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Title:
TRANS FREE PALM OIL AND PALM KERNAL OIL FRACTIONS
Document Type and Number:
WIPO Patent Application WO/2005/122777
Kind Code:
A2
Abstract:
A trans free non hydrogenated high C-16 type palm fat suitable for the manufacture of trans free non hydrogenated hard structural fat that is being suitable for use in the manufacture of low SAFA (Saturated Fatty Acid) poly/mono unsaturated margarine and spreads and shortening and fat blends incorporating such hard Structural fat. The Structural fat is made from selectively fractionated non-hydrogenated high melting palm oil fraction with a C-16 fatty acid residue of at least 70 % , which is subjected to chemical random interesterification using alkaline metal catalyst such as sodium methoxide/sodium methylate, with a dry fractionated non hydrogenated hard palm kernel stearin fraction. The structural fat that is produced has high yield ratios that can be economically and commercially incorporated in the oil blends for the manufacture of trans free margarine/spreads/shortening as well as other plastic W/O emulsions. Also described is a process for the manufacturing such structural fat as well as hard palm fraction including process for the manufacture of extra hard trans free structural fat by panning and pressing of above structural fat.

Inventors:
ULLANOORMADAM SAHASRANAMAM R (MY)
Application Number:
PCT/IB2005/001659
Publication Date:
December 29, 2005
Filing Date:
June 14, 2005
Export Citation:
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Assignee:
ULLANOORMADAM SAHASRANAMAM R (MY)
International Classes:
A23D7/00; A23D9/00; A23D9/02; A23G1/56; A23K1/16; A23K1/18; C11B7/00; C11C3/10; (IPC1-7): A23D7/00
Foreign References:
US5858445A1999-01-12
US6808737B22004-10-26
Other References:
HUI Y H.: 'Bailey's Industrial Oil and Fat Products.', 1996, JOHN WILLEY & SONS, INC. XP008059420
GHOSH S AND BHATTACHARYYA DK.: 'Utilization of high-melting palm stearin in lipase-catalyzed interesterification with liquid oils.' JOURNAL OF THE AMERICAN OIL CHEMIST'S SOCIETY. vol. 74, no. 5, May 1997, pages 589 - 592, XP000691987
SIEW WL ET AL: 'Identity characteriatics of Malaysian palm oil products: fatty acid and triglyceride composition and solid fat content.' ELAEIS. vol. 5, no. 1, June 1993, pages 38 - 46, XP008059407
KHEIRI MSA.: 'Palm oil products in cooking fats.' JOURNAL OF THE AMERICAN OIL CHEMIST'S SOCIETY. vol. 62, no. 2, February 1985, pages 410 - 416, XP008059422
Attorney, Agent or Firm:
Schweitzer III, Fritz L. (292 Madison Avenue - 19th Floor New York, NY, US)
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Claims:
Claims:
1. A method of producing a margarine, spread, shortening or fat blend comprising: providing a liquid oil selected from the group consisting of sunflower oil, Canola oil, soy oil, peanut oil, rice bran oil, olive oil, safflower oil, corn oil, marine oil, high oleic sunflower oil, high oleic Canola oil, flax seed oil, cotton seed oil or a blend of any of the above liquid oils; blending said liquid oils with a trans free hard structural fat, said margarine and spread fat blend comprising 6095% of said liquid oil and 540% of said trans free structural fat; said trans free hard structural fat is made from selectively fractionated nonhydrogenated hard palm oil fraction, which is interesterified with lauric fat such as palm kernel oil or dry fractionated nonhydrogenated palm kernel oil fraction, without using hydrogenation process and without using organic solvent or detergent for fractionation.
2. A method of producing a margarine and spread fat blend, according to claim , wherein: said hard palm oil fraction has a C16 fatty acid residue level of greater than 75%; said hard palm oil fraction is interesterified with a hard palm kernel oil or its fraction by random chemical interesterification, producing an interesterified fat ; and said interesterified fat is subjected to a physical fractionation method of panning and pressing at a temperature of less than 30 degrees Celsius to produce extra hard structural fat.
3. A fat blend suitable for the manufacture of margarine, spread and shortening, salad dressing , mayonnaise, bakery products, nutrition bars, beverages, soups, sauces, gravies, pizza and frozen dinner entrees said fat blend comprising 60 96% of a liquid oil selected from the group consisting of sunflower oil, canola oil, soy oil, peanut oil, rice bran oil, olive oil, rape seed oil, safflower oil, com oil, cotton seed oil, high oleic sunflower oil, palm oil or its fractions, marine oils, or a blend of any of the above liquid oils sunflower oil, palm oil or its fractions, marine oils, or a blend of any of the above liquid oils with a trans free hard structural fat or a trans free extra hard structural fat at 40 4% level, wherein said trans free structural fat as well as trans free extra hard structural fat is made by interesterifying a selectively fractionated nonhydrogenated hard palm oil fraction, with palm kernel oil or a fractionated nonhydrogenated hard palm kernel oil stearin fraction and wherein the said hard palm kernel oil stearin fraction is a stearin fraction of palm kernel oil with a C12 carbon chain fatty acid residue level of at least 50 % and a saturated fat level of at least 85%; the said hard palm oil stearin fraction'is a stearin fraction of palm oil with a C 16 carbon chain fatty acid residue of at least 70% and saturated fatty acid level of at least 85 %; the said trans free hard structural fat is obtained by interesterification of the said hard palm oil stearin fraction and said hard palm kernel oil stearin fraction.
4. A fat blend according to claim 3, wherein the fat blend has a poly or mono unsaturated level of at least 40 %.
5. A method of producing a trans free hard structural fat, comprising: selectively fractionating nonhydrogenated palm oil or a stearin fraction thereof such that the Cl 6 fatty acid residue level in the hard palm oil fraction is greater than 70%; interesterifying said hard palm oil fraction with lauric fat such as palm kernel oil or a dry fractionated nonhydrogenated palm kernel oil fraction without using hydrogenation process and without subjecting the said trans free hard structural fat to further fractionation process; said trans free hard structural fat being produced without using organic solvent or detergent for fractionation; said dry fractionating process is a melt crystallization process; separating a hard palm oil fraction in a high pressure membrane filter, such that said hard palm oil fraction has a C16 carbon chain fatty acid residue level of greater than 70%; using a pressure of between about 10 bar and 60 bar to inflate the membranes of said high pressure membrane filter to remove a liquid fraction occluded in the hard palm oil fraction collected in said high pressure membrane filter; said high pressure application resulting in increased concentration of C 16 carbon chain fatty acid in the recovered hard palm oil stearin fraction to a level of at least 70%.
