Dahili Membran Reaktörde Kullanılmak Üzere Yüksek Performanslı Polivinil Alkol Membran Üretimi ve Etanol-Propiyonik Asit Esterleşme Reaksiyonunda Uygulaması

Öz

Bu çalışmada, tek basamaklı reaktif ayırmanın yapıldığı bir membran reaktörde kullanılmak üzere yüksek dayanıma ve su tutma kapasitesine sahip çapraz bağlı polivinil alkol (PVA) membranı üretilmiş ve modül olarak kesikli reaktörde kullanılmıştır. Etanol ve propiyonik asit arasında Amberlit IR120 katalizörü eşliğinde gerçekleşen esterleşme reaksiyonunda membran modül eklenen kesikli reaktör ve klasik kesikli reaktörün asit dönüşüm sonuçları karşılaştırılmış, membranın klasik kesikli sistemde yaptığı dönüşüm iyileştirmesi değerlendirilmiştir. Reaksiyon sıcaklığının (50, 60, 70°C), katalizör miktarının (asit kütlesine göre %1, 2, 3) ve alkol:asit reaktan besleme oranının (M=1, 2, 3) her iki reaktördeki dönüşüme etkisi belirlenerek en iyi koşullar belirlenmiştir. Sonuç olarak membranın modül olarak eklendiği, sürekli ayırma yapmadığı ve suyu sorpladığı membran modüllü reaktörde klasik reaktöre göre %24-48 oranlarında dönüşüm iyileştirilmesi gerçekleştirilmiştir. En yüksek dönüşüm değeri ise 70°C sıcaklıkta ve M=3 besleme oranında modül kullanılan reaktörde %74 olarak elde edilmiştir.

Anahtar Kelimeler

• Esterleşme,Reaktif ayırma; Polivinil alkol membran; Membran reaktör

Kaynakça

1. [1] Stankiewicz, A. I., Moulijn, J. A. 2000. Process Intensification: Transforming Chemical Engineering. Chemical Engineering process, January (2000), 22-34.
2. [2] Hessel, V. 2009. Process Windows - Gate to Maximizing Process Intensification via Flow Chemistry. Chemical Engineering and Technology, 32(2009), 1655–81.
3. [3] Charpentier, J. C. 2007. In the Frame of Globalization and Sustainability, Process Intensification, a Path to the Future of Chemical and Process Engineering (Molecules into Money). Chemical Engineering Journal, 134(2007), 84–92.
4. [4] Athankar, K. K., Wasewar, K. L., Varma, M. N., Shende, D. Z. 2016. Reactive Separation of Benzeneacetic Acid with Tri -n-caprylyl Amine: Equilibrium and Modeling. J. Chem. Eng. Data, 61(2016) 2335−2345.
5. [5] Kiss, A. A., Sorin, C. 2012. A review of biodiesel production by integrated reactive separation technologies. J. Chem. Technol. Biotechnol., 87(2012), 861–879.
6. [6] Stankiewicz, A. 2003. Reactive separations for process intensification: an industrial perspective. Chemical Engineering and Processing, 42(2003), 137–144.
7. [7] Buchaly, C., Kreis, P., Andrzej, G. 2007. Hybrid separation processes — Combination of reactive distillation with membrane separation. Chemical Engineering and Processing, 46(2007), 790–799.
8. [8] Leuch, L. M., Le Bandosz, T. J. 2007. The role of water and surface acidity on the reactive adsorption of ammonia on modified activated carbons. Carbon, 45(2007), 568–578.

