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Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 1, pp 307–325 | Cite as

Effect of iron oxide precursor on the properties and ammonia synthesis activity of fused iron catalysts

  • Ali JafariEmail author
  • Abbas Ebadi
  • Saeed Sahebdelfar
Article
  • 90 Downloads

Abstract

Triply (Al, Ca and K) promoted wustite-based iron catalyst was prepared and compared with a similarly prepared magnetite catalyst for textural properties and performance in ammonia synthesis. The catalysts were synthesized by fusion method using Fe3O4 and metallic iron with similar nominal loading of promoters in both catalysts. The samples were characterized by N2 adsorption/desorption, XRD, H2-TPR, H2-TPD and EDS-mapping techniques. The Fe2+/Fe3+ ratio in the samples was measured by chemical titration. The stability and activity tests were performed in a fixed-bed reactor under kinetically controlled conditions (T = 350–530 °C, P = 30 bar, catalyst loading = 1 g, feed flow rate = 120 Nml/min and H2/N2 = 3/1 mol/mol). The catalysts exhibited different distribution of the promoters. Catalytic test results for ammonia synthesis showed that the activity of the wustite catalyst was higher than that of magnetite catalyst under the same reaction conditions. The former was also more readily activated by H2-reduction. The wustite catalyst showed similar thermostability and mechanical strength as the magnetite catalyst. The ammonia synthesis reaction was not intra-particle diffusion limited on either catalyst. The favorable properties of wustite-based catalysts can be employed to reduce the energy consumption and related emissions of ammonia plants significantly.

Keywords

Ammonia synthesis Iron catalyst Wustite Magnetite Diffusion limitation 

Notes

Compliance with Ethical Standard

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11144_2018_1498_MOESM1_ESM.docx (702 kb)
Supplementary material 1 (DOCX 701 kb)