6. A trans free hard structural fat, comprising: a hard palm oil fraction made by selectively dry fractionating non hydrogenated palm oil or a stearin fraction thereof, said hard palm oil fraction having a C16 carbon chain fatty acid residue level greater than 70%; interesterifying said hard palm oil fraction with lauric fat such as palm kernel oil or a dry fractionated nonhydrogenated palm kernel oil fraction , without using hydrogenation process and without subjecting the said trans free hard structural fat to further fractionation process; said trans free hard structural fat being produced without using organic solvent or detergent for fractionation; said interesterified mixture is subjected to a physical fractionation method of panning and pressing at a temperature of less than 30 degrees Celsius to yield an extra hard structural fat.
7. A trans free hard structural fat having a trisaturated triglyceride H3 type at most 25%, wherein "H" denotes saturated fatty acid residues with carbon numbers greater than or equal to 16, wherein: the said fat being produced by interesterification reaction of a hard palm oil stearin fraction having a C16 carbon chain fatty acid residue of at least 70% and a saturated fatty acid level (SAFA) of at least 85% with a hard palm kernel oil stearin fraction having a C 12 carbon chain fatty acid residue of at least 50 %, and a saturated fatty acid residue (SAFA) level of at least 85%.
8. A trans free hard structural fat, as in claim 7, wherein: said structural fat being used in the formulation of a fat blend suitable for the manufacture of margarine , spread , shortening, salad dressing , mayonnaise, bakery products, nutrition bars and beverages, soups and sauces, gravies, pizza and frozen dinner entrees along with liquid oils or blend of liquid oils with out subjecting it to further fractionation process and the said fat blend resulting in a low SAFA ,high mono or poly unsaturated products.
9. A trans free hard structural fat, as in claim 8, wherein: said structural fat is used in a chocolate fat system at very low levels to improve bloom resistance.
10. A trans free hard structural fat according to claim 7, wherein: the said trans free hard structural fat being further subjected to panning to form a hard crystallized slab at a temperature not exceeding about 30 Degrees Celsius and the said slab is wrapped in a filter cloth and then pressed in a hydraulic press to remove the liquid olein fraction entrapped in the cooled slab, the pressing operation resulting in a extra hard trans free structural fat , the yield of extra hard trans free structural fat being at least 60 %; the said trans free hard structural fat being further subjected to panning to form a hard crystallized slab at a temperature not exceeding 30 Degrees Celsius and the said slab is minced to form a thick slurry and pumped in to a membrane press to remove the liquid olein fraction entrapped in the slurry, the membrane filtration resulting in a extra hard trans free structural fat , the yield of extra hard trans free structural fat being at least 60 %; said extra hard trans free hard structural fat has a tri saturated tri glyceride H3 type is at most 20%, wherein "H" denotes saturated fatty acid residues with carbon numbers greater than or equal to 16.
11. A trans free hard structural fat, as in claim 10, wherein: said fat is used in blend with any liquid oil selected from the group consisting of sunflower oil, high oleic sunflower oil , canola oil, soy oil, peanut oil, rice bran oil, olive oil, rape seed oil, cotton seed oil , safflower oil, corn oil, palm oil or its fractions, and marine oils, or in a blend of any of the above liquid oils to formulate a trans free non hydrogenated fat suitable for formulating low SAFA, high mono or poly unsaturated products.
12. A trans free hard structural fat, as in claim 11, wherein said fat is used as a trans free crystallization promoter in confectionary fat applications.
13. A trans free hard structural fat, as in claim 11, wherein said fat is used to avoid oiling out of peanut butter.
14. A trans free hard structural fat, as in claim 11, wherein said fat is used for the formulation of margarine, spread, shortening, salad dressing, mayonnaise, bakery products, nutrition bars, beverages, soups, sauces, gravies, pizza or frozen dinner entrees.
15. A trans free hard structural fat, as in claim 11 , wherein said structural fat being used in a chocolate fat system to improve bloom resistance.
16. A method of producing trans free hard structural fat according to claim 7 or 10, wherein: said interesterifϊcation process is a random chemical interesterification process using sodium methoxide or sodium methylate as catalyst.
17. A method of producing of trans free hard structural fat according to claim 7, 10 or 16, wherein said interesterifϊcation process is a random or 1 ,3 specific enzymatic interesterification process.
18. A hard palm oil stearin fraction having a C16 carbon chain fatty acid residue of at least 70%, comprising: said fraction having a melt point of at least 57 Def Celsius and having a solid fat content of at least 75 % at 40 Deg Celsius; said hard stearin fraction is obtained by a single or two stage melt crystallization of palm oil or stearin fraction thereof ; said hard palm stearin fraction having a saturated fatty acid residue level of at least 85 %; and said hard palm oil stearin fraction can be flaked or sprayed and granulated for easy handling because of its high melting point in spite of not being required to undergo hydrogenation.
19. A method of producing hard palm oil stearin fraction according to claim 18, comprising: selectively dry fractionating the said palm oil or a stearin fraction thereof, by a melt crystallization process; separating said hard palm oil fraction from crystallized slurry of the said palm oil or it's stearin fraction in a high pressure membrane filter; subjecting the said separated hard palm oil fraction in the said filter press to a squeezing pressure exceeding 10 bar by inflating the membranes of the said filter; said hard palm oil fraction recovered as filter cake has a C 16 carbon chain fatty acid residue level of at least 70%; said high pressure membrane filter having a chamber depth of at most 35 millimeter.
20. A method of producing hard palm oil fraction according to claim 19, further comprising: said hard palm oil fraction being produced using a twostep melt crystallization process of palm oil or it's stearin fraction; a first step of said twostep melt crystallization process comprising of crystallizing said palm oil at a temperature between about 20 and 25 degrees Celsius and separating a crystallized slurry of said palm oil through a filter, said first step producing a medium hard palm stearin fraction having an iodine value varying from about 26 to about 40; second step of said twostep melt crystallization process comprising crystallizing said medium hard palm stearin fraction at a temperature between about 40 to about 55 degrees Celsius and filtering a crystallized slurry of said medium hard palm stearin fraction through a high pressure membrane filter; said second step producing a very hard palm stearin fraction with a Cl 6 carbon chain fatty acid residue level of at least 70%; and said high pressure membrane filter having a chamber depth of at most 35 millimeter.
