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Eur. J. Lipid Sci. Technol. 102 (2000) 648649

For the above-mentioned reasons, the value of partial catalytic hydrogenation is lower now, however, it will very probably be always a process of great interest and needful for both edible and nonedible purposes. For the producers of shortenings and emulsified fats, there still exists the demand to diminish the trans fatty acids content by the tune of the hydrogenation mode. Moreover, it seems that a decisive solution is the application of such processes as fractionation, total hydrogenation, and interesterification. Big companies have introduced trans zero margarines a couple of years ago, so the good and clear way has been done also for minor producers. However, to produce fat products without trans acids is not a real problem, the problem is to conserve some, mainly textural quality parameters, which are in the specific products induced with trans fatty acids. Finally, I would like to compare todays importance of hydrogenation to a traffic situation in front of the crossroad. For a mode of partial catalytic hydrogenation, it is likely to stop the lighting of green colour and will switch to orange colour, or somewhere even red one. However, this is not true for the hydrogenation itself, because in all the regime variances and applications of hardened fats, it is and will be the powerful technological step in any time. Here, I see the crossroad lights shining a bright green colour.

Formation of trans polyalkenoic fatty acids during vegetable oil refining

Walter Schwarz SETUZA AS, Ust nad Labem, Czech Republic Vegetable oils constitute an indispensable part of our diet because they provide not only an important source of essential fatty acids, but also oil soluble vitamins. In the last decades their consumption has been steadily increasing while animal fats decreased. In developed countries, vegetable oils intended for usual consumption are refined. During the refining process, undesirable substances, such as those of mucilaginous character, free fatty acids, pigments, and volatiles imparting unpleasant odours and flavours, are removed. The process results in products that consumers meet on the market vegetable oils of sparkling light yellow colour, neutral flavour, and odour. As shown by recent research, small amounts of trans unsaturated fatty acids are formed during refining, particularly in the last refining stage, i.e. during deodorisation. Initial work in this field was published by Wolff [13] in the early 90s. During the final refining stage, i.e. in the deodorisation, stripping steam is blown in oil under very low pressure and at temperatures above 200 C, to remove sensory, undesirable volatiles. Under these conditions, also other substances present in oil, such as free fatty acids, tocopherols, phytosterols, and other volatile substances, are partially entrained and distill with the stripping steam. In the chemical (alkali) refining process, free fatty acids present in oil are neutralised by sodium hydroxide, and the resulting soaps are to be washed out, the oil is then bleached and deodorised. In recent years, physical refining is an increasingly used refining method, not only for soybean oils, but due to economic reasons, also for other vegetable oils and fats [4, 5]. The physical refining is a process with increasing requirements for the efficiency of deodorising columns, because free fatty acids are not removed before the deodorisation itself, which is why higher deodorisation temperatures (by 1030 C) are used. Raw vegetable oils include just a negligible amount of trans unsaturated fatty acids, ranging between 0.10.3% of the total fatty acid content. As it follows from our own tests of refining processes on industrial scale, no trans isomerisation occurs during preceding refining stages,

References
[1] J. W. E. Coenen: Hydrogenation of edible oils. J. Am. Oil Chem. Soc. 53 (1976) 382389. [2] R. D. OBrien: Fats and Oils. Formulating and Processing for Applications. Technomic Publishing Co., Lancaster-Basel 1998. [3] V. Koman, J. Prokaj, S. Schmidt: Study on hydrogenation rate in dependence on catalytic inhibitors (in Slovak). Bull. Food Res. 22 (1983) 239250. [4] S. Schmidt, P. Bohov, J. Prokaj: The influence of partial catalytic hydrogenation on the structure of triacylglycerols in rapeseed oil (in Slovak). Bull. Food Res. 28 (1989) 395 404. [5] A. Celkov, B. Kavuliak, S. Schmidt: Effect of hydrogen distribution on hydrogenation of monoenoic oil (in Slovak). Bull. Food Res. 27 (1988) 431438. [6] A. Celkov, S. Schmidt, J. Zajc: Effect of ultrasound on hydrogenation of sunflower oil. Fat Sci. Technol. 91 (1989) 6265. [7] J. Klvanov: Trans fatty acids in fat products and metabolism (in Slovak). Lab. Diagnost. 4 (1997) 251255.

