Acrylic acid synthesis by oxidative condensation of methanol and acetic acid on B–P–V–W–Ox/SiO2 catalyst

Authors

DOI:

https://doi.org/10.15587/1729-4061.2019.156764

Keywords:

acrylic acid, methanol, acetic acid, heterogeneous catalysts, hydrothermal treatment

Abstract

The process of oxidative condensation of methanol with acetic acid to acrylic acid on B–P–V–W–Ox/SiO2 catalyst modified by hydrothermal method has been studied. Modification of the catalyst by hydrothermal treatment of the carrier changes its physical and chemical properties, and therefore its catalytic properties. The influence of the main technological parameters – temperature, contact time and ratio of reagents on the selectivity and yield of the reaction products and on the conversion of acetic acid has been studied when hydrothermally treated catalyst was used. The best time of contact was 8 sec. which allows to reach the highest selectivity and yield of acrylic acid and methyl acrylate. The highest catalytic activity of the designed catalyst is observed at the reaction temperature of 673 K, however, it is impossible to increase temperature over this value due to the limited thermal stability of the catalyst and the sharp increase in the formation of complete oxidation products. With an increase of methanol part in the ratio of reagents (methanol: acetic acid) to 1,2:1, the selectivity of acrylic acid and methyl acrylate increases, and the selectivity of by-products is significantly reduced. The highest yield of the target products in the reaction of oxidative condensation of methanol with acetic acid is observed at a ratio of oxygen: acetic acid 1,5:1. The growth of the oxygen: acetic acid ratio promotes reduce of acetone and methyl acetate selectivity but does not change the selectivity of methyl acrylate and significantly increases the selectivity and yield of acrylic acid. At the best conditions of the reaction it was possible to achieve 54.7 % total yield of acrylic acid and methyl acrylate. Due to the wide availability and relatively low cost of the initial reagents (methanol and acetic acid), the synthesis of acrylic acid by the oxidative condensation of methanol with acetic acid in the presence of the developed catalyst is very promising

Author Biographies

Roman Nebesnyi, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

PhD, Leading Researcher

Department of Organic Products Technology

 

Zorian Pikh, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

Doctor of Chemical Sciences, Professor

Department of Organic Products Technology

Iryna Kubitska, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

Junior Researcher

Department of Organic Products Technology

Oksana Orobchuk, Lviv Polytechnic National University S. Bandery str., 12, Lviv, Ukraine, 79013

PhD, Assistant

Department of Organic Products Technology

Andrii Lukyanchuk, Volynholding, OJSC Franka str., 4, township Torchin, Volyn region, Ukraine, 45612

