponent phase equilibria and free energies of transfer for alkanes by molecular simulation. J. Am. Chem. Soc. 119, 8921–8924 (1997).

  44. 44.

    , , , & Probing the relationship between slilicalite-1 defects and polyol adsorption properties. Langmuir 29, 6546–6555 (2013).

  45. 45.

    , , & Experimental and computational studies of the adsorption of CO2 and N2 on pure silica zeolites. Microporous Mesoporous Mater. 185, 157–166 (2014).

  46. 46.

    , , & Zeolites as alcohol adsorbents from aqueous solutions. Acta Period. Technol. 37, 83–87 (2006).

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Acknowledgements

Financial support from the Department of Energy Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG02–12ER16362 is gratefully acknowledged. This research used resources of the Argonne Leadership Computing Facility (ALCF) at Argonne National Laboratory, which is supported by the Office of Science of the Department of Energy under contract DE-AC02–06CH11357. Additional computer resources were provided by the Minnesota Supercomputing Institute.

Author information

Affiliations

  1. Departments of Chemistry and of Chemical Engineering and Materials Science and Chemical Theory Center, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, USA

    • Peng Bai
    • , Mi Young Jeon
    • , Limin Ren
    • , Michael Tsapatsis
    •  & J. Ilja Siepmann
  2. Leadership Computing Facility, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439, USA

    • Chris Knight
  3. Departments of Bioengineering and of Physics and Astronomy, Rice University, 6100 Main Street, Houston, Texas 77005, USA

    • Michael W. Deem

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Contributions

The screening studies for the water/ethanol and hydrocarbon mixtures were conceived by P.B., M.T. and J.I.S. and by P.B., M.W.D. and J.I.S., respectively. P.B. and C.K. collaborated on the implementation on Mira at ALCF, and all calculations and data analysis were performed by P.B. M.Y.J. and L.R. carried out the validation experiments. All authors contributed to the writing of the manuscript.

Competing interests

Ilja Siepmann, Peng Bai, and Michael Tsapatsis are declared to be inventors on provisional patent 62027529 and Ilja Siepmann, Peng Bai, Michael Tsapatsis, and Michael Deem are declared to be inventors on provisional patent 62027579 both filed by the University of Minnesota related to the work presented here.

Corresponding author

Correspondence to J. Ilja Siepmann.

Supplementary information

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    Supplementary Information

    Supplementary Figures 1-6, Supplementary Tables 1-2 and Supplementary References

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