KINETICS OF ADSORPTION OF 4,4-DIMETHYL-1,3-DIOXANE FROM AQUEOUS SOLUTIONS BY SYNTHETIC ZEOLITES IN PRESENCE OF PHOSPHORIC ACID

  • Grygoriy A. Ovchinnikov Bashkir State University
  • Valentina А. Gorskikh Bashkir State University
  • Ilyana I. Fassalovа Bashkir State University
  • Vadim S. Тukhvatshin Bashkir State University
  • Rifkat F. Talipov Bashkir State University
Keywords: synthetic zeolites, adsorption kinetics, 4,4-dimethyl-1,3-dioxane

Abstract

In this paper we studied the kinetics of adsorption of 4,4-dimethyl-1,3-dioxane by synthetic zeolites from aqueous solutions in the presence of phosphoric acid. Kinetic mechanism of DMD adsorption from aqueous solutions by synthetic zeolites were considered from the position of three kinetic models: the diffusion model (Boyd and Morris-Weber model), Lagergeren (pseudo-first order), and pseudo-second order. As sorbents we have used synthetic zeolites KA, NaA, CaA, CaX, NaX with a pore diameter of 3-9 Å. DMD (boiling point is 113-114 ºC) was synthesized from isobutylene. Chromatographic analysis was performed on Chromatec Crystal 5000.1 instrument (Russia) using columns (2.0 m in length) with silicone SE-30 (5%) stationary phase (0.16–0.20 mm, operating temperature is 50–220 °C) with nitrogen as a carrier gas. An adsorption of DMD from aqueous solutions was investigated at (75±1) °C from a limited volume under constant mixing (laboratory mechanical stirrer, 17 rps). The contact time of the solution with samples of sorbents varied from 120 to 3600 s. The DMD concentration in solution was determined by the chromatographic method (the internal standard is 4,4,5-trimethyl-1,3-dioxane). The values of the external and internal mass transfer diffusion coefficients were obtained. The effect of the size of zeolite’s pores on the contribution of the external or internal diffusion mass transfer in the process of adsorption of 4,4-dimethyl-1,3-dioxane was founded. The time of establishment of sorption equilibrium was determined. We have found that the process of adsorption of DMD by synthetic zeolites in the presence of phosphoric acid is determined by the values of the diameter of the pores. It is shown that the value of pore diameter of synthetic zeolites does not influence on the аdsorption equilibrium time of DMD. The adsorption equilibrium time for all used family zeolites is 900 s. The kinetics of adsorption of DMD on synthetic zeolites can be correctly described by a pseudo-second-order equation, which indicates the presence of sorbate (DMD) interaction with the sorbent (synthetic zeolite).

References

Yamabe S., Fukuda T., Yamazaki S. A new intermediate in the Prins reaction. Beilstein J. Org. Chem. 2013. V. 51. N 9. P. 476-485. DOI: 10.3762/bjoc.9.51.

Yadav J.S., Subba Reddy B.V., Jayasudhan Reddy Y., Phaneendra Reddy B., Adinarayana Reddy P. A novel Prins-alkynylation reaction for the synthesis of 4-phenacyl tetrahydropyrans. Tetrahedron Lett. 2010. V. 51. N 8. P. 1236-1239. DOI: 10.1016/j.tetlet.2009.12.117.

Pastor I.M., Yus M. Focused update on the Prins reaction and the Prins cyclization. Current Org. Chem. 2012. V. 16. N 10. P. 1277-1312. DOI: 10.2174/138527212800564196.

Dumitriu E., Hulea V., Fechete I., Catrinescu C., Au-roux A., Lacaze J.F., Guimon C. Isoprene by Prince con-densation over acidic molecular sieves. Appl. Catal. A: Gen. 1999. V. 181. N 1. P. 15-28.

Plate N.А., Slivinskii Е.V. The basics of chemistry and monomers technologies. М.: Nauka. 2002. 696 p. (in Rus-sian).

Тukhvatshin V.S., Nаsyrov I.Sh., Belanogov I.А., Таlipov R.F. Synthesis of isoprene. Ufa: Bashkir State Uni-versity. 2017. 72 p. (in Russian).

