Preparation of Ultradispersed Crystallites of Modified Natural Clinoptilolite with the Use of Ultrasound and Its Application as a Catalyst in the Synthesis of Methyl Salicylate
American Journal of Nano Research and Applications
Volume 5, Issue 3-1, May 2017, Pages: 26-32
Received: Jan. 11, 2017; Accepted: Jan. 12, 2017; Published: Feb. 6, 2017
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Authors
Tsiuri Ramishvili, P. Melikishvili Institute of Physical & Organic Chemistry, I. Javakhishvili Tbilisi State University, Tbilisi, Georgia
Vladimer Tsitsishvili, P. Melikishvili Institute of Physical & Organic Chemistry, I. Javakhishvili Tbilisi State University, Tbilisi, Georgia
Roin Chedia, P. Melikishvili Institute of Physical & Organic Chemistry, I. Javakhishvili Tbilisi State University, Tbilisi, Georgia
Ekaterine Sanaia, Laboratory of Chemical Technologies, I. Vekua Suchumi Institute of Physics & Technology, Tbilisi, Georgia
Vakhtang Gabunia, P. Melikishvili Institute of Physical & Organic Chemistry, I. Javakhishvili Tbilisi State University, Tbilisi, Georgia
Nino Kokiashvili, Department of Physical & Analytical Chemistry, I. Javakhishvili Tbilisi State University, Tbilisi, Georgia
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Abstract
The ultradispersed crystallites (300 – 325 nm) of the acid modified natural clinoptilolite (CL, ν(SiO2)/ν(AI2O3) = 8.9) from Dzegvi (Georgia) deposit with the use of simplest method – of the indirect effect of ultrasound – were prepared. Under the influence of ultrasound the happening changes of structure and the sizes of clinoptilolite particles are shown, by the XRD, FTIR spectroscopy and by means of laser particle size analyzer, respectively. Catalytic activities of the initial acid form of the clinoptilolite (H–CL, ν(SiO2)/ν(AI2O3) = 23.3) and its form processed by ultrasound (H–CL (UlS)) in reaction of esterification of salicylic acid by methanol into methyl salicylate were compared. The indirect irradiation with ultrasound of acid form of clinoptilolite has led to sharp improve its catalytic properties in the formation of methyl salicylate. The best catalytic performance is achieved with ultrasound treated catalyst. The conversion of the salicylic acid and the selectivity to methyl salicylate on H–CL (UlS) were very high, 90 and 95%, respectively, at 120°C.
Keywords
Ultrasound, Ultradisperse Clinoptilolite, Esterification, Methyl Salicylate
To cite this article
Tsiuri Ramishvili, Vladimer Tsitsishvili, Roin Chedia, Ekaterine Sanaia, Vakhtang Gabunia, Nino Kokiashvili, Preparation of Ultradispersed Crystallites of Modified Natural Clinoptilolite with the Use of Ultrasound and Its Application as a Catalyst in the Synthesis of Methyl Salicylate, American Journal of Nano Research and Applications. Special Issue:Nanotechnologies. Vol. 5, No. 3-1, 2017, pp. 26-32. doi: 10.11648/j.nano.s.2017050301.17
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Copyright © 2017 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
References
[1]
S. Mintova, J.-P. Gilson, and V. Valtchev, “Advances in nanosized zeolites,” Nanoscale, vol. 5, pp. 6693–6703, 2013.
[2]
S. Mintova, M. Jaber, and V. Valtchev, “Nanosized microporous crystals: Emerging applications,” Chem. Soc. Rev., vol. 44, pp. 7207–7233, 2015.
[3]
E. Koohsaryan and M. Anbia, “Nanosized and hierarchical zeolites: A short review”, Chin. J. Catal., vol. 37, pp. 447–467, 2016.
[4]
V. Valtchevand L. Tosheva, “Porous nanosized particles: Preparation, properties, and applications,” Chem. Rev., vol. 113, pp. 6734–6760, 2013.
[5]
L.Tosheva,“Nanocrystalline Zeolites: Synthesis, Mechanism, and Applications”, PhD Dissertation, The Ohio State University: Ohio, 2014.
[6]
Eds. J. Garcia–Martinez and K. Li, “Mesoporous Zeolites: Preparation, Characterization and Applications,” Wiley–VCH: Weinheim, 2015.
[7]
C. N. R. Rao, P. J. Thomas, and G. U. Kulkarni, “Nanocrystals: Synthesis, Properties and Applications. Springer–Verlag: Berlin, 2007.
[8]
M. Zaarour, B. Dong, I. Nayadenova, R. Retoux, and S. Mintova, “Progress in zeolite synthesis promotes advanced applications,” Micro- & Mesoporous Mater., vol., 189, pp. 11–21, 2014.
[9]
Z. Wang, H. Wang, A. Mitra, L. Huang, and Y. Yan, “Pure-silica zeolite low- dielectric thin films,” Adv. Mater., vol. 13, pp. 746–749, 2001.
[10]
Z. B. Wang, A. Mitra, H. T. Wang, L. M. Huang, and Y. Yan, “Pure silica zeolite films as low- dielectrics by spin-on of nanoparticle suspensions,” Adv. Mater., vol. 13, pp. 1463–1466, 2001.
[11]
H. Wang, Z. Wang, L. Huang, A. Mitra, and Y. Yan, “Surface patterned porous films by convection-assisted dynamic self-assembly of zeolite nanoparticles,” Langmuir, vol. 17, pp. 2572–2574, 2001.
