Alime ÇITAK, Halit Levent HOŞGÜN

Propiyonik Asitin İsobütil Alkol ile Amberlyst 36 ve Amberlyst 70 Katalizörleri varlığında Esterleşme Kinetiği

Propiyonik asidin izobütil alkol ile esterleşme tepkimesi, Amberlyst 36 ve Amberlyst 70 katalizörlerinin varlığında kesikli bir reaktörde çalışılmıştır. Bu çalışmada; karıştırma hızı (500-1000 rpm), katalizör tanecik boyutu (400-600 μm, 600+ μm), sıcaklık (318-348 K) ve katalizör miktarı (4-12 g kuru reçine / L) reaksiyon parametreleridir. Bir yalancı-homojen kinetik model türetilmiş ve tüm termodinamik ve kinetik parametreler hesaplanmıştır. Amberlyst 36 ve Amberlyst 70 için ileri reaksiyon hızı sabiti aşağıdaki gibi belirlenmiştir: $ k1 = 160171 exp(-56689/RT) (L mol-1 min-1)$ $ k1 = 293314 exp(-57292/RT) (L mol-1 min-1)$ Bu çalışmada kullanılan iki katalizörün karşılaştırmasında deneysel sonuçlar Amberlyst 70'in Amberlyst 36'dan daha etkili olduğunu göstermiştir.

KINETICS OF THE ESTERIFICATION OF PROPIONIC ACID WITH ISOBUTYL ALCOHOL OVER AMBERLYST 36 AND AMBERLYST 70

The esterification of propionic acid with isobutyl alcohol has been studied in a batch reactor in the presence of Amberlyst 36 and Amberlyst 70 catalysts. Reaction parameters applied in this study are speed of agitation (500-1000 rpm), particle size of catalyst (400-600 µm, 600+ µm), temperature (318-348 K) and catalyst loading (4-12 g-dry resin/L). A pseudo-homogeneous kinetic model was derived and all thermodynamic and kinetic parameters were calculated. Forward reaction rate constant for Amberlyst 36 and Amberlyst 70 determined as follows:$ k1 = 160171 exp(-56689/RT) (L mol-1min-1)$$ k1 = 293314 exp(-57292/RT) (L mol-1min-1)$In a comparison of the two catalysts used in this study, experimental results showed that Amberlyst 70 is more effective than Amberlyst 36.

