Skip to main content
SpringerLink
Log in

Light olefins synthesis from C1-C2 paraffins via oxychlorination processes

  • Research Article
  • Published:
Frontiers of Chemical Science and Engineering Aims and scope Submit manuscript

Abstract

A two-step process was employed to convert methane or ethane to light olefins via the formation of an intermediate monoalkyl halide. A novel K4RuOCl10/TiO2 catalyst was tested for the oxidative chlorination of methane and ethane. The catalyst had high selectivity for methyl and ethyl chlorides, 80% and 90%, respectively. During the oxychlorination of ethane at T⩾250°C, the formation of ethylene as a reaction product along with ethyl chloride was observed. In situ Fourier transform infrared studies showed that the key intermediate for monoalkyl chloride and ethylene formation is the alkoxy group. The reaction mechanism for the oxidative chlorination of methane and ethane over the Ru-oxychloride catalyst was proposed. The novel fiber glass catalyst was also tested for the dehydrochlorination of alkyl chlorides to ethylene and propylene. Very high selectivities (up to 94%–98%) for ethylene and propylene formation as well as high stability were demonstrated.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Wang W, Jiang Y, Hunger M. Mechanistic investigations of the methanol-to-olefin (MTO) process on acidic zeolite catalysts by in situ solid-state NMR spectroscopy. Catalysis Today, 2006, 113(1–2): 102–114

    Article  CAS  Google Scholar 

  2. Yang G, Wei Y, Xu S, Chen J, Li J, Liu Z, Yu J R. Nanosizeenhanced lifetime of SAPO-34 catalysts in methanol-to-olefin reactions. J Phys Chem C, 2013, 117(16): 8214–8222

    Article  CAS  Google Scholar 

  3. Vora B V, Marker T L, Barger P T, Nilsen H R, Kvisle S, Fuglerud T. Economic route for natural gas conversion to ethylene and propylene. Studies in Surface Science and Catalysis, 1997, 107: 87–98

    Article  CAS  Google Scholar 

  4. Wang C, Xu L, Wang Q. Review of directly producing light olefins via CO hydrogenation. Journal of Natural Gas Chemistry, 2003, 12(1): 10–16

    CAS  Google Scholar 

  5. Abelló D S, Montané D D. Exploring iron-based multifunctional catalysts for Fischer-Tropsch synthesis: A review. ChemSusChem, 2011, 4(11): 1538–1556

    Article  Google Scholar 

  6. Galvis H M T, Bitter J H, Khare C B, Ruitenbeek M, Dugulan A I, de Jong K P. Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science, 2012, 325(6070): 835–838

    Article  Google Scholar 

  7. Chen W, Fan Z, Pan X, Bao X. Effect of confinement in carbon nanotubes on the activity of Fischer-Tropsch iron catalyst. Journal of the American Chemical Society, 2008, 130(29): 9414–9419

    Article  CAS  Google Scholar 

  8. Olah G A, Gupta B, Farina M, Felberg J D, Ip W M, Husain A, Karpeles R, Lammertsma K, Melhotra A K, Trivedi N J. Selective Monohalogenation of methane over supported acid or platinum metal catalysts and hydrolysis of methyl halides over γ-aluminasupported metal oxide/hydroxide catalysts. A feasible path for the oxidative conversion of methane into methyl alcohol/dimethyl ether. Journal of the American Chemical Society, 1985, 107(24): 7097–7105

    Article  CAS  Google Scholar 

  9. Olah G A, Renner R, Schilling P, Mo Y K. Antimony pentafluoride aluminum trichloride, and silver antimony hexafluoride catalyzed chlorination and chlorolysis of alkanes and cycloalkanes. Journal of the American Chemical Society, 1973, 95(23): 7686–7692

    Article  CAS  Google Scholar 

  10. Jauman D, Su B L. Direct catalytic conversion of chloromethane to higher hydrocarbons over a series of ZSM-5 zeolites exchanged with alkali cations. Jounal of Molecular Catalysis A, 2003, 197(1–2): 263–273

    Article  Google Scholar 

  11. Wei Y, Zhang D, Liu Z, Su B. Highly efficient catalytic conversion of chloromethane to light olefins over HSAPO-34 as studied by catalytic testing and in situ FTIR. Journal of Catalysis, 2006, 238(1): 46–57

