Separation of Anisole and Valuable Byproducts from Liquid Reaction Mixtures by Solvent Extraction and Multicomponent Distillation

Abstract

Anisole (methoxybenzene) is a widely used organic intermediate that can be synthesized via vapor-phase alkylation of phenol by methanol in the presence of a commercial NaX zeolite as a catalyst (SiO2:Al2O3 ratio of 2.6:3). The indigenously synthesized anisole is then separated from the multicomponent liquid reaction mixture, consisting of o-cresol, p-cresol and p-xylen, along with unreacted methanol and phenol. The separated anisole has substantial demand for applications in the chemical, pharmaceutical, plastics and pesticides industries. Separation of individual components from the reaction mixture requires identification of techniques that could be scaled up. Distillation is one of the most dependable techniques for the separation of multicomponent liquid mixtures. The novelty of the present study is the synthesis and separation of anisole along with individual components of methanol, phenol and o-cresol from its reaction mixture using a single distillation column under atmospheric and vacuum conditions, respectively. Through this process, the purity of the resulting methanol, anisole and phenol were found to be 99.99, 99.80 and 98.29% by simple distillation, whereas 91.0% pure o-cresol was separated by vacuum distillation due to its high boiling point. The experimental results were used to calculate the material, individual component and energy balances, whereas the PRO/II™ process simulation was performed to scale-up the process. On the other hand, anisole recovery from a synthetic multicomponent liquid mixture was also successfully conducted using solvent extraction. The overall observations found the integration of solvent extraction with distillation to be an effective, economical and dependable solution for the isolation of anisole and other important by-products.

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References

  1. 1.

    Hiers, G.S., Hager, F.D.: Anisole. Org. Synth. 9, 12 (1929)

    CAS  Article  Google Scholar 

  2. 2.

    Christopher, H., Paul, N., David, W.R., Jillian, M.T.: Friedel−Crafts benzoylation of anisole in ionic liquids: catalysis, separation, and recycle studies-article. Org. Process Res. Dev. 12(6), 1156–1163 (2008)

    Article  Google Scholar 

  3. 3.

    Angelo, L., Amit, A., Ross, T.: Distillation pinch points and more. Sci. Direct Comput. Chem. Eng. 32, 1350–1372 (2008)

    Google Scholar 

  4. 4.

    Petlyuk, F.B., Platonov, V.M., Slavinskii, D.M.: Thermodynamically optimal method for separating multicomponent mixtures. Int. Chem. Eng. 5(3), 555–561 (1965)

    Google Scholar 

  5. 5.

    Ganapati, D.Y., Kalpesh, H.B.: Process of methylation of phenol with increased cresol and anisole selectivity. International patent WO/2017/138015A1. PCT/IN2017/000027 (2017)

  6. 6.

    Bernot, C., Doherty, M.F., Malone, M.F.: Patterns of composition change in multicomponent batch distillation. Chem. Eng. Sci. 45(5), 1207–1221 (1990)

    CAS  Article  Google Scholar 

  7. 7.

    Noble, R.D., Terry, P.A.: Principles of chemical separations with environmental applications. Angew. Chem. 117(2), 187–188 (2004)

    Google Scholar 

  8. 8.

    Alan, S.F., Leonard, A.W., Curtis, W.C., Louis, M.L.: Principles of Unit Operations. Wiley, Chichester (1980)

    Google Scholar 

  9. 9.

    Mccabe, W.L., Smith, J.C., Harriott, P.: Unit Operations of Chemical Engineering. Mcgraw-Hill, New York (1993)

    Google Scholar 

  10. 10.

    Basab, C., Ajit, A.P., Sharma, M.M.: Alkylation of substituted phenols with olefins and separation of close-boiling phenolic substances via alkylation/dealkylation. Ind. Eng. Chem. Res. 29(6), 1025–1031 (1990)

    Article  Google Scholar 

  11. 11.

    Suzuki, T., Hashimoto, S., Orisaks, M., Nakano. R.: Method for separation of m- or p-cresol. U. S. Patent 4032581 (1977)

  12. 12.

    Arthur, W.W., Oliver, W.: Synthesis of Distillation Based Separation Systems. Advances in Chemical Engineering. vol. 23, pp. 63–170. Academic Press, Inc. (1996)

  13. 13.

    Westerberg, A.W.: The synthesis of distillation-based separation systems. Computer Chem. Eng. 9(5), 421–429 (1985)

    CAS  Article  Google Scholar 

  14. 14.

    King, C.J.: Separation Processes. Mcgraw-Hill Inc., New York (1980)

    Google Scholar 

  15. 15.

    Fidkowski, Z., Kro, L.L.: Minimum energy requirements of thermally coupled distillation system. AIChE J. 33(4), 643–653 (1987)

    CAS  Article  Google Scholar 

  16. 16.

    Wang, Z., Li, S., Wang, C., Gao, X., Bai, P.: Dynamic-accumulative operation policy of continuous distillation for the purification of anisole. Pol. J. Chem. Technol. 18(1), 33–39 (2016)

    CAS  Article  Google Scholar 

  17. 17.

    Lee, K.R., Tan, C.-S.: Separation of m- and p-cresols in compressed propane using modified HZSM-5 pellets. Ind. Eng. Chem. Res. 39, 1035–1038 (2000)

    CAS  Article  Google Scholar 

  18. 18.