PDF

___

Aguiar V. M.,A. L. F.de Souza, F. S.Galdino, M. M. C.da Silva, V. G.Teixeira, E. R.Lachter, (2017), Sulfonated poly(divinylbenzene) and poly(styrene-divinylbenzene) as catalysts for esterification of fatty acids, Renewable Energy, 114, 725-732. doi:10.1016/j.renene.2017.07.084
Aguiar V. M.,A. L. F.de Souza, F. S.Galdino, M. M. C.da Silva, V. G.Teixeira, E. R.Lachter, (2017), Sulfonated poly(divinylbenzene) and poly(styrene-divinylbenzene) as catalysts for esterification of fatty acids, Renewable Energy, 114, 725-732. doi:10.1016/j.renene.2017.07.084
Akbay E.Ö., M.R. Altıokka, (2011), Kinetics of esterification of acetic acid with n-amyl alcohol in the presence of Amberlyst-36, Applied Catalysis A: General, 396, 14-19. doi:10.1016/j.apcata.2011.01.013
Akbay E.Ö., M.R. Altıokka, (2011), Kinetics of esterification of acetic acid with n-amyl alcohol in the presence of Amberlyst-36, Applied Catalysis A: General, 396, 14-19. doi:10.1016/j.apcata.2011.01.013
Altıokka M.R., A. Çıtak, (2003), Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst, Applied Catalysis A: General, 239, 141-148. doi:10.1016/S0926-860X(02)00381-2
Altıokka M.R., A. Çıtak, (2003), Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst, Applied Catalysis A: General, 239, 141-148. doi:10.1016/S0926-860X(02)00381-2
Bringué R., E. Ramírez, C. Fité, M. Iborra, J. Tejero, (2011), Kinetics of 1-Pentanol Etherification without Water Removal, Industrial & Engineering Chemistry Research, 50, 7911-7919. doi: 10.1021/ie1025776
Bringué R., E. Ramírez, C. Fité, M. Iborra, J. Tejero, (2011), Kinetics of 1-Pentanol Etherification without Water Removal, Industrial & Engineering Chemistry Research, 50, 7911-7919. doi: 10.1021/ie1025776
Bringué R., M. Iborra, J. Tejero, J.F. Izquierdo, F. Cunill, C. Fité, V.J. Cruz, (2006),
Bringué R., M. Iborra, J. Tejero, J.F. Izquierdo, F. Cunill, C. Fité, V.J. Cruz, (2006),
Thermally stable ion-exchange resins as catalysts for the liquid-phase dehydration of 1-pentanol to di-n-pentyl ether (DNPE), Journal of Catalysis, 244, 33-42. doi:10.1016/j.jcat.2006.07.035
Thermally stable ion-exchange resins as catalysts for the liquid-phase dehydration of 1-pentanol to di-n-pentyl ether (DNPE), Journal of Catalysis, 244, 33-42. doi:10.1016/j.jcat.2006.07.035
Casas, C., Bringué, R., Fité, C., Iborra, M. and Tejero, J. (2017), Kinetics of the liquid phase dehydration of 1-octanol to di-n-octyl ether on Amberlyst 70. AIChE J., 63: 3966– 3978. doi:10.1002/aic.15741
Casas, C., Bringué, R., Fité, C., Iborra, M. and Tejero, J. (2017), Kinetics of the liquid phase dehydration of 1-octanol to di-n-octyl ether on Amberlyst 70. AIChE J., 63: 3966– 3978. doi:10.1002/aic.15741
Chandak H.S., N.P. Lad, D.S. Dange, (2011), Greener and facile aqueous synthesis of pyrazoles using Amberlyst-70 as a recyclable catalyst, Green Chemistry Letters and Reviews, 5, 135-138. doi:10.1080/17518253.2011.585352
Chandak H.S., N.P. Lad, D.S. Dange, (2011), Greener and facile aqueous synthesis of pyrazoles using Amberlyst-70 as a recyclable catalyst, Green Chemistry Letters and Reviews, 5, 135-138. doi:10.1080/17518253.2011.585352
Chin S.Y., M.A.A. Ahmad, M.R. Kamaruzaman, C.K. Cheng, (2015), Kinetic studies of the esterification of pure and dilute acrylic acid with 2-ethyl hexanol catalysed by Amberlyst 15, Chemical Engineering Science, 129, 116-125. doi:10.1016/j.ces.2015.02.006
Chin S.Y., M.A.A. Ahmad, M.R. Kamaruzaman, C.K. Cheng, (2015), Kinetic studies of the esterification of pure and dilute acrylic acid with 2-ethyl hexanol catalysed by Amberlyst 15, Chemical Engineering Science, 129, 116-125. doi:10.1016/j.ces.2015.02.006
