Skip to main content
Log in

Catalytic structure and reaction performance of PtSnK/ZSM-5 catalyst for propane dehydrogenation: influence of impregnation strategy

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

In this study, a series of PtSnK/ZSM-5 catalysts for propane dehydrogenation were prepared by changing the impregnation sequence of platinum and tin precursors (co-impregnation and successive impregnation). To investigate the influence of impregnation strategy on the catalyst structure and the reaction performance, the prepared samples were studied by several techniques, including XRD, nitrogen adsorption, ICP, TEM, NH3-TPD, FT-IR, hydrogen chemisorption, H2-TPR, and TPO. It was found that the prepared sample with co-impregnation method showed the highest reaction stability and selectivity when comparing with the ones prepared by the sequential impregnation. As for the co-impregnated catalyst, high metal dispersion, strong interaction of Pt with Sn oxide together with the decreased catalyst acidity were all responsible for the improved reaction properties and better catalytic capacity to resist the coke. Nevertheless, over the sequentially impregnated catalysts, the increased catalyst acidity and the relatively easy reduction of tin species were found when the Pt components were deposited first. Furthermore, the successive impregnation with inverse sequence led to the wide metallic distribution and the restricted transformation of the active sites. All of these factors were disadvantageous to the reaction to be carried out. Finally, a model for the influences of impregnation sequence was proposed based on the obtained results.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Chantaravitoon P, Chavadej S, Schwank J (2004) Pt–Sn/Al2O3 catalysts: effect of catalyst preparation and chemisorption methods on H2 and O2 uptake. Chem Eng J 98:99–104

    Article  Google Scholar 

  2. Zhang YW, Zhou YM, Shi JJ, Zhou SJ, Sheng XL, Zhang ZW, Xiang SM (2014) Comparative study of bimetallic Pt–Sn catalysts supported on different supports for propane dehydrogenation. J Mol Catal A 381:138–147

    Article  Google Scholar 

  3. Zhou SJ, Zhou YM, Shi JJ, Zhang YW, Sheng XL, Zhang ZW (2015) Synthesis of Ce-doped mesoporous c-alumina with enhanced catalytic performance for propane dehydrogenation. J Mater Sci 50:3984–3993

    Article  Google Scholar 

  4. Zhang YW, Zhou YM, Huang L, Zhou SJ, Sheng XL, Wang QL, Zhang C (2015) Structure and catalytic properties of the Zn-modified ZSM-5 supported platinum catalyst for propane dehydrogenation. Chem Eng J 270:352–361

    Article  Google Scholar 

  5. Sattler JJHB, Beale AM, Weckhuysen BM (2013) Operando raman spectroscopy study on the deactivation of Pt/Al2O3 and Pt–Sn/Al2O3 propane dehydrogenation catalysts. Phys Chem Chem Phys 15:12095–12103

    Article  Google Scholar 

  6. Zhang YW, Zhou YM, Tang MH, Liu X, Duan YZ (2012) Effect of La calcination temperature on catalytic performance of PtSnNaLa/ZSM-5 catalyst for propane dehydrogenation. Chem Eng J 181–182:530–537

    Article  Google Scholar 

  7. Zhu H, Anjum DH, Wang Q, Abou-Hamad E, Emsley L, Dong H, Laveille P, Li L, Samal AK, Basset JM (2014) Sn surface-enriched Pt–Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation. J Catal 320:52–62

    Article  Google Scholar 

  8. Deng L, Shishido T, Teramura K, Tanaka T (2014) Effect of reduction method on the activity of Pt–Sn/SiO2 for dehydrogenation of propane. Catal Today 232:33–39

    Article  Google Scholar 

  9. Zhang YW, Zhou YM, Huang L, Xue MW, Zhang SB (2011) Sn-modified ZSM-5 as support for platinum catalyst in propane dehydrogenation. Ind Eng Chem Res 50:7896–7902