21. A high pressure membrane filter being used for the production of hard palm stearin fraction according to claim 19 or 20, wherein: said high pressure membrane filter having a chamber depth of at most 35 millimeter; said high pressure membrane filter suitable for application of squeeze or inflation pressure of at least 10 bar.
22. A high pressure membrane filter being used for the production of hard palm stearin fraction according to claim 19, 20 or 21, wherein: a pressure of at least 10 bar is applied to inflate the membranes of the high pressure membrane filter.
23. A high pressure membrane filter press, as in claim 22 wherein said filter is suitable for applying an inflation pressure up to about 60 bar.
24. A high pressure membrane filter being used for the production of hard palm stearin fraction having a C 16 fatty acid residue of at least 70% according to claim 19 or 20, wherein: said high pressure membrane filter press having a chamber depth of 5 to 15 millimeter; said pressure membrane filter suitable for application of squeeze or inflation pressure of at least 10 bar.
25. A high pressure membrane filter being used for the production of hard palm stearin fraction having a C 16 fatty acid residue of at least 70% according to claim 19 or 20, wherein: said high pressure membrane filter press having a chamber depth of 5 to 15 millimeter; said high pressure membrane filter suitable for application of squeeze or inflation pressure of at least about 10 bar.
26. A high pressure membrane filter as in claim 25, wherein said of squeeze or inflation pressure is up to about 60 bar.
27. A hard palm oil fraction, comprising: said hard palm oil fraction having a C16 carbon chain fatty acid residue level is greater than 70%; said hard palm oil fraction being produced by selectively dry fractionating palm oil or a stearin fraction thereof, by a melt crystallization process; separating the hard palm oil fraction from said dry fractionated palm oil or its stearin fraction, in a high pressure membrane filter; and subjecting the hard palm oil fraction collected in the said high pressure membrane filter to a pressure of between about 10 bar and about 60 bar by inflating the membranes of said high pressure membrane filter to remove a liquid fraction occluded in the hard palm oil fraction collected in said high pressure membrane filter; and said process producing a hard palm oil stearin fraction having a C16 carbon chain fatty acid residue of at least 70%.
28. A hard palm oil fraction, according to claim 27, further comprising: said hard palm oil fraction is produced using a twostep melt crystallization process; a first step of said twostep melt crystallization process comprising crystallizing said palm oil at a temperature between about 20 and 25 degrees Celsius and filtering a crystallized slurry of said palm oil through a membrane filter, said first step producing a medium hard palm oil fraction; and a second step of said twostep melt crystallization process comprising crystallizing said medium hard palm oil fraction at a temperature between about 45 to 55 degrees Celsius and filtering a crystallized slurry of said medium hard palm oil fraction through a high pressure membrane filter; subjecting the hard palm oil fraction collected in the said high pressure membrane filter to a pressure of between about 10 bar and about 60 bar by inflating the membranes of said high pressure membrane filter to remove a liquid fraction occluded in the hard palm oil fraction collected in said high pressure membrane filter; and said filtration step producing a very hard palm oil fraction with a Cl 6 carbon chain fatty acid residue level of greater than 70%.
29. A hard palm oil fraction having a C16 carbon chain fatty acid residue of at least 70 % as in claim 18, wherein: said hard fraction being used as a rumen bypass fat or a rumen inert fat; said fat being used at least 65 % in a blend with fatty acid being used as a rumen bypass or inert fat with or with out other additives; said fat being used as a trans free crystallization promoter in confectionary fat applications; said fat being used as an additive in soup blends or any dry blends; said fat being used to avoid oiling out of peanut butter; said fat being used in interesterification reaction with any liquid oil selected from the group consisting of sunflower oil, canola oil, soy oil, peanut oil, rice bran oil, olive oil, rape seed oil, safflower oil, corn oil, palm oil or its fractions, marine oils, or a blend of any of the above liquid oils to formulate a trans free non hydrogenated fat for any applications.
30. A method of producing hard palm stearin fraction according to claim 16 wherein: palm stearin fraction is cooled to form a slab of thickness preferably more than 0.5 inch; the said cooled slab being wrapped in a filter cloth of tight air permeability; the said wrapped slabs are subjected to hydraulic pressure to remove the occluded olein fraction; the said process resulting in a hard palm stearin fraction having C 16 carbon chain fatty acid residue level of at least 70 %.
31. A soft trans free olein fraction having a slip melt point of 3249 Deg Celsius being used as confectionary filling fat, mil fat replacer, or shortening.
32. A trans free soft palm olein fraction, comprising: the said olein fraction being obtained by melt crystallization and single or two stage fractionation of palm oil stearin fraction having an iodine number between 26 to 40; said olein fraction being obtained as a byproduct while separation of hard palm stearin fraction having C 16 carbon chain fatty acid residue level of 70 % and above; the said olein fraction having a melt point varying from 32 Deg Celsius to 48 Deg Celsius; the said olein fraction having a level of solid fat of 3454 % at 20 degrees Celsius, 1214% at 30 degrees Celsius; 35% at 35 degrees Celsius; and 24% at 40 degrees Celsius; and the said olein fraction having substantially no trans fats other than very low levels developed during high temperature deodorization.
33. A trans free soft palm olein fraction, as in claim 32, wherein said trans free olein fraction is produced by filtering a crystallized slurry of palm stearin fraction in a membrane filter to remove a hard stearin fraction having high C 16 carbon chain fatty acid residue of at least 70%.
34. A trans free soft palm olein fraction, as in claim 32, wherein said olein fraction being obtained as byproduct while producing hard palm oil stearin fraction as per claim 3.
35. A trans free soft palm olein fraction, as in claim 32, wherein said soft olein fraction being used as such or blending with other fats or oils for confectionary filling.
36. A trans free soft palm olein fraction, as in claim 32, wherein said trans free olein fraction being used to replace milk fat in confections.
Description:
Trans Free Non-Hydrogenated Hard Structural Fat and Non-Hydrogenated Hard Palm Oil Fraction Component