9. [9] Wasewar, K. L. A., Heesink, B. M., Versteeg, G. F., Pangarkar, V. G. 2002. Reactive extraction of lactic acid using alamine 336 in MIBK: equilibria and kinetics. Journal of Biotechnology, 97(2002), 59–68.
10. [10] Basile, A. 2013. Handbook of membrane reactors Volume 1: Fundamental materials science, design and optimisation. Woodhead Publishing Limited, Cambridge, 696s.
11. [11] Basile, A., Gallucci, F. 2011. Membranes for Membrane Reactors Preparation, Optimization and Selection. John Wiley & Sons, United Kingdom, 615s.
12. [12] Khajavi, S., Jansen, J. C., Kapteijn, F. 2010. Application of a Sodalite Membrane Reactor in Esterification- oupling Reaction and Separation. Catalysis Today, 156(2010), 132–39.
13. [13] Zhang,W., Qing, W., Chen, N., Ren, Z., Chen, J., Sun, W. 2014. Enhancement of Esterification Conversion Using Novel Composite Catalytically Active Pervaporation Membranes. Journal of Membrane Science, 451(2014), 285–92.
14. [14] Drioli, E., Fontananova, E. 2010. Catalytic Membranes Embedding Selective Catalysts: Preparation and Applications. ss.223-228. Barbaro P., Liguori F., ed. 2010. Heterogenized Homogeneous Catalysts for Fine Chemicals Production, Catalysis by Metal Complexes 33. Springer Science Business Media B.V., Heslington, 462s.
15. [15] Julbe, A., Ayral, A. 2007. Catalytic Membrane Reactors Involving Inorganic Membranes. Water Quality Control and Health, 1(2007), 30-43.
16. [16] Vankelecom, I. F. J. 2002. Polymeric Membranes in Catalytic Reactors. Chemical Reviews, 102(2002), 3779–3810.
17. [17] Dittmeyer, R., Svajda, K., Reif, M. 2004. A Review of Catalytic Membrane Layers for Gas/Liquid Reactions. Topics in Catalysis, 29(2004), 3–27.
18. [18] Nigiz, U. F., Hilmioglu, N. D. 2016. Simultaneous separation performance of a catalytic membrane reactor for ethyl lactate production by using boric acid coated carboxymethyl cellulose membrane. Reaction Kinetics, Mechanisms and Catalysis, 118(2016), 557–575.
19. [19] Hasanoğlu, A., Salt, Y., Keleşer, S., Dinçer, S. 2009. The esterification of acetic acid with ethanol in a pervaporation membrane reactor, Desalination, 245(2009), 662–669.
20. [20] Han, Y., Enmin, L., Lingling, M., Jie, L., Kexun, C., Jincheng, D. 2015. Coupling membrane pervaporation with a fixed-bed reactor for enhanced esterification of oleic acid with ethanol. Energy Conversion and Management, 106(2015), 1379–1386.
21. [21] Shao, P., Huang, R. Y. M. 2007. Polymeric Membrane Pervaporation. Journal of Membrane Science, 287(2007), 162–79.
22. [22] Semenova, S. I., Ohya, H., Soontarapa, K. 1997. Hydrophilic Membranes for Pervaporation: An Analytical Review. Desalination, 110(1997), 251–86.
23. [23] Liu, Q. L., Chen, H. F. 2002. Modeling of Esterification of Acetic Acid with N-Butanol in the Presence of Zr(SO4)2•4H2O Coupled Pervaporation. Journal of Membrane Science, 196(2002), 171–78.
24. [24] Peters, T. A., Benes, N. E., Keurentjes, J. T. F. 2007. Preparation of Amberlyst-Coated Pervaporation Membranes and Their Application in the Esterification of Acetic Acid and Butanol. Applied Catalysis A: General 317(2007), 113–19.
25. [25] Ali, S. H. Merchant, S. Q. 2006. Kinetics of the Esterification of Acetic Acid with 2-Propanol: Impact of Different Acidic Cation Exchange Resins on Reaction Mechanism. International Journal of Chemical Kinetics, 38(2006), 593–612.
26. [26] Pereira, C. S. M., Silva, V. M. T. M. Pinho, S. P., Rodrigues, A. E. 2010. Batch and continuous studies for ethyl lactate synthesis in a pervaporation membrane reactor. Journal of Membrane Science, 361(2010), 43–55.
27. [27] Chandane, V. S., Rathod, A.P., Wasewar, K.L., 2016. Enhancement of esterification conversion using pervaporation membrane reactor. Resource-Efficient Technologies, 2:S47–S52.
28. [28] Rathod, A. P., Wasewar, K. L., Yoo, C. K. 2014. Enhancement of Esterification of Propionic Acid with Isopropyl Alcohol by Pervaporation Reactor. Journal of Chemistry, 2014:1-4 (ID 539341).
29. [29] Zhang, W., Na, S., Li, W., Xing, W. 2015. Kinetic Modeling of Pervaporation Aided Esterification of Propionic Acid and Ethanol Using T ‑ Type Zeolite Membrane. Ind. Eng. Chem. Res., 54(2015), 4940−4946.
30. [30] Chandane, V. S., Rathod, A. P., Wasewar, K. L. 2017. Chemical Engineering & Processing : Process Intensi fi cation Coupling of in-situ pervaporation for the enhanced esteri fi cation of propionic acid with isobutyl alcohol over cenosphere based catalyst. Chemical Engineering&Processing:Process Intensification, 119(2017), 16–24.
31. [31] Toukoniitty, B., Mikkola, J. P., Eranen, K., Salmi, T., Murzin, D. Y. 2005. Esterification of propionic acid under microwave irradiation over an ion-exchange resin. Catalysis Today, 100(2005), 431–435.
32. [32] Lee, M., Chiu, J., Lin, H. 2002. Kinetics of Catalytic Esterification of Propionic Acid and n -Butanol over Amberlyst 35. Ind. Eng. Chem. Res., 41(2002), 2882–2887.
33. [33] Tsai, Y., Lin, H., Lee, M. 2011. Kinetics of Catalytic Esterification of Propionic Acid with Methanol over Amberlyst 36. Ind. Eng. Chem. Res., 50(2011), 1171–1176.
34. [34] Nigiz, F. U., Hilmioglu, N. D. 2014. Novel environmental friendly process for reducing the sulphur level in fuel: Pervaporation. International Journal of Global Warming 6(2014), 455-465.
35. [35] Lilja, J., Warna, J., Salmi, T., Lars J. P., Johan A., Henrik, G., Mats, R., Dmitry Yu, M. 2005. Esterification of propanoic acid with ethanol, 1-propanol and butanol over a heterogeneous fiber catalyst. Chemical Engineering Journal, 115(2005), 1–12.
36. [36] Tiwari, A., Amit, K., Shubhankar, B. 2017. Pervaporation study of Propionic Acid with Ethanol using heterogeneous catalyst in integrated Esterification-Pervaporation system. International Journal of ChemTech Research, 10(2017), 148-162.