    Shiau, L.-D., Wen, C.-C., Lin, B.-S.: Separation of p-xylene from the multicomponent xylene system by stripping crystallization. AIChE J. 54(1), 337–342 (2008)

    CAS  Article  Google Scholar 

  19. 19.

    Vilas, G.G., Alpana, M., Sharma, M.M.: Separation of close boiling point mixtures (p-cresol/m-cresol, guaiacol/alkylphenols, 3-picoline/4-picoline, substituted anilines) through dissociation extractive crystallization. Ind. Eng. Chem. Res. 28(2), 199–204 (1989)

    Article  Google Scholar 

  20. 20.

    Ylinen, R.E.: Application of Azeotropic Distillation to the Separation of Para-Vresol and Meta Cresol. M.S. thesis in Chemical Engineering. Montana State University (1965)

  21. 21.

    Lie, D.S., Chih, H.H., Keng, F.L.: Separation of the cresol isomers by stripping crystallization. Asia-Pacific J. Chem. Eng. 7(1), S26–S31 (2012)

    Google Scholar 

  22. 22.

    Novak, Z., Kravanja, Z., Grossmann, I.E.: Simultaneous optimization model for multicomponent separation. Computers Chem. Eng. 18, S125–S129 (1994)

    Article  Google Scholar 

  23. 23.

    Kodera, Y., Ukegawa, K., Matsumura, A., Ma, X.: Methanol-mediated extraction process for the separation of phenolic compounds from coal liquids. Fuel 72(1), 57–58 (1993)

    CAS  Article  Google Scholar 

  24. 24.

    Dewi, S.F., Panut, M., Wahyudi, B.S., Muslikhin, H.: Extraction of phenol, o-cresol and p-cresol from coal tar: effect of temperature and mixing. Int. Schol. Sci. Res. Innov. 7(6), 454–458 (2013)

    Google Scholar 

  25. 25.

    Masashi, I., Yoshikazu, H., Kimikatsu, J., Mitsugi, K., Norio, S., Masayuki, H.: Method of separating components of phenols mixture by distillation. Patent. US 5264085 A (1993)

  26. 26.

    Raghu, V.K., Usha, V., Sreepriya, V.: Study of effect of parameters on separation of cresol isomers. J. Environ. Chem. Eng. 5(5), 5280–5284 (2017)

    Article  Google Scholar 

  27. 27.

    Pereira, C.C.M., de la Cruz, M.H.C., Lachter, E.R.: Liquid phase alkylation of anisole and phenol catalyzed by niobium phosphate. J. Braz. Chem. Soc. 21(2), 367–370 (2010)

    CAS  Article  Google Scholar 

  28. 28.

    Thompson, R.W., King, C.J.: Systematic synthesis of separation scheme. AIChE J. 18(5), 941–948 (1972)

    CAS  Article  Google Scholar 

  29. 29.

    Majer, V., Svoboda, V.: Enthalpies of Vaporization of Organic Compounds: A Critical Review and Data Compilation. Blackwell Scientific Publications, Oxford (1985)

    Google Scholar 

  30. 30.

    Tatiana, V.V., Sergey, P.V., Eckard, B., Andreas, H.: Thermodynamic properties of mixtures containing ionic liquids. Activity coefficients of ethers and alcohols in 1-methyl-3-ethyl-imidazolium bis(trifluoromethyl-sulfonyl) imide using the transpiration method. J. Chem. Eng. Data 50, 142–148 (2005)

    Article  Google Scholar 

  31. 31.

    Chickos, J.S., Hosseini, S., Hesse, D.G.: Determination of vaporization enthalpies of simple organic molecules by correlations of changes in gas chromatographic net retention times. Thermochim. Acta 249, 41–62 (1995)

    CAS  Article  Google Scholar 

  32. 32.

    Hayens, W.M.: CRC Handbook of Chemistry and Physics. CRC Press, Boca Raton (2014)

    Google Scholar 

  33. 33.

    Sargent, R.W.H., Gaminibandara, K.: Optimum design of plate distillation columns. In: Dixon, L.W.C. (ed.) Optimization in Action, pp. 267–314. Academic Press, London (1976)

    Google Scholar 

  34. 34.

    Dimian, A.C., Bildea, C.S., Kiss, A.A.: Integrated Design and Simulation of Chemical Processes. Elsevier (2014)

  35. 35.

    Pinheiro, A., Hudebine, D., Dupassieux, N., Geantet, C.: Impact of oxygenated compounds from lignocellulosic biomass pyrolysis oils on gas oil hydrotreatment. Energy Fuels 23(2), 1007–1014 (2009)

    CAS  Article  Google Scholar 

Download references

Acknowledgements

The first author wishes to acknowledge CSIR-IICT-AcSIR for providing funding and the opportunity to carry out PhD research. We thank the Director, CSIR-IICT, for supporting this research work of communication no. IICT/Pubs./2020/059.

Funding

This funding was supported by CSIR Grant No. [31/014(2764)/2018-EMR-1].

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Correspondence to Sundergopal Sridhar.

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Vani, B., Pabba, M., Kalyani, S. et al. Separation of Anisole and Valuable Byproducts from Liquid Reaction Mixtures by Solvent Extraction and Multicomponent Distillation. J Solution Chem 50, 160–177 (2021). https://doi.org/10.1007/s10953-020-01049-0

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Keywords

  • Vapor-phase alkylation
  • Anisole
  • Multi-component liquid mixtures
  • Distillation
  • Material and energy balance
  • Solvent extraction