Background of the Invention

Historically emulsified fat system in margarine/spreads has been designed to satisfy customer requirements such as significant cooling impact, a rapid sharp melt sensation, and no coated or waxy feel on the tongue. In addition, it should impart temperature cycling stability (heat stability) as well as spread ability when taken out frequently from the refrigerators is the prominent features.

To achieve these objectives, margarine fat blend is being formulated using hard stocks derived by hydrogenation of liquid oils.

However, with the adverse effect of Trans fatty acids being published, consumers are looking for margarine/spreads with practically no trans fatty acids. Recent studies have indicated that trans fatty acids produced during the hydrogenation process is considered much more harmful compared to saturated fatty acids (SAFA). Low trans fatty acid levels can be achieved by using fully hydrogenated fats as structural fat, which visually does not contain trans fatty acid or very negligible amount. Such hydrogenated fats were subjected interesterification with lauric fats and solvent fractionated to derive premium quality structural fat that could be incorporated in smaller level to produce Low SAFA products.

Hydrogenation process is generally viewed as the main reason for the development of trans fatty acids in oils and fats. Hence, there is a strong consumer perception against usage of and hydrogenated oil/fat in the food products including margarine/spreads/shortening. Further use of organic solvent as well detergent for fractionation process are viewed by the consumers are unhealthy processing.

Hence research work is being carried out for developing margarine/spreads and shortening using no hydrogenated oils in their hard stock at the same time looking at the possibility of reducing the saturated fatty acid levels (SAFA) in the products At the same time work were carried out to develop new fractionation process to eliminate usage of solvent/detergents in the fractionation process.

For manufacturing Margarine/Spreads, the fat blend should be such that it has a flat melt profile from 5 to 30 Deg C at the same time low solids at 35 and 40 deg C so that the product has good mouth feel. The blend should be such that the product does not oil out and has good temperature cycling stability.

Further in recent years due to high publicity in the media with respect to adverse effect of Saturated as well as trans fatty acids, many manufacturers have taken a nutritional approach to manufacture the product by reducing the saturated as well as trans fatty acids and increasing poly /mono unsaturated fatty acids in the margarine/spreads as well as shortening.

Margarine/Spreads have been on the market for some time aiming to meet this need. Typically, the margarine fat of these products consists of about 87% liquid oil, e.g. sunflower oil and 13% of a hard stock consisting of a random interesterified mixture of fully hardened lauric fat, e.g. fully hardened palm kernel oil, and fully hardened palm oil.

