Zirconium Doped Precipitated Fe-Based Catalyst for Fischer–Tropsch Synthesis to Light Olefins at Industrially Relevant Conditions

  • Sanpeng Zhang
  • Dailin Li
  • Yi LiuEmail author
  • Yi ZhangEmail author
  • Qing WuEmail author


Direct conversion of synthesis gas to light olefins (ethylene, propylene, and butylenes) over Fe–Zr co-precipitated catalysts was investigated in a continuous-flow fixed-bed reactor at industrially relevant conditions. The effect of incorporation of zirconium on the textural properties, surface physicochemical properties, and reduction/carburization ability of Fe-based multi-component catalysts were examined by N2 adsorption–desorption, X-ray diffraction, transmission electron microscope, H2 temperature-programmed reduction (H2-TPR), CO temperature-programmed reduction, and X-ray photoelectron spectroscopy. The results indicated that the addition of less zirconium can promote the dispersion of iron oxide particles and increase the specific surface area of catalyst, leads to a higher Fischer–Tropsch synthesis activity. However, excessive addition of the zirconium promoter will cover the surface active sites and suppress the reduction and carburization of catalyst, which lead to lower activity. Meanwhile, the catalytic stability was destroyed by the addition of less Zr. The charge transfer between Fe and other promoter was redistributed by Zr, which disturbed the original Fe–Mg interaction. When the content of Zr further increased, the stability was improved again by a new formed Fe–Zr interaction. The zirconium promoter can effectively inhibit the chain growth probability and hydrogenation ability, resulting in the improvement of light olefins selectivity.

Graphical Abstract


Fischer–Tropsch synthesis Heterogeneous catalysis Zirconium Fe-based catalyst Light olefins 



This work was supported by National Natural Science Foundation of P. R. China (No. 91334206 and 21606011), National “863” program of P. R. China (No. 2013AA031702), and China Postdoctoral Science Foundation (2016M591051 and 2017T100029).

Compliance with Ethical Standards

Conflict of interest

The authors declare no competing interest.