Telalović S., Maheswari J. F., Ramanathan R., Chuah A., Hanefeld U. Synergy between Bronsted acid sites and Lewis acid sites. Chem. Commun. (Cambridge, England). 2008. V. 7345. N 38. Р. 4631. DOI: 10.1039/b807953f.

Оrdomskii V.V., Syhkevich V.L., Ivanova I.I. RF Patent N 2412148. 2011 (in Russian).

Mazina L.А. RF Patent N 2459790. 2012.

Оrdomskii V.V., Sushkevich V.L., Ivanova I.I. RF Patent N 2446138. 2012 (in Russian).

Кotelnikov G.R., Sidnev V.B., Кachalov D.V., Lygovkin S.N., Коmarov S.М., Churkin V.N., Glushakov M.I. RF Patent N 2448939. 2012 (in Russian).

Bikbulatov I.Kh., Daminev R.R., Yunusov D.Sh., Bacho-nina E.I. RF Patent N 2417977. 2011 (in Russian).

Bikbulatov I.Kh., Daminev R.R., Yunusov D.Sh., Bachonina E.I. RF Patent N 2417979. 2011 (in Russian).

Fadeeva V.I., Shekhovtsova Т.N., Ivanova V.М. The basics of analytical chemistry. Practical course. М.: Vyssh. shk. 2003. 463 p. (in Russian).

Кrasnova T.А., Golybeva N.S., Belyaeva О.V. Extraction of phenol from organo-minerals mixtures. Akt. Probl. Sov-rem. Nauki. 2006. N 4. P. 143-146 (in Russian).

Neudachkina L.К., Petrova Yu.S., Zasykhin А.S., Оsipova V.А., Gorbunova E.М., Larina Т.Yu. Kinetics of sorption of heavy metal ions by pyridylethylated ami-nopropylpolysiloxane. Analitika Kontrol. 2011. V. 15. N 1. P. 87-95 (in Russian).

Кrizhanovskaya О.О., Sinyaeva L.А., Каrpov S.I., Sel-emenev V.F., Borodina Е.V., Ressner F. Kinetic models in describing the sorption of fat-soluble physiologically active substances by highly ordered inorganic siliceous materials. Sorpts. Khroma-togr. Protsessy. 2014. V. 14. N 5. P. 784-794 (in Russian).

Romantsova I.V., Burakov A.E., Kucherova A.E. Study of the kinetics process of the liquid-phase adsorption of or-ganic substances on hybrid nanostructured carbon sorbents. Abstracts of VI Russian scientific-practical conference "Modern science-intensive innovative technologies". Samara: Samara Scientific Center of the Russian Academy of Scienc-es. 2014. P. 611-614. (in Russian).

Kupova O.Yu., Vakulin I.V., Talipov R.F. Ab initio study of 1,3-dioxanes formation from formaldehyde dimer and al-kenes. Computat. Theor. Chem. 2013. V. 1013. P. 57-61. DOI: 10.1016/j.comptc.2013.02.024.

Kupova O.Yu., Vakulin I.V., Talipova G.R., Talipov R.F. Quantum-chemical study of the formation of 1,3-dioxanes from formaldehyde dimer and alkenes. Butlerov Soobshch. 2012. V. 32. N 13. P. 123-127 (in Russian).

Vakulin I.V., Kupova O.Yu., Talipov R.F. Quantum-chemical study of the features of addition of oligomers of formaldehyde to alkenes. Vest. Bashkir Gos. Un-ta. 2010. V. 15. N 2. P. 294-297 (in Russian).

Published
2018-12-12
How to Cite
Ovchinnikov, G. A., GorskikhV. А., FassalovаI. I., ТukhvatshinV. S., & Talipov, R. F. (2018). KINETICS OF ADSORPTION OF 4,4-DIMETHYL-1,3-DIOXANE FROM AQUEOUS SOLUTIONS BY SYNTHETIC ZEOLITES IN PRESENCE OF PHOSPHORIC ACID. ChemChemTech, 61(12), 81-86. https://doi.org/10.6060/ivkkt.20186112.5542
Section
CHEMISTRY (inorganic, organic, analytical, physical, colloid and high-molecular compounds)