Attempts have been made over the years to formulate margarine/spread fat blends by using much lower levels of hard stock. For example EP 89,082 recommended H2M rich hard stocks. The preferred method described in EP 89,082 for producing such hard stock is randomly interesterifying a partly or fully hydrogenated lauric fat having a melting point ranging from 30 to 41.degree. C, with a fat, which can be fully or partly hydrogenated, fractionated or non-fractionated, wherein at least 60% of the fatty acid residues are C.sub.16 - or C.sub.18 -fatty acid residues. This C.sub.16 -C.sub.18 fat is preferably selected from palm fat, soybean oil, groundnut oil, sunflower oil, maize oil, and rapeseed oil, having a melting point ranging from 50 to 71.degree. C; and fractionating the interesterified mixture. Fractionation is preferably done in an organic solvent. The examples of EP 89,082 illustrate spreads comprising margarine fats containing 90 or even 93% sunflower oil and only 7 or 10% hard stock. This hard stock is produced by means of 2-stage fractionation in acetone to obtain a mid fraction of a random interesterified mixture of 50 parts fully hydrogenated palm kernel fat and 50 parts fully hydrogenated palm fat. Thus EP 89,082 met the objective of manufacture of Margarine/Spreads with very Low SAFA as well as very PUFA/MUFA by producing a hard Structural fat that can be used at levels as low as 4 %.

However, recently consumers have been expressing concern about chemically modifying fats e.g. by hydrogenating or hardening, which result in trans fatty acid residues if partial hardening is involved. Also consumers have been voicing their concern over use of solvent such as Acetone etc as well detergents for fractionation of fats. Even though full hydrogenation eliminates the presence of trans fatty acid residues, still there is a consumer perception that any hydrogenated product is undesirable. Because of this the manufacturers of margarine/Spreads have been looking for alternate hard stock, which do not undergo hydrogenation as well as solvent fractionation processes. To meet the need for spreads with low contents of SAFA in the margarine fat which have been produced without using hydrogenation, CA 2 098 314 proposes to prepare hard stock by chemically interesterifying a blend of generally equal proportions of palm stearin and palm kernel stearin.

However the usage level of such hard stock was 14-21 % especially about 16 % to obtain a good quality product. This high level of usage resulted in higher level of SAFA in the final products. Hence attempts have been made to prepare hard stock that can be used at much reduced levels of even 5 to 14 %. This objective was reached to a considerable extent in recent years. For Example in US 5,858,445, US 6,156,370, CA 2207954, as well as in WO 96/19115, the inventers have found that a hard structural fat that can be used at level of 5-14% can be produced with out Solvent fractionation, random chemical interesterifϊcation as well as hydrogenation process that has been used in EP 89,082. Accordingly, the invention provides a margarine fat blend essentially comprising 86-95% liquid oil and 5- 14% of a hard stock, this hard stock being a stearin fraction of an enzymatically interesterified mixture of 25-65%, and preferably 35-55%, unhardened lauric fat stearin and 75-35%, and preferably 65-45%, unhardened C.sub.l6+ fat stearin.

By selecting unhardened natural vegetable fat products having sufficient saturated fatty acids, such as lauric fat fractions and palm oil fractions for the enzymatic interesterification, the chemical modification of the fats were reduced to a minimum and the trans fatty acid level in the final fat blend were to almost zero. The hard stock produced from un-hydrogenated fat under US 5,858,445, US 6,156,370, CA 2207954and WO 96/19115, could achieve quite similar results with respect to the nutritional properties of the spread as in EP 89,082. How ever EP 89,082 focus on fully concentrates on achieving the minimum SAFA content in the product with acceptable product properties and heat cycling stabilities. To meet this requirement, the inventors used all the fat modification techniques including hydrogenation, chemical interesterifϊcation, solvent fractionation and even chemical synthesis of triglycerides.

By using Structural fat produced under US 5,858,445, US 6,156,370, CA 2207954 and WO 96/19115 the inventers could substantially match the performance of EP 89,082 without using Hydrogenation, solvent fractionation, and chemical interesterifϊcation. However to achieve this, they had to resort to expensive multi stage dry fractionation process as per EP 399,597 to produce hard palm C16 fraction. Further, they had to use expensive enzymatic interesterification process for interesterifϊcation of Laurie fat as well as palm fat. Further, the interesterifϊed fat was required to undergo an additional dry fractionation process at 31-41 Deg C to produce hard Structural fat for use in margarine blend. Solvent fractionation process improved the yield of the hard fraction but is considered very expensive and not natural because of usage of solvent in the process . Such solvent fractionation plant are highly capital intensive and require very high safety and environmental feature. This, however, resulted in low yields of structural fat ranging from 14 to 45 %. Since this process produced excessive olein fraction (liquid fraction) as a byproduct, alternate use for olein fraction need to be found to get economical value for such fraction. This resulted in the process being commercially un-attractive. Further, inventors used enzymatic interesterifϊcation method. To date, the cost of immobilized enzymes required and high capital and variable processing cost involved has made this process un competitive with respect to chemical random interesterifϊcation process. This is especially true in case of manufacture of low value products like fats for margarine/spreads/shortening.

Further, many consumers do not consider enzymatic interesterifϊcation as a "truly" natural process. For example, in recent EU Parliament directive No.20000/36/EC of 23 rd June 2000 relating to cocoa and chocolate products intended for human consumption, has prohibited use of vegetable fat which has under gone "enzymatic" fat modification of the triglyceride structure. Further, many of the new enzymes are produced by genetic modification and there is again very strong consumer perception against products derived using genetically modified substances.