  1. 1.
    Wender I (1996) Fuel Process Technol 48:189CrossRefGoogle Scholar
  2. 2.
    Dry ME (2002) Catal Today 71:227CrossRefGoogle Scholar
  3. 3.
    Khodakov AY, Chu W, Fongarland P (2007) Chem Rev 107:1692CrossRefGoogle Scholar
  4. 4.
    Galvis HMT, de Jong KP (2013) ACS Catal 3:2130CrossRefGoogle Scholar
  5. 5.
    Zhong LS, Yu F, An YL, Zhao YH, Sun YH, Li ZJ, Lin TJ, Lin YJ, Qi XZ, Dai YY, Gu L, Hu JS, Jin SF, Shen Q, Wang H (2016) Nature 538:84CrossRefGoogle Scholar
  6. 6.
    Galvis HMT, Bitter JH, Khare CB, Ruitenbeek M, Dugulan AI, de Jong KP (2012) Science 335:835CrossRefGoogle Scholar
  7. 7.
    Cheng Y, Lin J, Xu K, Wang H, Yao X, Pei Y, Yan S, Qiao MH, Zong BN (2016) ACS Catal 6:389CrossRefGoogle Scholar
  8. 8.
    Liu Y, Chen JF, Bao J, Zhang Y (2015) ACS Catal 5:3905CrossRefGoogle Scholar
  9. 9.
    Yang Y, Xiang HW, Xu YY, Bai L, Li YW (2004) Appl Catal A 266:181CrossRefGoogle Scholar
  10. 10.
    Zhai P, Xu C, Gao R, Liu X, Li M, Li W, Fu X, Jia C, Xie J, Zhao M, Wang X, Li YW, Zhang QW, Wen XD, Ma D (2016) Angew Chem Int Ed 55:9902CrossRefGoogle Scholar
  11. 11.
    Li S, Li A, Krishnamoorthy S, Iglesia E (2001) Catal Lett 77:197CrossRefGoogle Scholar
  12. 12.
    Zhang CH, Yang Y, Teng BT, Li TZ, Zheng HY, Xiang HW, Li YW (2006) J Catal 237:405CrossRefGoogle Scholar
  13. 13.
    Yang J, Sun Y, Tang Y, Liu Y, Wang H, Tian L, Wang H, Zhang Z, Xiang H, Li YW (2006) J Mol Catal A 245:26CrossRefGoogle Scholar
  14. 14.
    Liu Y, Chen J, Zhang Y (2015) Reac Kinet Mech Cat 114:433CrossRefGoogle Scholar
  15. 15.
    Zhang Q, Kang J, Wang Y (2010) ChemCatChem 2:1030CrossRefGoogle Scholar
  16. 16.
    Lohitharn N, Goodwin JG, Lotero E (2008) J Catal 255:104CrossRefGoogle Scholar
  17. 17.
    Johnson GR, Werner S, Bell AT (2015) ACS Catal 5:5888CrossRefGoogle Scholar
  18. 18.
    Johnson GR, Bell AT (2016) ACS Catal 6:100CrossRefGoogle Scholar
  19. 19.
    Enache DI, Roy-Auberger M, Revel R (2004) Appl Catal A 268:51CrossRefGoogle Scholar
  20. 20.
    Li Z, Wu J, Yu J, Han D, Wu L, Li J (2016) J Mol Catal A 424:384CrossRefGoogle Scholar
  21. 21.
    Wu YJ, Zhang WT, Yang MM, Zhao YH, Liu ZT, Yan JY (2017) RSC Adv 7:24157CrossRefGoogle Scholar
  22. 22.
    Qing M, Yang Y, Wu B, Xu J, Zhang C, Gao P, Li YW (2011) J Catal 279:111CrossRefGoogle Scholar
  23. 23.
    Lohitharn N, Goodwin JG (2008) J Catal 257:142CrossRefGoogle Scholar
  24. 24.
    Liu Y, Fang K, Chen J, Sun Y (2007) Green Chem 9:611CrossRefGoogle Scholar
  25. 25.
    Cao J, Wang Y, Yu X, Wang S, Wu S, Yuan Z (2008) Appl Catal B 79:26CrossRefGoogle Scholar
  26. 26.
    Kumar S, Kumar S, Tiwari S, Srivastava S, Srivastava M, Yadav BK, Kumar S, Tran TT, Dewan AK, Mulchandani A, Sharma JG, Maji S, Malhotra BD (2015) Adv Sci 2:1500048CrossRefGoogle Scholar
  27. 27.
    Suo H, Wang S, Zhang C, Xu J, Wu B, Yang Y, Xiang H, Li YW (2012) J Catal 286:111CrossRefGoogle Scholar
  28. 28.
    Wan H, Wu B, Xiang H, Li Y (2012) ACS Catal 2:1877CrossRefGoogle Scholar
  29. 29.
    Dang S, Gao P, Liu Z, Chen X, Yang C, Wang H, Zhong L, Li S, Sun Y (2018) J Catal 364:382CrossRefGoogle Scholar
  30. 30.
    Liu Y, Chen JF, Zhang Y (2015) RSC Adv 5:29002CrossRefGoogle Scholar
  31. 31.
    Zhang W, Gao R, Su C, Yin Y (1993) Stud Surf Sci Catal 75:2793CrossRefGoogle Scholar
  32. 32.
    Chen N, Zhang J, Ma Q, Fan S, Zhao T (2016) RSC Adv 6:34204CrossRefGoogle Scholar
  33. 33.
    Graciani J, Mudiyanselage K, Xu F, Baber AE, Evans J, Senanayake SD, Stacchiola DJ, Liu P, Hrbek J, Sanz JF, Rodriguez JA (2014) Science 345:546CrossRefGoogle Scholar
  34. 34.
    Park JB, Graciani J, Evans J, Stacchiola D, Senanayake SD, Barrio L, Liu P, Sanz JF, Hrbek J, Rodriguez JA (2010) J Am Chem Soc 132:356CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Organic-Inorganic Composites, Department of Chemical EngineeringBeijing University of Chemical TechnologyBeijingChina
  2. 2.Department of Science & Technology DevelopmentChina National Offshore Oil CorporationBeijingChina

Personalised recommendations