    Article  CAS  Google Scholar 

  12. Seki K. Development of RuO2/Rutile TiO2 catalyst for industrial HCl oxidation process. Catalysis Surveys from Asia, 2010, 14(3–4): 168–175

    Article  CAS  Google Scholar 

  13. Taylor C E, Noceti R P, Schehl R R. Direct conversion of methane to liquid hydrocarbons through chlorocarbon intermediates. Studies in Surface Science and Catalysis, 1988, 36: 483–489

    Article  CAS  Google Scholar 

  14. Taylor C E. Conversion of substituted methanes over ZSM-catalyst. Stud Surf Sci Catal, 2000, 130D: 3633–3638

    Article  CAS  Google Scholar 

  15. Sun Y, Campbell S M, Lunsford J H, Lewis G E, Palke D, Tau L M. The catalytic conversion of methyl chloride to ethylene and propylene over phosphorus-modified Mg-ZSM-5 zeolites. Journal of Catalysis, 1993, 143(1): 32–44

    Article  CAS  Google Scholar 

  16. Zhang D, Wei Y, Xu L, Chang F, Liu Z, Meng S, Su B L, Liu Z. MgAPSO-34 molecular sieves with various Mg stoichiometries: Synthesis, characterization and catalytic behavior in the direct transformation of chloromethane into light olefins. Micro Meso Mater, 2008, 116(1–3): 684–692

    Article  CAS  Google Scholar 

  17. Liu Z, Huang L, Li W S, Yang F, Au C T, Zhou X P. Higher hydrocarbons from methane condensation mediated by HBr. Journal of Molecular Catalysis, 2007, 273(1–2): 14–20

    CAS  Google Scholar 

  18. Lin R, Ding Y, Gong L, Dong W, Wang J, Zhang T. Efficient and stable silica-supported iron phosphate catalysts for oxidative bromination of methane. Journal of Catalysis, 2010, 272(1): 65–73

    Article  CAS  Google Scholar 

  19. Degirmenci V, Yilmaz A, Uner D. Selective methane bromination over sulfated zirconia in SBA-15 catalysts. Catalysis Today, 2009, 142(1–2): 30–33

    Article  CAS  Google Scholar 

  20. Peringer E, Podkolzin S G, Jones M E, Olindo R, Lercher J A. LaCl3-based catalysts for oxidative chlorination of CH4. Topics in Catalysis, 2006, 38(1–3): 211–220

    Article  CAS  Google Scholar 

  21. Podkolzin S G, Stangland E E, Jones M E, Peringer E, Lercher J A. Methyl chloride production from methane over lantanium-based catalysts. Journal of the American Chemical Society, 2007, 129(9): 2569–2576

    Article  CAS  Google Scholar 

  22. Peringer E, Salzinger M, Hutt M, Lemonidou A A, Lercher J A. Modified lantanum catalysts for oxidative chlorination of methane. Topics in Catalysis, 2009, 52(9): 1220–1231

    Article  CAS  Google Scholar 

  23. He J, Xu T, Wang Z, Zhang Q, Deng W, Wang Y. Tranformation of methane to propylene: A two-step reaction route catalyzed by modified CeO2 nanocrystals and zeolites. Angewandte Chemie International Edition, 2012, 51(10): 2438–2442

    Article  CAS  Google Scholar 

  24. Xu T, Zhang Q, Song H, Wang Y. Fluoride-treated H-ZSM-5 as a highly selective and stable catalyst for the production of propylene from methyl halides. Journal of Catalysis, 2012, 295: 232–241

    Article  CAS  Google Scholar 

  25. Bal’zhinimaev B S, Paukshtis E A, Lapina O B, Suknev A P, Kirillov V L, Mikenin P E, Zagoruiko A N. Glass fiber materials as a new generation of structured catalysts. Studies in Surface Science and Catalysis, 2010, 175: 43–50

    Article  Google Scholar 

  26. Crihan D, Knapp M, Zweidinger S, Lundgren E, Weststrate C J, Andersen J N, Seitsonen A P, Over H. Stable deacon process for HCl oxidation over RuO2. Angewandte Chemie International Edition, 2008, 120(11): 2161–2164