We, therefore, consider random chemical interesterification process is more "natural" and a mild process as the alkaline metal catalyst, namely, sodium methoxide used in the process breaks down as sodium hydroxide. Sodium hydroxide has been used historically and even to day for the refining of soft oils such as soybean, sunflower, canola etc and such refined oil is consumed widely and even for manufacture of margarine/spreads. Further, chemical interesterification is a well known art in the industry and needs low level of technology and cost.

We, therefore, found that this economic and commercial issue involved could be addressed by inventing a new process to manufacture hard palm fraction that could be interesterified with a hard palm kernel fat. We wanted to avoid further fractionation steps of such interesterified fat so that the yield of structural fat is approx 97%. Even if, a further fractionation step was required to produce extra hard structural fat, the focus was how to improve the yield of such hard stock to level of 65 % and above compared to 14-45 % that were achieved under US 5,858,445, US 6,156,370, CA 2207954 and WO 96/19115.

To this, our approach was to use single or two stages melt crystalization and dry fractionation method to produce a hard palm stearin fraction with a C+ 16 level of greater than 83% and total saturated fatty acid level of greater than 90 %. Further our approach was also to use commercially available palm stearin fraction, which is priced much cheaper to palm oil, with a single stage dry fractionation step to obtain high C- 16 hard palm stearin fraction. Further, our objective was to avoid prior art multi stage counter current dry fractionation process to achieve such hard palm stearin fraction which is considered expensive and produced low yield of such hard fraction.

It is considered essential to achieve max level of C- 16 type fatty acids while enriching C-16 type fatty acids in the palm stearin fraction. If this could be achieved automatically, other saturated fatty acids mainly C -14 as well as C-18 type also get enriched resulting in over all increase of total saturated fatty acids in such hard palm stearin fraction to over 90 %. When such fraction is mixed with hard palm kernel stearin fraction with a C- 12 level of higher than 52 %, the total saturated fatty acid level in the blend exceeds 90 %. Higher levels of saturated fatty acids in the blend before interesterifϊcation reaction is highly preferred, as this resulted in higher level of tri-saturated triglycerides in the interesterified blend. The reason for this has been explained in detail under the "Detailed Description of The Invention."

This goal was achieved in commercial scale operation in the plant by selectively crystallizing the commercially traded palm stearin fraction and then filtering the slurry through a high pressure membrane press and after completion of filtration, applying high squeeze pressure on the membrane (10-60 bar) so as to squeeze out the occluded liquid oil ( olein fraction) in the hard palm stearin fraction recovered in the filter chamber. This high pressure squeezing of the filter cake recovered in the filter resulted in the enrichment of the C- 16 fatty acid residue as well as saturated fatty acids levels in the hard stearin fraction thus recovered to achieve maximum de-oiling of hard stearin fraction, the chamber depth of commercial membrane press were required to be reduced from 40 to 50 mm which is considered as an industrial standard for normal palm oil filtration process to 10-30 mm. High inflation pressure necessitated reduction in chamber depth so that the stretch required in the member is kept as small as possible so that higher pressure could be applied during squeezing operation by inflating the membrane with out over stretching the same due to excess expansion. Applying of higher squeezing pressure resulted in enrichment of C- 16 fatty acid residue level to over 80 %, in the hard stearin fraction thus obtained .This also increased total saturated fatty acid level in the hard stearin fraction.

It was difficult to obtain such hard palm stearin fraction in the prior art processes, even by solvent fractionation method as well as expensive multi stage counter current dry fractionation method. This could be seen in the examples given in the prior art process, wherein the C-16 level in the hard palm fat obtained was only 79.4% and the level of total saturated fat in this fat was only 84.6 %, even though it was produced by using expensive multi stage counter current fractionation method. Even usage of very expensive solvent fractionation process yielded a hard palm stearin fraction with a C-16 level of only 77.9 % only as given in the examples of the prior art processes.

Detailed Description of the Invention The present invention is concerned with a hard high C- 16 type palm stearin fraction as well as a trans free hard structural fat suitable for the manufacture of low SAFA (Saturated Fatty Acid) poly/mono unsaturated margarine and spreads and fat blends as well as W/O emulsions. The structural fat is made from selectively fractionated non- hydrogenated, high C-16 type palm oil stearin fraction, which is subjected to random chemical interesterification using alkali metal catalyst such as sodium methoxide/sodium methylate, with a dry fractionated non-hydrogenated hard palm kernel stearin fraction to obtain hard structural fat with high yield ratios that can be economically and commercially incorporated in the oil blend for the manufacture of trans free, low SAFA, high poly unsaturated/mono unsaturated margarine/spreads/shortening and other food preparations.

Abbreviations :FA = fatty acid, FAC = fatty acid composition, PUFA = poly¬ unsaturated acid(s), SAFA = saturated fatty acid(s), MUFA= Mono unsaturated Fatty Acids, H = saturated FAs with carbon numbers greater than or equal to 16, M = saturated FAs with carbon numbers less than or equal to or les thanl4. H-3 refers to triglycerides with 3-carbon chain of length Cl 6 and above that are saturated. H2M refers to triglycerides which has 2 carbon chain that are Cl 6 and above and saturated and one chain of carbon length C 14 and below. Tg's = tri glycerides.

In this description all parts, proportions and percentages are by weight; the amount of fatty acids in an oil or fat is based on the total amount of fatty acids in said oil or fat and the amount of hard stock and/or hard fat in the fat composition is based on the total weight of said fat composition, unless otherwise stated.

