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Journal of the American Oil Chemists’ Society

, Volume 73, Issue 10, pp 1311–1316 | Cite as

Catalytic hydrogenation of linoleic acid on nickel, copper, and palladium

  • Yoshie Kitayama
  • Masahiro Muraoka
  • Megumi Takahashi
  • Tatsuya Kodama
  • Hirofumi Itoh
  • Eriko Takahashi
  • Mutsuo Okamura
Article

Abstract

The catalytic activity and selectivity for hydrogenation of linoleic acid were studied on Ni, Cu, and Pd catalysts. A detailed analysis of the reaction product was performed by a gas-liquid chromatograph, equipped with a capillary column, and Fourier transform-infrared spectroscopy. Geometrical and positional isomerization of linoleic acid occurred during hydrogenation, and many kinds of linoleic acid isomers (trans-9,trans-12; trans-8,cis-12 orcis-9,trans-13; cis-9,trans-12; trans-9,cis-12 andcis-9,cis-12 18∶2) were contained in the reaction products. The monoenoic acids in the partial hydrogenation products contained eight kinds of isomers and showed different isomer distributions on Ni, Cu, and Pd catalysts, respectively. The positional isomers of monoenoic acid were produced by double-bond migration during hydrogenation. On Ni and Pd catalysts, the yield ofcis-12 andtrans-12 monoenoic acids was larger than that ofcis-9 andtrans-9 monoenoic acids. On the contrary, the yield ofcis-9 andtrans-9 monoenoic acids was larger than that ofcis-12 andtrans-12 monoenoic acids on Cu catalyst. From these results, it is concluded that the double bond closer to the methyl group (Δ12) and that to the carboxyl group (Δ9) show different reactivity for hydrogenation on Ni, Cu, and Pd catalysts. Monoenoic acid formation was more selective on Cu catalyst than on Ni and Pd catalysts.

Key Words

Catalytic hydrogenation Cu geometrical and positional isomers linoleic acid Ni Pd reaction mechanism 