    Article  Google Scholar 

  10. Zangeneh F, Mehrazma S, Sahebdelfar S (2013) The influence of solvent on the performance of Pt–Sn/theta-Al2O3 propane dehydrogenation catalyst prepared by co-impregnation method. Fuel Process Technol 109:118–123

    Article  Google Scholar 

  11. Coloma F, Sepúlveda-Escribano A, Fierro JLG, Rodríguez-Reinoso F (1996) Crotonaldehyde hydrogenation over bimetallic Pt–Sn catalysts supported on pregraphitized carbon black. Effect of the preparation method. Appl Catal A Gen 148:63–80

    Article  Google Scholar 

  12. Margitfalvi JL, Borbáth I, Lázár K, Tfirst E, Szegedi A, Hegedűs M, Gőbölös S (2001) In situ characterization of Sn–Pt/SiO2 catalysts used in low temperature oxidation of CO. J Catal 203:94–103

    Article  Google Scholar 

  13. Baronetti GT, de Miguel SR, Scelza OA, Fritzler MA, Castro AA (1985) Pt–Sn/Al2O3 catalysts—studies of the impregnation step. Appl Catal 19:77–85

    Article  Google Scholar 

  14. Shu Y, Murillo LE, Bosco JP, Huang W, Frenkel AI, Chen JG (2008) The effect of impregnation sequence on the hydrogenation activity and selectivity of supported Pt/Ni bimetallic catalysts. Appl Catal A Gen 339:169–179

    Article  Google Scholar 

  15. Chantaravitoon P, Chavadej S, Schwank J (2004) Temperature-programmed desorption of methanol and oxidation of methanol on Pt–Sn/Al2O3 catalysts. Chem Eng J 97:161–171

    Article  Google Scholar 

  16. Morales R, Melo L, Llanos A, Zaera F (2005) Characterization of bifunctional PtSn/H[Al]ZSM5 catalysts: a comparison between two impregnation strategies. J Mol Catal A 228:227–232

    Article  Google Scholar 

  17. Zhang YW, Zhou YM, Qiu AD, Wang Y, Xu Y, Wu PC (2006) Propane dehydrogenation on PtSn/ZSM-5 catalyst: effect of tin as a promoter. Catal Commun 7:860–866

    Article  Google Scholar 

  18. Bhasin MM, McCain JH, Vora BV, Imai T, Pujado PR (2001) Dehydrogenation and oxydehydrogenation of paraffins to olefins. Appl Catal A Gen 221:397–419

    Article  Google Scholar 

  19. Siri GJ, Bertolini GR, Casella ML, Ferretti OA (2005) PtSn/γ-Al2O3 isobutane dehydrogenation catalysts: the effect of alkaline metals addition. Matt Lett 59:2319–2324

    Article  Google Scholar 

  20. Zhang SB, Zhou YM, Zhang YW, Huang L (2010) Effect of K addition on catalytic performance of PtSn/ZSM-5 catalyst for propane dehydrogenation. Catal Lett 135:76–82

    Article  Google Scholar 

  21. Zhang YW, Zhou YM, Qiu AD, Wang Y, Xu Y, Wu PC (2006) Effect of alumina binder on catalytic performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation. Ind Eng Chem Res 45:2213–2219

    Article  Google Scholar 

  22. Nawaz Z, Tang X, Chu Y, Wei F (2010) Influence of calcination temperature and reaction atmosphere on the catalytic properties of Pt–Sn/SAPO-34 for propane dehydrogenation. Chin J Catal 31:552–556

    Article  Google Scholar 

  23. Zhang YW, Zhou YM, Liu H, Wang Y, Xu Y, Wu PC (2007) Effect of La addition on catalytic performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation. Appl Catal A 333:202–210

    Article  Google Scholar 

  24. Yu CL, Ge QJ, Xu HY, Li WZ (2006) Effects of Ce addition on the Pt–Sn/gamma-Al2O3 catalyst for propane dehydrogenation to propylene. Appl Catal A Gen 315:58–67

