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Thermal maps of gases in heterogeneous reactions

Nature volume 502, pages 537–540 (2013)Cite this article

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Abstract

More than 85 per cent of all chemical industry products are made using catalysts1,2, the overwhelming majority of which are heterogeneous catalysts2 that function at the gas–solid interface3. Consequently, much effort is invested in optimizing the design of catalytic reactors, usually by modelling4 the coupling between heat transfer, fluid dynamics and surface reaction kinetics. The complexity involved requires a calibration of model approximations against experimental observations5,6, with temperature maps being particularly valuable because temperature control is often essential for optimal operation and because temperature gradients contain information about the energetics of a reaction. However, it is challenging to probe the behaviour of a gas inside a reactor without disturbing its flow, particularly when trying also to map the physical parameters and gradients that dictate heat and mass flow and catalytic efficiency1,2,3,4,5,6,7,8,9. Although optical techniques10,11,12 and sensors13,14 have been used for that purpose, the former perform poorly in opaque media and the latter perturb the flow. NMR thermometry can measure temperature non-invasively, but traditional approaches applied to gases produce signals that depend only weakly on temperature15,16 are rapidly attenuated by diffusion16,17 or require contrast agents18 that may interfere with reactions. Here we present a new NMR thermometry technique that circumvents these problems by exploiting the inverse relationship between NMR linewidths and temperature caused by motional averaging in a weak magnetic field gradient. We demonstrate the concept by non-invasively mapping gas temperatures during the hydrogenation of propylene in reactors packed with metal nanoparticles and metal–organic framework catalysts, with measurement errors of less than four per cent of the absolute temperature. These results establish our technique as a non-invasive tool for locating hot and cold spots in catalyst-packed gas–solid reactors, with unprecedented capabilities for testing the approximations used in reactor modelling.

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Figure 1: Temperature mapping by motional averaging.
Figure 2: The chemical reactor system.
Figure 3: Temperature mapping.
Figure 4: Thermal map of gases in an operating catalytic microreactor.

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Acknowledgements

We thank J. Reimer, C. T. Campbell, W. S. Warren, I. Oppenheim and R. Bruinsma for discussions; N. K. Garg, C. T. Campbell, W. Gelbart and C. Knobler for reading the manuscript; M. T. Yeung for technical help with MATLAB; and J. Brown and R. Sharma for assistance with chemical synthesis. This work was funded by a Dreyfus New Faculty Award (L.-S.B.); a Beckman Young Investigator Award (L.-S.B.); US NSF CHE-1153159 (L.-S.B., O.M.Y.); BASF, Germany (synthesis); and the US DOE (O.M.Y.; porosity measurements).

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  1. William Morris

    Present address: Present address: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Tech Institute, K-156, Evanston, Illinois 60208, USA.,

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California at Los Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, USA,

    Nanette N. Jarenwattananon, Stefan Glöggler, Trenton Otto, Arek Melkonian, William Morris, Omar M. Yaghi & Louis-S. Bouchard

  2. Department of Chemistry and Biochemistry, Brigham Young University, C100 Benson Science Building, Provo, Utah 84602, USA,

    Scott R. Burt

  3. Department of Chemistry, University of California at Berkeley, 419 Latimer Hall, Berkeley, California 94720-1460, USA,

    Omar M. Yaghi

  4. Materials Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS 66R00200, Berkeley, California 94720, USA,

    Omar M. Yaghi

  5. NanoCentury KAIST Institute and Graduate School of Energy, Environment, Water, and Sustainability (World Class University), 291 Daehak-ro (373-1 Guseong-dong), Yuseong-gu, Daejeon 305-701, South Korea,

    Omar M. Yaghi

  6. California NanoSystems Institute at UCLA, 570 Westwood Plaza, Building 114, Los Angeles, California 90095, USA,

    Louis-S. Bouchard

  7. Department of Bioengineering, University of California at Los Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, USA,

    Louis-S. Bouchard

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  1. Nanette N. Jarenwattananon
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Contributions

N.N.J., S.G., T.O., A.M. and S.R.B. performed the experiments and collected the data. N.N.J. and W.M. performed the chemical synthesis. N.N.J., S.G., T.O., A.M., S.R.B. and L.-S.B. conducted the data processing and error analysis. N.N.J., S.G., S.R.B., O.M.Y. and L.-S.B. wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Louis-S. Bouchard.

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The authors declare no competing financial interests.

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This file contains Supplementary Methods, Supplementary Figures 1-15, Supplementary Text and Data, Supplementary Tables 1-4 and additional references. (PDF 2037 kb)

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Jarenwattananon, N., Glöggler, S., Otto, T. et al. Thermal maps of gases in heterogeneous reactions. Nature 502, 537–540 (2013). https://doi.org/10.1038/nature12568

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