Laboratory assistant

References

  1. Taniguchi, A., Kokubo, T., Takesada, K., Kondo, K., Chiba, T., Kumasaki, A., Kaneda, Yu. (2003). Pat. No. US7309736B2 USA. Acrylic block copolymer and thermoplastic resin composition. No. 10/522,869; declareted: 31.07.2003; published: 18.12.2007.
  2. Olson, J. M., Srinivasan, K. R. (2005). Pat. No. US7435523B2 USA. Chemically prepared toners with size limiting binders. No. 43013714; declareted: 1.06.2005; published: 14.10.2008.
  3. James, S. (2016). Acrylic Acid Market Size. San Francisco: Grand View Research, 115.
  4. Liu, C.-H., Lai, N.-C., Lee, J.-F., Chen, C.-S., Yang, C.-M. (2014). SBA-15-supported highly dispersed copper catalysts: Vacuum–thermal preparation and catalytic studies in propylene partial oxidation to acrolein. Journal of Catalysis, 316, 231–239. doi: https://doi.org/10.1016/j.jcat.2014.05.013
  5. Sert, E., Atalay, F. S. (2012). Esterification of Acrylic Acid with Different Alcohols Catalyzed by Zirconia Supported Tungstophosphoric Acid. Industrial & Engineering Chemistry Research, 51 (19), 6666–6671. doi: https://doi.org/10.1021/ie202609f
  6. Peterson, C. J., Chapman, J. T., Gallacher, J., Pan T. (2013). Pat. No. US058441B2 USA. Processes for producing acrylic acids and acrylates. No. WO2013052471A1; published: 11.04.2013.
  7. Ai, M. (1988). Vapor-phase reaction of methanol with methyl acetate and acetic acid in the presence of oxygen. Journal of Catalysis, 112 (1), 194–200. doi: https://doi.org/10.1016/0021-9517(88)90133-9
  8. Ormsby, G., Hargreaves, J. S. J., Ditzel, E. J. (2009). A methanol-only route to acetic acid. Catalysis Communications, 10 (9), 1292–1295. doi: https://doi.org/10.1016/j.catcom.2009.02.005
  9. Da Silva, M. J. (2016). Synthesis of methanol from methane: Challenges and advances on the multi-step (syngas) and one-step routes (DMTM). Fuel Processing Technology, 145, 42–61. doi: https://doi.org/10.1016/j.fuproc.2016.01.023
  10. Nebesnyi, R. (2015). Complex oxide catalysts of acrylic acid obtaining by aldol condensation method. Eastern-European Journal of Enterprise Technologies, 1 (6 (73)), 13–16. doi: https://doi.org/10.15587/1729-4061.2015.37405
  11. Nebesna, Yu., Ivasiv, V., Nebesnyi, R. (2015). The study of technological and kinetic regularities of simultaneous methacrylates obtaining over zirconium-containing catalysts. Eastern-European Journal of Enterprise Technologies, 5 (6 (77)), 49–52. doi: https://doi.org/10.15587/1729-4061.2015.51348
  12. Khalameida, S., Nebesnyi, R., Pikh, Z., Ivasiv, V., Sydorchuk, V., Nebesna, Y., Kucio, K. (2018). Catalytic aldol condensation of formaldehyde with acetic acid on titanium phosphates modified by different techniques. Reaction Kinetics, Mechanisms and Catalysis, 125 (2), 807–825. doi: https://doi.org/10.1007/s11144-018-1443-8
  13. Whiting, G. T., Bartley, J. K., Dummer, N. F., Hutchings, G. J., Taylor, S. H. (2014). Vanadium promoted molybdenum phosphate catalysts for the vapour phase partial oxidation of methanol to formaldehyde. Applied Catalysis A: General, 485, 51–57. doi: https://doi.org/10.1016/j.apcata.2014.07.029
  14. Behera, G. C., Parida, K. (2012). Selective gas phase oxidation of methanol to formaldehyde over aluminum promoted vanadium phosphate. Chemical Engineering Journal, 180, 270–276. doi: https://doi.org/10.1016/j.cej.2011.11.047
  15. Ai, M. (1990). Reaction of acetic acid with methanol over vanadium-titanium binary phosphate catalysts in the presence of oxygen. Applied Catalysis, 59 (1), 227–235. doi: https://doi.org/10.1016/s0166-9834(00)82200-9
  16. Nebesnyi, R., Pikh, Z., Shpyrka, I., Ivasiv, V., Nebesna, Yu., Fuch, U. (2015). Oderzhannia akrylovoi kysloty z metanolu ta otstovoi kysloty v prysutnosti skladnykh oksydnykh katalizatoriv. Visnyk NTU "KhPI". Novi rishennia v suchasnykh tekhnolohiyakh, 62, 125–130.
  17. Nebesnyi, R. V., Pikh, Z. G., Ivasiv, V. V., Sydorchuk, V. V., Shpyrka, I. I., Lapychak, N. I. (2016). Improving the efficiency of B2O3–P2O5–WO3–V2O5/SIO2 catalyst of aldol condensation of acetic acid with formaldehyde by hydrothermal treatment of the carrier. Visnyk Natsionalnoho universytetu “Lvivska politekhnika”. Khimiya, tekhnolohiya rechovyn ta yikh zastosuvannia, 841, 113–117.
  18. Leboda, R., Charmas, B., Sidorchuk, V. V. (1997). Physicochemical and Technological Aspects of the Hydrothermal Modification of Complex Sorbents and Catalysts. Part II. Modification of Phase Composition and Mechanical Properties. Adsorption Science & Technology, 15 (3), 215–236. doi: https://doi.org/10.1177/026361749701500306
  19. Jahangiri, H., Osatiashtiani, A., Bennett, J. A., Isaacs, M. A., Gu, S., Lee, A. F., Wilson, K. (2018). Zirconia catalysed acetic acid ketonisation for pre-treatment of biomass fast pyrolysis vapours. Catalysis Science & Technology, 8 (4), 1134–1141. doi: https://doi.org/10.1039/c7cy02541f

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Published

2019-02-15

How to Cite

Nebesnyi, R., Pikh, Z., Kubitska, I., Orobchuk, O., & Lukyanchuk, A. (2019). Acrylic acid synthesis by oxidative condensation of methanol and acetic acid on B–P–V–W–Ox/SiO2 catalyst. Eastern-European Journal of Enterprise Technologies, 1(6 (97), 21–27. https://doi.org/10.15587/1729-4061.2019.156764

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Section

Technology organic and inorganic substances