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References

  1. 1.
    Heertje, I., and H. Boerma, Selectivity and Monoene Isomerization in the Catalytic Hydrogenation of Polyenoic Fatty Acid Methyl Esters,J. Catal. 21:20–26 (1971).CrossRefGoogle Scholar
  2. 2.
    Gut, G., J. Kosinka, A. Prabucki, and A. Schuerch, Kinetics of the Liquid-Phase Hydrogenation and Isomerization of Sunflower Seed Oil with Nickel Catalysts,Chem. Eng. Sci. 34:1051–1056 (1979).CrossRefGoogle Scholar
  3. 3.
    Rodrigo, M. T., and S. Mendioroz, A New Catalyst for the Selective Hydrogenation of Sunflower Seed Oil,J. Am. Oil Chem. Soc. 69:802–805 (1992).Google Scholar
  4. 4.
    Bern, L., M. Hell, and N.-H. Schöön, Kinetics of the Hydrogenation of Rapeseed Oil: 11. Rate Equations of Chemical Reactions,Ibid. 52:391–394 (1975).Google Scholar
  5. 5.
    Köseoglu, S.S., and E.W. Lusas, Recent Advances in Canola Oil Hydrogenation,Ibid. 67:39–47 (1990).Google Scholar
  6. 6.
    Scholfield, C.R., R.O. Butterfield, and H.J. Dutton, Calculation of Catalyst Selectivity in Vegetable Oil Hydrogenation,Ibid. 56:664–667 (1979).Google Scholar
  7. 7.
    Anderson, J.A., M.T. Rodrigo, L. Daza, and S. Mendioroz, Influence of the Support in the Selectivity of Ni/Clay Catalysts for Vegetable Oil Hydrogenation,Langmuir 9:2485–2490 (1993).CrossRefGoogle Scholar
  8. 8.
    Hsu, N., L.L. Diosady, and L.J. Rubin, Catalytic Behavior of Palladium in the Hydrogenation of Edible Oils,J. Am. Oil Chem. Soc. 65:349–356 (1988).Google Scholar
  9. 9.
    Wisniak, J., and L.F. Albright, Hydrogenating Cottonseed Oil at Relatively High Pressure,Ind. Eng. Chem. 53:375–380 (1961).CrossRefGoogle Scholar
  10. 10.
    Coenen, J.W.E., The Rate of Change in the Perspective of Time,Chem. Ind. 16:709–722 (1978).Google Scholar
  11. 11.
    Albright, L.F., and J. Wisniak, Selectivity and Isomerization During Partial Hydrogenation of Cottonseed Oil and Methyl Oleate: Effect of Operating Variables,J. Am. Oil Chem. Soc. 39:14–19 (1962).Google Scholar
  12. 12.
    Albright, L.F., R.R. Allen, and M.C. Moore, Quantitative Measure of Geometrical Isomerization During the Partial Hydrogenation of Triglyceride Oils,Ibid. 47:295–298 (1970).Google Scholar
  13. 13.
    Hashimoto, K., K. Muroyama, and S. Nagata, Kinetics of the Hydrogenation of Fatty Oils,Ibid. 48:291–295 (1971).Google Scholar
  14. 14.
    Ackman, R.G., and S.N. Hooper,Cis andTrans Isomerism in Some Polyethylenic C18 Fatty Acids,J. Chromatogr. Sci. 12:131–138 (1974).Google Scholar
  15. 15.
    Metcalfe, L.D., and C.N. Wang, Rapid Preparation of Fatty Acid Methyl Esters Using Organic Base-Catalyzed Transestrification,Ibid. 19:530–535 (1981).Google Scholar
  16. 16.
    Sebedio, J.-L., and R.G. Ackman, Calculation of GLC Retention Data for Some Accessible C20 IsomericCis-Unsaturated Fatty Acids,Ibid. 20:231–234 (1982).Google Scholar
  17. 17.
    Ratnayake, W.M.N., and J.L. Beare-Rogers, Problems of Analyzing C18 Cis- andTrans-Fatty Acids of Margarine on the SP-2340 Cappillary Column,Ibid. 28:633–639 (1990).Google Scholar
  18. 18.
    Wolff, R.L., Resolution of Linoleic Acid Geometrical Isomers by Gas-Liquid Chromatography on a Capillary Column Coated with a 100% Cyanopropyl Polysiloxane Film (CPTM Sil88),Ibid. 30:17–22 (1992).Google Scholar
  19. 19.
    Wolff, R.L.,Trans-Polyunsaturated Fatty Acids in French Edible Rapeseed and Soybean Oils,J. Am. Oil Chem. Soc. 69:106–110 (1992).Google Scholar
  20. 20.
    Ratnayake, W.M.N., and G. Pelletier, Positional and Geometrical Isomers of Linoleic Acid in Partially Hydrogenated Oils,Ibid. 69:95–105 (1992).Google Scholar
  21. 21.
    Ratnayake, W.M.N., Z.Y. Chen, G. Pelletier, and D. Weber, Occurrence of 5c,8c,11c,15t-Eicosatetraenoic Acid and Other Unusual Polyunsaturated Fatty Acids in Rats Fed Partially Hydrogenated Canola Oil,Lipids 29:707–714 (1994).Google Scholar
  22. 22.
    Dutton, H.J., C.R. Scholfield, E. Selke, and W.K. Rohwedder, Double-Bond Migration, Geometric Isomerization, and Deuterium Distribution During Heterogeneous Catalytic Deuteration of Methyl Oleate,J. Catal 15:316–327 (1968).CrossRefGoogle Scholar
  23. 23.
    Hammer, B., and J.K. Norskov, Why Gold Is the Noblest of All the Metals,Nature 376:238–240 (1995).CrossRefGoogle Scholar
  24. 24.
    Hsu, N., L.L. Diosady, W.F. Graydon, and L.J. Rubin, Heterogeneous Catalytic Hydrogenation of Canola Oil Using Palladium,J. Am. Oil Chem. Soc. 63:1036–1042 (1986).CrossRefGoogle Scholar

Copyright information

© AOCS Press 1996

Authors and Affiliations

  • Yoshie Kitayama
    • 3
  • Masahiro Muraoka
    • 3
  • Megumi Takahashi
    • 3
  • Tatsuya Kodama
    • 3
  • Hirofumi Itoh
    • 1
  • Eriko Takahashi
    • 1
  • Mutsuo Okamura
    • 2
  1. 1.Nikki Chemical Co. Ltd. Niitsu Plant OfficeNiitsu CityJapan
  2. 2.Department of Chemistry, Faculty of ScienceNiigata UniversityIkarashi NiigataJapan
  3. 3.Department of Chemistry and Chemical Engineering, Faculty of EngineeringNiigata UniversityNiigataJapan

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