The solid fat content (SFC) in this description and claims is expressed, as N-value using nuclear magnetic resonance method. The method used is IUPAC method 2.323. The fat is heated to a temperature of 8O.degree. C and filtered and filled in SFC tubes Maintain at 60 Deg for at least 5 minutes, keeping the sample for 1 hour at O.degree. C. And then 30 minutes at the measuring temperature. The SFC values are measured using Bruker Minispec-120 instrument.

For a better understanding of the invention some practical embodiments thereof has been described in the following examples. Parts and percentages as used in these examples, the description and the claims refer to weights unless otherwise indicated. For manufacturing spreads may be referred to various text books, e.g. The Chemistry and Technology of Edible Oils and Fats and their High Fat Products by G. Hoffmann; Academic Press London 1989, page 319 ff and in particular page 320-321.

Carbon number analysis is a well-known technique in the art. A suitable description is e.g. given in EP 78,568. The terms "fat" and "oil" are used in this invention are synonyms. The term "liquid oil" is used in this invention refers to glyceride mixtures that are pourable at 5 degrees C. Preferably the solid fat content of the liquid oil is 0 at 20 degree C.

"Fractionation" is a process used for separation of high melting component from a feed stock, The higher melting solid fraction obtained is called as "stearin" fraction or hard fraction and lower melting liquid fraction is called "olein" fraction or soft fraction. Through out this illustrations, the term stearin fraction as well as term olein fraction means higher melting fraction and lower melting fraction, respectively.

Interesterification process is a well-known art and a more recent review of the same is published by Rozendaal & Macrae (1997). When interesterification process is carried out using alkali metal catalyst (0.1-0.2% sodium methoxide catalyst ((sodium methylate (NaOCH3)-UN No.143 also known as Natrium Methylate is used as catalyst), it leads to a random distribution of triglycerides in which the fatty acids are distributed randomly over the 1-2-and 3 -position of the glycerol moiety. The number of tri-glycerides produced by interesterifying a fatty mixture containing n fatty acids is: V2(n2+n3).

Since the process involved is of statistical nature, the final equilibrium triglyceride composition of the interesterified fat can be easily calculated and properties are easily predicted. The table- 1 below gives the relationship in the number of fatty acids in the tri¬ glyceride mixture and number of tri-glycerides in fat mixture after chemical random interesterification

Table-1

It has been found that actual reaction product is always in line with the statistical prediction. In an edible plastic spread or margarine, hard stock contributes triglycerides especially of the tri-saturated type. A certain minimum quantity of these is essential to provide the "structuring effect" and to prevent oiling out of the liquid oil by providing temperature cycling stability.

From the patent literature and general experience, this minimum quantity requirement of such tri saturated tri-glycerides is around 6%. More is acceptable and desirable the limitation being the SAFA content limit in the fat blend if any. How ever, the amount of H3 type tri-glycerides, and especially tri-stearin, should not exceed a 2 % max limit. Because of it's high melt point as well as crystalline structure, if the level is greater than 2 %, it can cause product complaint such as sandiness and graininess and result in poor mouth feel. Hence content of H2M type of triglycerides is valuable, to give the required structuring effect, at the same time with out giving raise to sandiness/graininess as well as poor mouth feel to the product. To achieve this, it is essential to use a fat/oil with lower carbon chain residues such as lauric oils. Random interesterification process resulted in the rearrangement of the fat triglyceride geometry.

When the hard stock components are interesterified, the amounts of tri-saturated triglycerides in the interesterified product are determined entirely by the content of saturated fatty acids in the blend. The amount of tri-saturated triglyceride in the product after random interesterification will be the cube of the amount of saturated fatty acid in the fat blend before interesterification. . For example, the amount of tri-saturated tri-glycerides produced by interesterifying a fatty mixture containing '/« ' level of saturated fatty acids (SAFA) is: (m3).

Because this relationship is very critical, as shown in the table-2below, attempts are made to produce very hard palm as well as lauric fractions with very high levels of saturated fatty acids, which in turn will result in high levels of tri saturated tri-glycerides after random chemical interesterification process.

Table-2

Consider that the SAFA content of polyunsaturated margarine should not exceed 20% when using a fat level of 80 % in the finished margarine. The fat blend is considered consisting of 80 % sunflower oil as the PUFA oil to be used in the blend and 20 % hard stock (high usage level). At this level of blend, the SAFA contributed by sunflower oil works out to 10.3% . This means that the maximum SAFA that can be contributed by the hard stock at usage level of 20 %, cannot exceed 11.7 % to be able not to exceed the 20 % SAFA limit . Further the hard stock should contribute to minimum of 6% tri-saturated Tgs in the final blend.

This means that the hard stock should contribute to 6% tri-saturated triglycerides at the usage level of 20 %. It can be seen from the above table-2 that the SAFA content of the hard stock must be about 67% so that interesterified hard stock has 30% tri-saturated triglyceride, which in turn will contribute to 6 % tri-saturated triglycerides at 20 % usage level.

Assuming only 15% hard stock is to be used, then the SAFA content of the hard stock must be about 74%, so that it has 40% tri-saturated triglyceride after interesterification. Further assuming that only 7 % hard stock is to be used, then the SAFA content of the hard stock must be around 93.90% so that it has 82.79 % tri-saturated triglycerides after interesterification.

These are minimum requirements and a higher amount of tri-saturated tri-glycerides would be desirable. How ever it is preferable to limit H3 type triglyceride in the blend to max 2 % level to achieve good organolapitic characteristics.