    Article  Google Scholar 

  25. Zhang YW, Zhou YM, Shi JJ, Sheng XL, Duan YZ, Zhou SJ, Zhang ZW (2012) Effect of zinc addition on catalytic properties of PtSnK/γ-Al2O3 catalyst for isobutane dehydrogenation. Fuel Process Technol 96:220–227

    Article  Google Scholar 

  26. Zhang YW, Zhou YM, Sheng XL, Wan LH, Li Y, Xiao YM, Yu B, Zeng Z (2012) Effect of the competitive adsorbates on the catalytic performances of PtSnK/γ-Al2O3 catalyst for isobutane dehydrogenation. Fuel Process Technol 104:23–30

    Article  Google Scholar 

  27. Yu CL, Xu HY, Ge QJ, Li WZ (2007) Properties of the metallic phase of zinc-doped platinum catalysts for propane dehydrogenation. J Mol Catal A 266:80–87

    Article  Google Scholar 

  28. Bariås OA, Holmen A, Blekkan EA (1995) Propane dehydrogenation over supported platinum catalysts-effect of tin as a promoter. Catal Today 24:361–364

    Article  Google Scholar 

  29. Bariås OA, Holmen A, Blekkan EA (1996) Propane dehydrogenation over supported Pt and Pt–Sn catalysts: catalyst preparation, characterization, and activity measurements. J Catal 158:1–12

    Article  Google Scholar 

  30. Shi JJ, Zhou YM, Zhang YW, Zhou SJ, Zhang ZW, Kong J, Guo M (2014) Synthesis of magnesium-modified mesoporous Al2O3 with enhanced catalytic performance for propane dehydrogenation. J Mater Sci 49:5772–5781

    Article  Google Scholar 

  31. Balakrishnan K, Schwank J (1991) A chemisorption and XPS study of bimetallic Pt–Sn/Al2O3 catalysts. J Catal 127:287–306

    Article  Google Scholar 

  32. Nawaz Z, Tang X, Wang Y, Wei F (2010) Parametric characterization and influence of tin on the performance of Pt–Sn/SAPO-34 catalyst for selective propane dehydrogenation to propylene. Ind Eng Chem Res 49:1274–1280

    Article  Google Scholar 

  33. Lin LW, Yang WS, Jia JF, Xu ZS, Zhang T, Fan YN, Kou Y, Shen JY (1999) Surface structure and reaction performances of highly dispersed and supported bimetallic catalysts. Sci Chin Ser B 42:571–580

    Article  Google Scholar 

  34. Treesukol P, Srisuk K, Limtrakul J, Truong TH (2005) Nature of the metal-support interaction in bifunctional catalytic Pt/H-ZSM-5 zeolite. J Phys Chem B 109:11940–11945

    Article  Google Scholar 

  35. Bai LY, Zhou YM, Zhang YW, Liu H, Tang MH (2009) Influence of calcium addition on catalytic properties of PtSn/ZSM-5 catalyst for propane dehydrogenation. Catal Lett 129:449–456

    Article  Google Scholar 

  36. Larsson M, Hultén M, Blekkan EA, Andersson B (1996) The effect of reaction conditions and time on stream on the coke formed during propane dehydrogenation. J Catal 164:44–53

    Article  Google Scholar 

  37. Lin LW, Zhang T, Zang JL, Xu ZS (1990) Dynamic process of carbon deposition on Pt and Pt–Sn catalysts for alkane dehydrogenation. Appl Catal 67:11–23

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant nos. 21376051, 21106017 and 21306023), Natural Science Foundation of Jiangsu Province of China (Grant no. BK20131288), Fund Project for Transformation of Scientific and Technological Achievements of Jiangsu Province of China (Grant no. BA2011086), and Instrumental Analysis Fund of Southeast University.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yuming Zhou.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, Y., Zhou, Y., Zhang, S. et al. Catalytic structure and reaction performance of PtSnK/ZSM-5 catalyst for propane dehydrogenation: influence of impregnation strategy. J Mater Sci 50, 6457–6468 (2015). https://doi.org/10.1007/s10853-015-9201-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-015-9201-z

Keywords

Navigation