    Google Scholar 

  27. Hevia M A G, Amrute A P, Schmidt T, Perez-Ramirez J. Transient mechanistic study of the gas-phase HCl oxidation to Cl2 on bulk and supported RuO2 catalysts. Journal of Catalysis, 2010, 276(1): 141–151

    Article  CAS  Google Scholar 

  28. Borello E, Zecchina A, Morterra C. Infrared study of methanol adsorption on Aerosil. I. Chemisorption at room temperature Journal of Physical Chemistry, 1967, 71(9): 2938–2945

    CAS  Google Scholar 

  29. Murray D K, Chang J W, Haw J F. Conversion of methyl halides to hydrocarbons on basic zeolites: A discovery by in situ NMR. Journal of the American Chemical Society, 1993, 115(11): 4732–4741

    Article  CAS  Google Scholar 

  30. Murray D K, Howard T, Goguen P W, Krawietz T R, Haw J F. Methyl halide reactions on multifunctional metal-exchanged zeolite catalysts. Journal of the American Chemical Society, 1994, 116(14): 6354–6360

    Article  CAS  Google Scholar 

  31. Paes L W, Faria R B, Machuca-Herrera J O, Machado S P. The linear μ-oxo-bis[pentachlororuthenate(IV)]_anion. Molecular orbital calculaions. Inorganica Chimica Acta, 2001, 321(1–2): 22–26

    Article  CAS  Google Scholar 

  32. Gazsi A, Koysa A, Bansagi T, Solymosi F. Adsorption and decomposition of ethanol on supported Au catalysts. Catalysis Today, 2011, 160(1): 70–78

    Article  CAS  Google Scholar 

  33. Hauchecorne B, Tytgat T, Verbruggen SW, Hauchecorne D, Terrens D, Smits M, Vinken K, Lenaerts S. Photocatalytic degradation of ethylene: An FTIR in situ study under atmospheric conditions. App Catal B Environ, 2011, 105(1–2): 111–116

    Article  CAS  Google Scholar 

  34. Singh M, Zhou N, Paul D K, Klabunde K J. IR spectral evidence of aldol condensation: Acetaldehyde adsorption over TiO2 surface. Journal of Catalysis, 2008, 260(2): 371–379

    Article  CAS  Google Scholar 

  35. Opre Z, Ferri D, Krumeich F, Mallat T, Baiker A. Insight into the nature of active redox sites in Ru-containing hydroxyapatite by DRIFT spectroscopy. Journal of Catalysis, 2007, 251(1): 48–58

    Article  CAS  Google Scholar 

  36. Wu W C, Chuang C C, Lin J L. Bonding geometry and reactivity of methoxy and ethoxy groups adsorbed on powdered TiO2. Journal of Physical Chemistry B, 2000, 104(36): 8719–8724

    Article  CAS  Google Scholar 

  37. Bhattacharyya K, Varma S, Tripathi A K, Bharadwaj S R, Tyagi A K. Mechanistic insight by in situ FTIR for the gas phase photooxidation of ethylene by V-doped titania and nano titania. Journal of Physical Chemistry B, 2009, 113(17): 5917–5928

    Article  CAS  Google Scholar 

  38. Bal’zhinimaev B S, Paukshtis E A, Vanag S V, Suknev A P, Zagoruiko A N. Glass Fiber Catalysts: Novel oxidation catalysts and catalytic technologies for environmental protection. Catalysis Today, 2010, 151(1–2): 195–199

    Article  Google Scholar 

  39. Gulyaeva Yu K, Suknev A P, Paukshtis E A, Bal’zhinimaev B S. Gas phase nitridation of silicate fiber glass materials with ammonia. Journal of Non-Crystalline Solids, 2011, 357(18): 3338–3344

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia

    Anton Shalygin, Evgenii Paukshtis, Evgenii Kovalyov & Bair Bal’zhinimaev

Authors
  1. Anton Shalygin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Evgenii Paukshtis
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Evgenii Kovalyov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bair Bal’zhinimaev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Bair Bal’zhinimaev.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shalygin, A., Paukshtis, E., Kovalyov, E. et al. Light olefins synthesis from C1-C2 paraffins via oxychlorination processes. Front. Chem. Sci. Eng. 7, 279–288 (2013). https://doi.org/10.1007/s11705-013-1338-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-013-1338-1

Keywords

Search

Navigation