Golets M., S. Ajaikumar, W. Larsson, D. Blomberg, H. Grundberg, J. Wärnå, T. Salmi, J.P. Mikkola, A (2012), Kinetic Study of the Liquid Phase Acetoxylation of α-Pinene, Top Catal, 55, 649-656. doi:10.1007/s11244-012-9844-9
Golets M., S. Ajaikumar, W. Larsson, D. Blomberg, H. Grundberg, J. Wärnå, T. Salmi, J.P. Mikkola, A (2012), Kinetic Study of the Liquid Phase Acetoxylation of α-Pinene, Top Catal, 55, 649-656. doi:10.1007/s11244-012-9844-9
Guilera J., E. Ramirez, C. Fite, J. Tejero, F. Cunill, (2015), Synthesis of ethyl hexyl ether over acidic ion-exchange resins for cleaner diesel fuel, Catalysis Science & Technology, 5, 2238-2250. doi:10.1039/C4CY01548G
Guilera J., E. Ramirez, C. Fite, J. Tejero, F. Cunill, (2015), Synthesis of ethyl hexyl ether over acidic ion-exchange resins for cleaner diesel fuel, Catalysis Science & Technology, 5, 2238-2250. doi:10.1039/C4CY01548G
Hosseininejad S., A. Afacan, R.E. Hayes, (2012), Catalytic and kinetic study of methanol dehydration to dimethyl ether, Chemical Engineering Research and Design, 90, 825-833. doi:10.1016/j.cherd.2011.10.007
Hosseininejad S., A. Afacan, R.E. Hayes, (2012), Catalytic and kinetic study of methanol dehydration to dimethyl ether, Chemical Engineering Research and Design, 90, 825-833. doi:10.1016/j.cherd.2011.10.007
Izci A., F. Bodur, (2007), Liquid-phase esterification of acetic acid with isobutanol catalyzed by ion-exchange resins, Reactive and Functional Polymers, 67, 1458-1464. doi:10.1016/j.reactfunctpolym.2007.07.019
Izci A., F. Bodur, (2007), Liquid-phase esterification of acetic acid with isobutanol catalyzed by ion-exchange resins, Reactive and Functional Polymers, 67, 1458-1464. doi:10.1016/j.reactfunctpolym.2007.07.019
Ju I.B., H.-W. Lim, W. Jeon, D.J. Suh, M.-J. Park, Y.-W. Suh, (2011), Kinetic study of catalytic esterification of butyric acid and n-butanol over Dowex 50Wx8-400, Chemical Engineering Journal, 168, 293-302. doi:10.1016/j.cej.2010.12.086 Komoń T., P. Niewiadomski, P. Oracz, M.E. Jamróz, (2013), Esterification of acrylic acid with 2-ethylhexan-1-ol: Thermodynamic and kinetic study, Applied Catalysis A: General, 451, 127-136. doi:10.1016/j.apcata.2012.11.018
Ju I.B., H.-W. Lim, W. Jeon, D.J. Suh, M.-J. Park, Y.-W. Suh, (2011), Kinetic study of catalytic esterification of butyric acid and n-butanol over Dowex 50Wx8-400, Chemical Engineering Journal, 168, 293-302. doi:10.1016/j.cej.2010.12.086 Komoń T., P. Niewiadomski, P. Oracz, M.E. Jamróz, (2013), Esterification of acrylic acid with 2-ethylhexan-1-ol: Thermodynamic and kinetic study, Applied Catalysis A: General, 451, 127-136. doi:10.1016/j.apcata.2012.11.018
Merchant S.Q., K.A. Almohammad, A.A.M. Al Bassam, S.H. Ali, (2013), Biofuels and additives: Comparative kinetic study of Amberlite IR 120-catalyzed esterification of ethanol with acetic, propanoic and pentanoic acids to produce eco-ethyl-esters, Fuel, 111, 140-147. doi:10.1016/j.fuel.2013.04.016
Merchant S.Q., K.A. Almohammad, A.A.M. Al Bassam, S.H. Ali, (2013), Biofuels and additives: Comparative kinetic study of Amberlite IR 120-catalyzed esterification of ethanol with acetic, propanoic and pentanoic acids to produce eco-ethyl-esters, Fuel, 111, 140-147. doi:10.1016/j.fuel.2013.04.016
Mitran G., É. Makó, Á. Rédey, I.-C. Marcu, (2012), Esterification of acetic acid with n- Butanol using vanadium oxides supported on γ-alumina, Comptes Rendus Chimie, 15, 793- doi:10.1016/j.crci.2012.06.004