Correspondence: Walter Schwarz, SETUZA AS, CZ-401 29 Ust nad Labem, Czech Republic. Phone: +420-47529-1111, Fax: +420-47529-3999; e-mail: walter.schwarz@setuza.cz

Eur. J. Lipid Sci. Technol. 102 (2000) 648649 i.e. during hydration (degumming), deacidification, and bleaching. The content of all original trans fatty acids remains at their original level. During the deodorisation carried out at a temperature of 230 C and a pressure of 670 Pa in a Bernardini equipment the content of trans unsaturated fatty acids increased three to ten times. The highest increase was observed in polyenoic fatty acids with a double bond predominantly in position 9. Trienoic fatty acids isomerise significantly faster than dienoic acids. Monoenoic fatty acids are the most resistant to trans isomerisation, and it is interesting that only the content of trans-11 octadecenoic acid increased, while the content of trans-9 octadecenoic isomer remained unchanged. Crude rapeseed oil contains also a very small amount of conjugated fatty acids which are formed already in the seeds by enzymatic oxidation of essential fatty acids to the corresponding hydroperoxides with conjugated double bonds. In the course of deacidification and bleaching in the refining process their content remains unchanged (0.100.25%). The conjugated diene content roughly doubles in laboratory tests, but only at high temperatures, as tested in the range of 210230 C under nitrogen [6]. Conjugated trienoic systems probably decompose and disappear completely [7]. Deodorisation temperature is the main factor influencing the speed of isomerisation reactions. In deodorisation columns, used for physical refining of vegetable oils on industrial scale, the content of trans unsaturated fatty acids took place within the range of 230270 C, e.g. in case of erucic acid-free rapeseed oil, the trans fatty acid content rose up to 5.2%. At normal operating conditions of 250 C, the content of trans acids increased to 2.02.4%. Also, under conditions of physical refining, a more significant increase is observed in trans isomers of linolenic acid than linoleic acid. Monoenoic fatty acids were practically not isomerised. At the same time, conjugated dienes increased to 0.5%, and conjugated triene systems again probably decomposed to a level under the detection limit. Suitable modifications of deodorisation columns, particularly the increase of live steam/oil contact area, resulted in the decrease of necessary operation temperature down to 230240 C, while other quality parameters were retained, which also brought about a drop of the formation of corresponding trans fatty acids [8]. Under such operation conditions, the level of unsaturated trans fatty acids oscillated between 0.61.0%, which is within the limits required in trade relations [9]. Similar and maybe better results are now being achieved in the deodorisation of soybean and sunflower oils by physical refining. In this sphere of vegetable oil processing, there is no other step on the horizon bringing a further reduction of the content

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of trans unsaturated fatty acids. The only degree of freedom is the operating pressure, whose further reduction is improbable due to technical reasons.

Conclusions
Edible oils as rich sources of essential fatty acids are also a negligible source of trans unsaturated fatty acids formed during deodorisation, which is the last stage of the refining process. The isomerisation rate is controlled by temperature, while the quantity of originating trans fatty acids is influenced also by the kind of oil used and the duration of heating period. A suitable design of deodorisation equipment used for physical refining resulted in the decrease of the content of trans unsaturated fatty acids in edible oils under 1%.

References
[1] R. L. Wolff: Further sturies on artificial geometrical isomers of alpha-linolenic and in edible linolenic acid-containing oils. J. Am. Oil Chem. Soc. 70 (1993) 219. [2] R. L. Wolff: Heat-induced geometrical isomerisation of alphalinolenic acid: Effect of temperature and heating time on the appearance of individual isomers. J. Am. Oil Chem. Soc. 70 (1993) 425. [3] J. Cmolk, J. Pokorny: Physical refining of edible oils. Eur. J. Lipid Sci. Technol. 102 (2000) 472486. [4] H. Staage: The physical refining process. J. Am. Oil Chem. Soc. 62 (1985) 299308. [5] J. Cmolk, W. Schwarz, Z. Svoboda, J. Pokorny, Z. Rblov, M. Dolez H. Valentov: Effects of plant scale alkali refining al, and physical refining on the quality of rapeseed oil. Eur. J. Lipid Sci. Technol. 102 (2000) 1522. [6] K. Kovari, J. Denise, F. Zwobada, Z. Kemeny, K. Recseg, G. Henon: Kinetics of trans isomer fatty acid formation during heating. Olaj, Szappan, Kozmet. 47 (1998) 712. [7] W. Schwarz, J. Cmolk, J. Pokorny: Isomerisierung der Poly enfettsuren whrend der Desodorisierung von Speiselen. Fat Sci. Technol. 97 (1995) 491495. [8] Neue innere Einrichtung zweier Desodorierungsstufen: 301 3340 CDE Lurgi l Gas Chemie GmbH, Frankfurt a/M 1997. [9] J. Cmolk, W. Schwarz, Z. Svoboda, J. Pokorny, Z. Rblov, M. Dole al: Physical refining of rapeseed oil. Presentation on the 22nd World Congress and Exhibition of the ISF, Kuala Lumpur (Malaysia), 1997.