PROPİYONİK ASİTİN İZOBUTİL ALKOL İLE AMBERLYST 36 VE AMBERLYST 70 KATALİZÖRLERİ VARLIĞINDA ESTERLEŞME KİNETİĞİ

Abstract

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: 

k_1=160171 exp⁡((-56689)/RT) (L mol-1 min-1)

k_1=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.

Keywords

• Esterleşme,yalancı homojen kinetik model,Amberlyst 36,Amberlyst 70,Heterojen kataliz

Kinetics of the Esterification of Propionic Acid with Isobutyl Alcohol over Amberlyst 36 and Amberlyst 70

Abstract

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:

k_1=160171 exp⁡((-56689)/RT) (L mol-1 min-1)

k_1=293314 exp⁡((-57292)/RT) (L mol-1 min-1)

In a comparison of the two catalysts used in this study, experimental results showed that Amberlyst 70 is more effective than Amberlyst 36.

Keywords

• Esterification,pseudohomogeneous kinetics,Amberlyst 36,Amberlyst 70,Heterogeneous Catalysis

References

1. 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
2. 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
3. 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
4. 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
5. 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
6. 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
7. 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
8. 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

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
10. 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
11. 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
12. 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
13. 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
14. 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
15. 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
16. 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, 793-798. doi:10.1016/j.crci.2012.06.004
17. 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
18. 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
19. 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
20. Schmid B., M. Döker, J. Gmehling, (2008), Esterification of Ethylene Glycol with Acetic Acid Catalyzed by Amberlyst 36, Industrial & Engineering Chemistry Research, 47, 698-703. doi: 10.1021/ie0707117
21. 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
22. 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
23. 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