Malaysian Journal of Analytical Sciences Vol 18 No 3 (2014): 584 - 591

 

 

 

PREPARATION OF EPOXIDIZED PALM OLEIN AS RENEWABLE MATERIAL BY USING PEROXY ACIDS

 

(Penyediaan Minyak Sawit Olein Terepoksida Sebagai Bahan Keterbaharuan Menggunakan Asid Peroksi)

 

Darfizzi Derawi*, Jumat Salimon, Waled Abdo Ahmed

 

Oleochemistry Research Laboratory, School of Chemical Sciences and Food Technology,

Faculty of  Science and Technology,

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

*Corresponding author: darfizzi@ukm.edu.my

 

 

Abstract

Epoxidized palm olein (EPO_o) was prepared through generated in situ of performic acid (HCOOOH), and peracetic acid (CH₃COOOH) as epoxidation agent with the presence of sulphuric acid (H₂SO₄) 3 % v/wt as catalyst. Formic acid (HCOOH) or acetic acid (CH₃COOH) as oxygen carrier and hydrogen peroxide (H₂O₂) as oxygen donor in the reaction system. Highly conversion (95.5 %) of oxirane ringwas obtained by usingperformicacid as epoxidation agent at 150 minutes of reaction time. The reaction yield was 90 % by weight. EPO_o has showed good physicochemical properties as renewable material for industrial applications. Carbon (¹³C-NMR) and proton (¹H-NMR) spectra showed the present of epoxy profile at 54 ppm and 2.9 ppm. Epoxy group was detected on 844 cm^-1 byfourier transformation infra-red (FTIR) spectra.

 

Keywords: epoxidation, palm olein, in-situ, peroxy acid, renewable material

 

Abstrak

Minyak sawit olein terepoksida (EPO_o) disediakan melalui proses pengepoksidaan secara in situ menggunakan asid performik (HCOOOH), asid perasetik (CH₃COOOH) sebagai agen pengepoksidaan dengan kehadiran mangkin asid sulfurik (H₂SO₄) 3 % v/wt. Asid formik (HCOOH) atau asid asetik (CH₃COOH) sebagai pembawa oksigen dan hydrogen peroksida (H₂O₂) sebagai penderma oksigen dalam sistem tindak balas. Peratus penukaran gelang oksirana yang tinggi (95.5 %) diperolehi dengan menggunakan asid performik pada 150 minit tindak balas. Peratus hasil tindak balas adalah sebanyak 90 % berdasarkan berat. EPO_o telah menunjukan sifat fiziko kimia yang baik sebagai bahan keterbaharuan untuk aplikasi industri. Spektrum karbon (¹³C-NMR) dan proton (¹H-NMR) menunjukan kehadiran profil epoksi pada 54 ppm dan 2.9 ppm. Kumpulan epoksi dikesan pada nombor gelombang 844 cm^-1 dengan merujuk spektrum transformasi fourier inframerah (FTIR).

 

Kata kunci: pengepoksidaan, minyak sawit olein, in-situ, asid peroksi, bahan keterbaharuan

 

References

1.       Goud, V. V., Patwardhan, A. V., & Pradhan, N. C. (2006). Studies on the epoxidation of mahua oil by    hydrogen peroxide. Bioresource technology, 97 (12), 1365 – 1371.

2.       Wang, X., Zhang, H., Wang, Z., & Jiang, B. (1997). In situ epoxidation of ethylene propylene diene rubber by performic acid. Polymer, 38 (21), 5407 – 5410.

3.       Rangarajan, B., Havey, A., Grulke, E. A., & Culnan, P. D. (1995). Kinetic parameters of a two-phase model for in situ epoxidation of soybean oil. J. Am. Oil. Chem. Soc., 72 (10), 1161 – 1169.

4.       Scala, J. L. and Wool, R. P. (2002). Effect of FA composition on epoxidation kinetic of TAG. J. Am. Oil. Chem. Soc., 79 (4), 373 – 378.

5.       Gan, L. H., Goh, S. H. & Ooi, K. S. (1992). Kinetic studies of epoxidation and oxirane cleavage of palm olein methyl esters. J. Am. Oil. Chem. Soc., 69 (4), 347 – 351.