Mitran G., É. Makó, Á. Rédey, I.-C. Marcu, (2012), Esterification of acetic acid with n- Butanol using vanadium oxides supported on γ-alumina, Comptes Rendus Chimie, 15, 793- doi:10.1016/j.crci.2012.06.004
Pappu V.K.S., V. Kanyi, A. Santhanakrishnan, C.T. Lira, D.J. Miller, (2013), Butyric acid esterification kinetics over Amberlyst solid acid catalysts: The effect of alcohol carbon chain length, Bioresource Technology, 130, 793-797. doi:10.1016/j.biortech.2012.12.087
Pappu V.K.S., V. Kanyi, A. Santhanakrishnan, C.T. Lira, D.J. Miller, (2013), Butyric acid esterification kinetics over Amberlyst solid acid catalysts: The effect of alcohol carbon chain length, Bioresource Technology, 130, 793-797. doi:10.1016/j.biortech.2012.12.087
Park S.-W., H.-B. Cho, D.-S. Suh, C.-W. Kim, (1999), Esterification of lauric acid with isopropyl alcohol by tricaprylylmethylammonium chloride as a catalyst in a liquid-liquid heterogeneous system, Korean J. Chem. Eng., 16, 221-228. doi:10.1007/BF02706840
Park S.-W., H.-B. Cho, D.-S. Suh, C.-W. Kim, (1999), Esterification of lauric acid with isopropyl alcohol by tricaprylylmethylammonium chloride as a catalyst in a liquid-liquid heterogeneous system, Korean J. Chem. Eng., 16, 221-228. doi:10.1007/BF02706840
Rezende S.M. de, M. de Castro Reis, M.G. Reid, P. Lúcio Silva Jr, F.M.B. Coutinho, R.A. da Silva San Gil, E.R. Lachter, (2008), Transesterification of vegetable oils promoted by poly(styrene-divinylbenzene) and poly(divinylbenzene), Applied Catalysis A: General, 349, 198-203. doi:10.1016/j.apcata.2008.07.030
Rezende S.M. de, M. de Castro Reis, M.G. Reid, P. Lúcio Silva Jr, F.M.B. Coutinho, R.A. da Silva San Gil, E.R. Lachter, (2008), Transesterification of vegetable oils promoted by poly(styrene-divinylbenzene) and poly(divinylbenzene), Applied Catalysis A: General, 349, 198-203. doi:10.1016/j.apcata.2008.07.030
Schmid B., M. Döker, J. Gmehling, (2008), Esterification of Ethylene Glycol with Acetic
Schmid B., M. Döker, J. Gmehling, (2008), Esterification of Ethylene Glycol with Acetic
Acid Catalyzed by Amberlyst 36, Industrial & Engineering Chemistry Research, 47, 698- doi: 10.1021/ie0707117
Acid Catalyzed by Amberlyst 36, Industrial & Engineering Chemistry Research, 47, 698- doi: 10.1021/ie0707117
Sharma M., R.K. Wanchoo, A.P. Toor, (2012), Adsorption and Kinetic Parameters for Synthesis of Methyl Nonanoate over Heterogeneous Catalysts, Industrial & Engineering Chemistry Research, 51, 14367-14375. doi: 10.1021/ie301661n
Sharma M., R.K. Wanchoo, A.P. Toor, (2012), Adsorption and Kinetic Parameters for Synthesis of Methyl Nonanoate over Heterogeneous Catalysts, Industrial & Engineering Chemistry Research, 51, 14367-14375. doi: 10.1021/ie301661n
Siril P.F., H.E. Cross, D.R. Brown, (2008), New polystyrene sulfonic acid resin catalysts with enhanced acidic and catalytic properties, Journal of Molecular Catalysis A: Chemical, 279, 63-68. doi:10.1016/j.molcata.2007.10.001
Siril P.F., H.E. Cross, D.R. Brown, (2008), New polystyrene sulfonic acid resin catalysts with enhanced acidic and catalytic properties, Journal of Molecular Catalysis A: Chemical, 279, 63-68. doi:10.1016/j.molcata.2007.10.001
Tsai Y.-T., H.-m. Lin, M.-J. Lee, (2011), Kinetics of Catalytic Esterification of Propionic Acid with Methanol over Amberlyst 36, Industrial & Engineering Chemistry Research, 50, 1171-1176. doi: 10.1021/ie1001179
Tsai Y.-T., H.-m. Lin, M.-J. Lee, (2011), Kinetics of Catalytic Esterification of Propionic Acid with Methanol over Amberlyst 36, Industrial & Engineering Chemistry Research, 50, 1171-1176. doi: 10.1021/ie1001179