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Sustainable Catalytic Process for Synthesis of Triethyl Citrate Plasticizer over Phosphonated USY Zeolite

Catalysis and Inorganic Chemistry Division, CSIR - National Chemical Laboratory, Pune- 411008, India

Received: 28 Jun 2016; Published: 11 Oct 2016.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2016 by Authors, Published by BCREC Group under http://creativecommons.org/licenses/by-sa/4.0.

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Abstract

Fruits wastage is harmful to health and environment concerning spreading diseases and soil pollution, respectively. To avoid this issue, use of citrus fruit waste for the production of citric acid (CA) is one of viable mean to obtain value added chemicals. Moreover, synthesis of triethyl citrate (TEC), a non-toxic plasticizer by esterification of CA with ethanol over heterogeneous catalyst would be renewable and sustainable catalytic process. In this context, parent Ultrastable Y (USY) and different percentage phosphonated USY (P-USY) zeolites were used for the synthesis of TEC in a closed batch reactor, for the first time. The synthesized catalysts were characterized by N2-adsorption desorption isotherm, powder X-ray diffraction (XRD) and NH3 temperature programmed desorption (TPD. Effect of reaction conditions, such as the molar ratio of ethanol to CA (5:1 - 20:1), the catalyst to CA ratio (0.05 - 0.25) and reaction temperature (363-403 K), were studied in view to maximizing CA conversion and TEC yield. Phosphonated USY catalysts were found to be superior in activity (CA conversion and TEC yield) than parent USY, which is attributed to the increased in total acidity with phosphonation. Among the studied catalysts, the P2USY (2% phosphorous loaded on USY) was found to be an optimum catalyst with 99% CA conversion and 82% TEC yield, which is higher than the reported values. This study opens new avenues of research demonstrating principles of green chemistry such as easy separable and reusable catalyst, non-toxic product, bio-renewable synthetic route, milder operating parameters and waste minimization. 

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Keywords: citric acid; plasticizer; ethanol; tri-ethyl citrate; phosphonated USY

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  1. Kolah, A.K., Asthana, N.S., Vu, D.T., Lira, C.T., Miller, D.J. (2007). Reaction Kinetics of the catalytic esterification of citric acid with ethanol. Ind. Eng. Chem. Res. 46: 3180-3187
  2. Kolah, A.K., Asthana, N.S., Vu, D.T., Lira, C.T., Miller, D.J. (2008). Triethyl citrate synthesis by reactive distillation. Ind. Eng. Chem. Res. 47: 1017-1025
  3. Nandiwale, K.Y., Borikar, S.P., Bokade, V.V. (2015). Synthesis of non-toxic tri-ethyl citrate plasticizer by esterification of renewable citric acid over modified zeolite. Clean-Soil Air Water. 43: 927-931
  4. Schroter, J., Konetzke, G., Weidemann, F., Klein,T., Bohnen, H., Bergrath, K., Schmidt, K. (2003). Method for producing citric acid esters. Patent WO 2003008369 A1
  5. Tao, X. (1998). Optimization of conditions for tri-ethyl citrate synthesis. Huazue. Shijie. 39: 302-304
  6. Nandiwale, K.Y., Gogoi, P., Bokade, V.V. (2015). Catalytic upgrading of citric acid to environmental friendly tri-butyl citrate plasticizer over ultra stable phosphonated Y zeolite. Chem. Eng. Res. Des. 98: 212-219
  7. Millikin, C.L., Bissett, D.L. (2008). Personal care composition. US Patent 2008206169 A1
  8. Khemani, K., Mccaffrey, N., John, M. (2008). Biodegradable polymer. Patent: WO2008014573 A1
  9. Xu. J., Jiang. J., Zuo. Z., Li, J. (2010). Synthesis of tributyl citrate using acid ionic liquid as catalyst. Process. Saf. Environ. 88: 28-30
  10. Xu. J., Jiang. J., Wei. L.V., Gao. Y. (2011). Synthesis of tributyl citrate using solid acid as a catalyst. Chem. Eng. Comm. 198: 474-482
  11. Yang. H., Song. H., Zhang. H., Chen. P., Zhao. Z. (2014).Esterification of citric acid with n-butanol over zirconium sulfate supported on molecular sieves. J. Mol. Catal. A. 381: 54-60
  12. Corma, A., Fornes, V., Juan-Rajadell, M.I., Nieto, J.M.L. (1994). Influence of preparation conditions on the structure and catalytic properties of SO42-/ZrO2 super acid catalysts. Appl. Catal. A: Gen. 116:151-163
  13. Ghoreishi, K.B., Asim, N., Yarmo, M.A., Samsudin, M.W. (2014). Mesoporous phosphated and sulphated silica as solid acid catalysts for glycerol acetylation. Chem. Pap. 68: 1194-1204

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