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Effects of Support on Sulfur Tolerance and Regeneration of Pt Catalysts Measured by Ethylene Hydrogenation and EXAFS

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Abstract

The effect of support on sulfur tolerance and regenerability under reducing environments was investigated by rate measurements for ethylene hydrogenation, hydrogen chemisorption, and extended X-ray absorption fine structure (EXAFS). Catalysts, 1 % Pt/Al2O3 and 1 % Pt/P25 (TiO2), were tested after sulfidation in H2S/H2 at 250 °C followed by regeneration treatments in H2 at 250, 350 and 450 °C. Our combined results showed a 20–27 times decrease in the rate of ethylene hydrogenation on both sulfided catalysts, accompanied by a 4–6 times drop in the Pt surface area. Regenerations up to 450 °C were unable to remove all the sulfur, as evidenced by the presence of Pt–S bonds by EXAFS at about 2.25–2.33 Å, characteristic lengths for chemisorbed sulfur and bulk-type PtS. However, a partial recovery of the hydrogenation rate per mole of Pt was observed on sulfided Pt/Al2O3 after reduction at 450 °C, while the induction of strong metal support interactions (SMSI) at reduction temperature above 350 °C was observed on Pt/P25, regardless of the presence of sulfur. For Pt/P25, the reversal of the SMSI state together with sulfur removal by mild oxidation suggests that sequential reduction/oxidation treatments may be more effective in restoring the S-free state of TiO2-supported catalysts.

Graphical Abstract

Pt/Al2O3 and Pt/TiO2 (P25) sulfur tolerance and regenerability were evaluated after reduction treatments in H2. Both catalysts were equally poisoned by sulfur based on C2H4 hydrogenation. Reduction treatments up to 450 °C were not able to remove sulfur on either catalyst. Sulfur on Pt may inhibit the formation of the SMSI state on Pt/TiO2, especially below 350 °C.

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Acknowledgments

The authors would like to acknowledge Drs. Stuart Soled, Michael Daage, Pallassana S. Vankataraman, Prasenjeet Ghosh and Yogesh V. Joshi for useful discussions and active participation in this work and ExxonMobil Research and Engineering Company for financial support.

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Authors and Affiliations

  1. School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN, 47907-2100, USA

    Jorge H. Pazmiño, Fabio H. Ribeiro & W. Nicholas Delgass

  2. ExxonMobil Research and Engineering Company, Route 22, Annandale, NJ, 08801, USA

    Chuansheng Bai

  3. Chemical Technology Division, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL, 60439, USA

    Jeffrey T. Miller

Authors
  1. Jorge H. Pazmiño
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  2. Chuansheng Bai
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  4. Fabio H. Ribeiro
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  5. W. Nicholas Delgass
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Correspondence to W. Nicholas Delgass.

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Pazmiño, J.H., Bai, C., Miller, J.T. et al. Effects of Support on Sulfur Tolerance and Regeneration of Pt Catalysts Measured by Ethylene Hydrogenation and EXAFS. Catal Lett 143, 1098–1107 (2013). https://doi.org/10.1007/s10562-013-1135-y

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