[12]
S. Askari, S. M. Alipour, R. Haladji, and M. H. D. Abodi Farahani, “Effects of ultrasound on the synthesis of zeolites: A review,” J. Porous Mater., vol. 20, pp. 285–302, 2013.
[13]
J. H. Bang and S. Suslick, “Applications of ultrasound to the synthesis of nanostructured materials,” Adv. Mater., vol. 22, pp. 1039–1059, 2010.
[14]
X. Fu, X. Sheng, Y. Zhou, Z. Fu, S. Zhao, Z. Zhang, and Y. Zhang, “Ultrasonic / microwave synergistic synthesis of well-dispersed hierarchical zeolite Y with improved alkylation catalytic activity,” Korean J. Chem. Eng., vol. 33, pp. 1931–1937, 2016.
[15]
S. M. Solyman, N. A. K. Aboul–Gheit, F. M. Tawfik, M. Sadek, and H. A. Ahmed, “Performance of ultrasonic treated nano-zeolites employed in the preparation of dimethyl ether,” Egypt J. Pet., vol. 22, pp. 91–99, 2013.
[16]
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=4133#x321.
[17]
Sh. R. Kirumaki, N. Nagaraju, K. V. V. S. B. S. R. Murthy, and S. Narayanan, “Esterification of salicylic acid over zeolites using dimethyl carbonate,” Appl. Catal. A, vol. 226, pp.175–182, 2002.
[18]
J. D. Souzaand N. Nagaraju, “Esterification of salicylic acid with methanol/dimethyl carbonate over anion-modified metal oxides,” Ind.J.Chem.Technol., vol. 14, pp. 292–300, 2007.
[19]
M. Zhang, W. Sh. Zhu, H. M. Li, H. Shi, Y. Sh. Yan, and Z. Wang, “Esterification of salicylic acid using Ce4+ modifiedcation-exchange resin as catalyst,” J. Chil. Chem. Soc., vol. 57, pp. 1477–1481, 2012.
[20]
J. Z. Gui, X. H. Cong, D. Liu, X. T. Zhang, Z. D. Hu, and Z. L. Sun, “Novel Brønsted acidic ionic liquid as efficient and reusable catalyst system for esterification,” Catal. Commun., vol. 5, pp. 473–477, 2004.
[21]
“Microwave synthetic method for preparing methyl salicylate,” CN101973873B, Jan 9, 2013. Google patent CN101225045A: www.google.com/patents/CN101225045.
[22]
N. I. Skhirtladze, “Sedimentary Zeolites of Georgia. Geology and Composition of Zeolite-Containing Sedimentary and Volcanic-Sedimentary Rocks, Tbilisi: Publ. House “Tbilisi State Univ.”, 1991.
[23]
Y. Garci–Basabe, I. Rodriguez–Iznaga, L.-C. De Menorval, Ph. Llewellyn, G. Maurin, D. W. Lewis, R. Binions, M. Autie, and A. R. Ruiz–Salvador, “Step-wise dealumination of natural clinoptilolite: Structural and physicochemical characterization,” Micro- & Mesoporous Mater., vol. 135, pp. 187–196, 2010.
[24]
W. Kim, O. Choi, and S. Kim, “Sonochemical synthesis of zeolite A from metakaolinite in NaOH solution,” Mater. Trans., vol. 51, pp. 1694–1698, 2010.
[25]
https://pubchem.ncbi.nlm.nih.gov/compound/methyl_salicylate#section=Dissociation-Constants.
[26]
Eds. M. M. J. Treacy and J. B. Higgins, “Collection of simulated XRD powder patterns for zeolites,” Amsterdam: Elsevier, pp. 184–187, 2001.
[27]
E. M. Flanigen, “Zeolite chemistry and catalysis,” In: ACS Monograph, vol. 171, (Ed. J. A. Rabo), Washington: Am. Chem. Soc., pp. 80–117, 1976.
[28]
W. Mozgava, M. Kröl, and K. Barczyk, “FT–IR studies of zeolites from different structural groups”, Chemik, vol. 65, pp. 667–674, 2011.
[29]
E. M. Flanigen, H. Khatami, and H. A. Szymanski, “Infrared structural studies of zeolite frame works,” Adv. Chem., vol. 101, pp. 201–229, 1971.
[30]
B. Modhera, M. Chakraborty, P. A. Parikh, and R. V. Jasra, “Synthesis of nano-crystalline zeolite β: Effects of crystallization parameters,” Cryst. Res. Technol., vol. 44, pp. 379–385, 2009.
[31]
A. J. M. De Man, S. Ueda, M. J. Annen, M .E. Davis, and R. A. Van Santen, “The stability and vibrational spectra of three-ring containing zeolitic silica polymorphs,” Zeolites, vol. 12, pp. 789–800, 1992.
[32]
F. Cakicioglu–Ozkan and S. Ulku, “The effect of HCl treatment on water vapour adsorption characteristics of clinoptilolite rich natural zeolite,” Micro- & Mesoporous Mater., vol. 77, pp. 47–63, 2005.
[33]
S. M. Baghbanian, N. Rezaei and H. Tashakkorian, “Nano zeolite clinoptilolite as a highly efficient heterogeneous catalyst for the synthesis of various 2-amino-4H-chromene derivatives in aqueous media,” Green Chem., vol. 15, pp. 3446–3458, 2013.
[34]
http://www.chemyq.com/En/xz/xz12/113961tonyl.htm
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