References

  1. 1.
    Bicer Y, Dincer I, Zamfirescu C, Vezina G, Raso F (2016) Comparative life cycle assessment of various ammonia production methods. J Clean Prod 135:1379–1395CrossRefGoogle Scholar
  2. 2.
    Afif A, Radenahmad N, Cheok Q, Shams S, Kim JH, Azad AK (2016) Ammonia-fed fuel cells: a comprehensive review. Renew Sust Energ Rev 60:822–835CrossRefGoogle Scholar
  3. 3.
    Schüth F, Palkovits R, Schlögl R, Su DS (2012) Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition. Energy Environ Sci 5:6278–6289CrossRefGoogle Scholar
  4. 4.
    Liu HZ (2014) Ammonia synthesis catalyst 100 years: practice, enlightenment and challenge. Chin J Catal 35:1619–1640CrossRefGoogle Scholar
  5. 5.
    Kojima R, Aiwa K (2001) Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis part 1. preparation and characterization. Appl Catal A: Gen 215:149–160CrossRefGoogle Scholar
  6. 6.
    Somorjai G, Materer N (1994) Surface structures in ammonia synthesis. Top Catal 1:215–231CrossRefGoogle Scholar
  7. 7.
    Lendzion-Bielun Z, Jedrzejewski R, Ekiert E, Arabczyk W (2011) Heterogeneity of ingot of the fused iron catalyst for ammonia synthesis. Appl Catal A: Gen 400:48–53CrossRefGoogle Scholar
  8. 8.
    Shen J, Zhu SY, Feng XT (2001) Ammonia synthesis, in fertilizer engineering science series. Chemical Industry Press, BeijingGoogle Scholar
  9. 9.
    Saadatjou N, Jafari A, Sahebdelfar S (2015) Ruthenium nanocatalysts for ammonia synthesis: a review. Chem Eng Commun 202:420–448CrossRefGoogle Scholar
  10. 10.
    Jafari A, Saadatjou N, Sahebdelfar S (2015) Influence of chemical treatments of activated carbon support on the performance and deactivation behavior of promoted Ru catalyst in ammonia synthesis. Int J Hydrogen Energy 40:3659–3671CrossRefGoogle Scholar
  11. 11.
    Zheng X, Zhang SH, Xu J, Wei K (2002) Effect of thermal and oxidative treatments of activated carbon on its surface structure and suitability as a support for barium promoted ruthenium in ammonia synthesis catalysts. Carbon 40:2597–2603CrossRefGoogle Scholar
  12. 12.
    Wang WX, Zhao HQ, Du BS, Wen JM, Li F, Wang DM (1995) Activity and reduction behavior of fused iron catalysts containing cobalt for ammonia synthesis: a structure study. Appl Catal A: Gen 122:5–20CrossRefGoogle Scholar
  13. 13.
    Kaleficzuk RJ (2000) Cobalt promoted fused iron catalyst for ammonia synthesis. Int J Inorg Mater 2:233–239CrossRefGoogle Scholar
  14. 14.
    Stretsov OA, Dvornik OS, Lytkin VP (1977) Study of ammonia synthesis catalyst with different iron (II) content. Khim KhimTekhnol 20:1622–1626Google Scholar
  15. 15.
    Artyukh YN, Fedun OS, Zyuzya LA (1980) Activity of once-promoted catalysts of ammonia synthesis containing a different amount of iron (II). Katal Katal 18:20–23Google Scholar
  16. 16.
    Liu HZ, Li XN (2000) Precursor of iron catalyst for ammonia synthesis: Fe3O4, Fel.xO, Fe2O3 or their mixture? Stud Surf Sci Catal 130:2207–2212CrossRefGoogle Scholar
  17. 17.
    Pu Z, Zheng Y, Liu HZ, Li XN (2011) Influence of promoter and Fe2+/Fe3+ ratio on microstructure of fused iron catalysts for ammonia synthesis. Ind J Chem 50:156–162Google Scholar
  18. 18.
    Hazen RM, Jeanloz R (1984) Wustite (Fe1−xO): a review of its defect structure and physical properties. Rev Geophys Space Phys 22:37–46CrossRefGoogle Scholar
  19. 19.
    Galaria A, Kahn ML, Lecante P, Barbara B, Chaudret B (2008) Fe1-yO nanoparticles: organometallic synthesis and magnetic properties. Chem Phys Chem 9:776–780CrossRefGoogle Scholar
  20. 20.
    Figurski MJ, Arabczyk W, Lendzion-Bielun Z, Kalenczuk RJ, Lenart S (2003) On the distribution of aluminium and magnesium oxides in wustite catalysts for ammonia synthesis. Appl Catal A: Gen 247:9–15CrossRefGoogle Scholar
  21. 21.
    Czekajlo L, Lendzion-Bielun Z (2017) Wustite based iron-cobalt catalyst for ammonia synthesis. Catal Today 286:114–117CrossRefGoogle Scholar
  22. 22.
    Han W, Huang S, Cheng T, Tang H, Li Y, Liu HZ (2015) Promotion of Nb2O5 on the wustite-based iron catalyst for ammonia synthesis. Appl Surf Sci 353:17–23CrossRefGoogle Scholar
  23. 23.
    Liu HZ (2013) Ammonia synthesis catalysts, innovation and practice. World Scientific Publishing Co., Pte. Ltd. and Chemical Industry Press, New JerseyCrossRefGoogle Scholar
  24. 24.
    Cullity BD, Stock SR (2001) Elements of X-ray diffraction. Prentice-Hall, New JerseyGoogle Scholar
  25. 25.
    Chaklader ACD, Blair GR (1970) Differential thermal study of FeO and Fe3O4. J Therm Anal 2:165–179CrossRefGoogle Scholar
  26. 26.
    Pernicone N (2003) Catalysis at the nanoscale level. Cattech 7:196–204CrossRefGoogle Scholar
  27. 27.
    Zheng Y, Liu HZ, Liu Li X (2009) In situ X-ray diffraction study of reduction processes of Fe3O4- and Fe1−xO-based ammonia-synthesis catalysts. J Solid State Chem 182:2385–2391CrossRefGoogle Scholar
  28. 28.
    Redhead PA (1962) Thermal desorption of gases. Vacuum 12:203–211CrossRefGoogle Scholar
  29. 29.
    Argyle MD, Bartholomew CH (2015) Heterogeneous catalyst deactivation and regeneration: A review. Catalysts 5:145–269CrossRefGoogle Scholar
  30. 30.
    Li X, Cen Y, Liu HZ, Xu Y, Lv G (2004) Thermal stability of wustite structure modified with calcium cations. React Kinet Catal Lett 81:313–320CrossRefGoogle Scholar
  31. 31.
    Xiao F, Jin Y (2012) The study on mechanism of thermostability of wustite-based ammonia synthesis catalyst. Adv Mater Res 550–553:266–269CrossRefGoogle Scholar
  32. 32.
    Stoltze P (1987) Surface science as the basis for the understanding of the catalytic synthesis of ammonia. Phys Scr 36:824–864CrossRefGoogle Scholar
  33. 33.
    Pernicone N, Ferrero F, Rossetti I, Forni L, Canton P, Riello P, Fagherazzi G, Signoretto M, Pinna F (2003) Wustite as a new precursor of industrial ammonia synthesis catalysts. Appl Catal A: Gen 251:121–129CrossRefGoogle Scholar
  34. 34.
    Fogler HS (2006) Elements of chemical reaction engineering, 4th edn. Prentice-Hall, New JersyGoogle Scholar
  35. 35.
    Petersen EE (1965) A general criterion for diffusion influenced chemical reactions in porous solids. Chem Eng Sci 20:587–591CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Catalyst Research Group, Petrochemical Research and Technology CompanyNational Petrochemical CompanyTehranIran

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