6.       Goud, V. V., Pradhan, N. C., & Patwardhan, A. V. (2006). Epoxidation of karanja (Pongamiaglabra) oil by H₂O₂. J. Am. Oil. Chem. Soc., 83 (7), 635 – 640.

7.       Gunstone, F. D. (2004). “The Chemistry of Oils and Fats: Sources, Composition, Properties and Uses” Blackwell Publishing Ltd., UK.

8.       Carlson, K. D. & Chang, S. P. (1985). Epoxidation of a Natural Unsaturated Epoxy Seed Oil from Vernoniagalamensis and a Look at Epoxy Oil Markets, J. Am. Oil. Chem. Soc., 62, 934 – 939.

9.       Hang, X., & Yang, H. (1999). Model for a cascade continuous epoxidation process. J. Am. Oil. Chem. Soc., 76 (1), 89 – 92.

10.    Guenter, S., Rieth, R., Rowbottom, K. T. (2003). “Ullmann’s Encyclopedia of Industrial Chemistry” Wiley-VCH, 6th Edition.

11.    Rios, L. A., Weckes, P., Schuster, H.. & Hoelderich, W. F. (2005). Mesoporous and amorphous Ti–silicas on the epoxidation of vegetable oils J. Catal., 232, 19 – 26.

12.    Warwel, S. & Klaas, M. R. (1995). Chemo-enzymatic epoxidation of unsaturated carboxylic acids. J. Mol. Cat. B: Enzym, 1, 29 – 35.

13.    Sharpless, K. B., Woodard, S. S. & Finn, M. G. (1983). On the mechanism of titanium-tartrate catalyzed asymmetric epoxidation. Pure Applied Chemistry. 55 (4), 1823 – 1836.

14.    Dinda, S., Patwardhan, A. V, Goud, V. V. & Pradhan, N.C. (2008). Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids. Bioresource Technology, 99, 3737 – 3744.

15.    O’Brien, R. D. (1998). “Fats and Oils; Formulating and Processing for Applications”, Technomic Publishing AG, Switzerland.

16.    Scrimgeour, C. (2005). “Chemistry of Fatty Acids” John Wiley & Sons Inc., Scotland, 6th Edition.

17.    Campanella, A., Fontanini, C. & Baltanás, M. A. (2005). Catalysis Today, 107-108, 208-214.

18.    Campanella, A., Fontanini, C. & Baltanás, M. A., (2008), High yield epoxidation of fatty acid methyl esters with performic acid generated in-situ, Chemical EngineeringJournal, 144, 466 – 475.

19.    Klaas, M. R. & Warwel, S. (1999). Complete and partial epoxidation of plant oil by lipase-catalysed perhydrolysis. Ind.  Crops Prod., 9 (2), 125 – 132.

20.    Derawi, D. & Salimon, J. (2010). Optimization on epoxidation of palm olein by using performic acid. E-Journal of Chemistry, 7 (4), 1440 – 1448.

21.    A.O.C.S. (1998). Official Metthods and Recommended Practices of AOCS, AOCS, Illionis.

22.    Paquot, C. (1979). “Standards Methods for the Analysis of Oils, Fats and Derivatives Part-1” Pergamon Press, Germany, 5th Edition

23.    Pavia, D. L. (2001). “Introduction to Spectroscopy” Thomson Learning, Inc., United States

24.    Derawi, D. & Salimon, J. (2013). Palm olein based biolubricant basestocks: synthesis, characterisation, tribological and rheological analysis. Malaysian Journal of Analytical Sciences, 17 (1), 153 – 163.

25.    Findley, T. W., Swern, D. & Scanlan, J. T. (1945). Epoxidation of unsaturated fatty materials with peracetic acid in glacial acetic acid solution. J. Am. Oil. Chem. Soc., 67(3), 412 – 414.

26.    Greenspan, F. P. (1946). The convenient preparation of per-acids. J. Am. Oil. Chem. Soc., 68(5), 907 – 907.

27.    Socrates, G. (2001). “Infrared and Raman Characteristic Group Frequencies” John Wiley & Sons Ltd., England, 3rd Edition.