The usage of hard structural fat in the blend can be 5 to 40% and the liquid oil or its blends can be 95 -60%. Table 3 below gives the level of tri-saturated triglycerides in the margarine blend with two types of hard fats.

Table - 3

Sunflower Oil Hard Stock-A Hard Stock-B BIend-1 BIend-2 100% 100% 100% Sunflower Oil 92.00% 93.00°/

Hard Stock - 8.00% A Hard Stock -B 7.00%

C:8 0.72 0.48 0.06 0.03 C:10 1.08 0.76 0.09 0.05 C:12 21.14 17.1 1.69 1.20 C:14 8.79 7.83 0.70 0.55 C:16 5.3 54.86 63.33 9.26 9.36 C:18:0 3.9 4.18 3.77 3.92 3.89 C:18:l 27.1 7.76 6.05 25.55 25.63 C:18:2 62.6 1.48 0.68 57.71 58.27 SAFA 9.2 90.77 93.27 15.73 15.08 SSS 76.93 82.88 6.15 5.80 HHH 17.06 26.84 1.36 1.88 H2M 27.38 . 31.05 2.19 2.17

It could be seen from the above two examples that, even at very low usage levels of hard structural fat at 7 to 8 %, the required tri-saturated triglycerides of H2M level in the blend could be achieved, at the same time restricting the level of H-3 type tri-glycerides below 2 %. H-3 type triglycerides imparts adverse organoleptic properties in the final product and hence it is desired to keep the same at around 2% levels.

While the invention has been described with reference to specific embodiments, modifications and variations of the inventions may be constructed with out departing from the scope of the invention, which is defined in the following claims.

EXAMPLE-I Hard Stock -A

Palm oil was fractioned using standard single stage melt crystallization method in a fractionation plant of a commercial scale to produce palm stearin fraction similar to the one commercially traded in the market. The capacity of the crystallizer used was 40,000 Kg per batch.

Palm oil was melted to and heated to 70 degrees C. and held at this temperature of at least 15 minutes so that the oil lost its crystal memory. The oil was then cooled to crystallize the hard palm fraction by control of water temperature as well as oil temperature such that oil temperature was brought down to 23 degrees C. The stearin fraction, which crystallized out, was then separated in a membrane type filter and squeezed to 4 bar to remove entrained liquid olein. After core blow, the medium hard stearin fraction was discharged to stearin tank kept below the membrane filter. The entire cycle took 8 hours. The iodine no of the stearin fraction obtained was 33. The yield of the stearin fraction was 20 %.

This stearin fraction collected was again charged to another crystallizer and was heated again to 75 deg C and held at this temperature for 15 minutes so that the oil lost its crystal memory. The oil was then cooled to crystallize the hard palm fraction by control of water temperature as well as oil temperature such that oil temperature was brought down to 48 Deg C. At this temperature mainly C-16 type of fats crystallized.

The cooled fat was filtered at 48 Deg C through a high-pressure membrane filter with a chamber depth of 10 mm. (Netzch type) After filtration of each batch, the hard fraction collected in the chamber of the filter was subjected to progressive squeezing pressure to remove the occluded olein in the crystal matrix of the hard fraction. The squeezing pressure was increased up to 20 bar and then held at this pressure for 5 minutes. Thereafter, the filter was core blowed to remove all the feed slurry from the core of the press and the cake were discharged in to the Stearin tank.

The hard stearin fraction was tested to contain 80.77 % C- 16 fatty acid residues and 12.35 % unsaturated fatty acid residues. The yield of the hard palm stearin fraction was 30 %. Both fractionation steps yielded liquid fraction, which was valued in the trade at a higher value, compared to feed stock.

This hard palm fraction was then blend in the ratio of approx. 65%to 35% with hard commercially available palm kernel fraction having a C- 12 level of 53.78 %. The resultant mixture was randomly interesterified with 0.15% sodium methoxide catalyst ((sodium methylate (NaOCHs)-UN No.143 also known as Natrium Methylate) supplied by M/S.Degussa HuIs. The interesterified mixture was washed with citric acid solution and bleached and deodorized. The resultant hard structural fat was found to have the desired specifications required in a hard structural fat. The analytical values of the blends used as well as resultant hard structural fat obtained are given in the Table 4A-Table-4 E below.

Table- 4A

TABLE - 4B Fatty acid profile of interesterified fat

TABLE 4-C

Triglyceride Composition after interesterification reaction (More than 1% mole level only taken in to account)

TABLE- 4D

The resulting hard structural fat was blended with fully refined sunflower oil at various ratios and the solid fat content was analyzed to find the best blend level for the manufacture

of Margarine. The blending was done from 1 % level to 20 % level and the SFC profile of the blend is shown in the Table 5.

Table -5

Margarine was produced using a blend level of 7 % hard structural fat with 93 % sunflower oil and following composition was used.

Oil Blend 82.000% Water 16.000% Salt 2.000% Flavor 0.010% Dimodan PV 0.300% Distilled Momo Glyceride B Carotene 0.00300% temperature of A unit was 17 Deg C and that of second A unit was 12 deg C. The exit temperature of the product was 8.8 deg C. The rpm of the pin worker was maintained at 200. The margarine produced was found to be soft, shining, of good spreadability and imparted good salt release. The solid fat profile of the blend after tempering for 1 hour as well as 16 hours at 0 Deg C is given as below:

Table - 6

Tempering at 0 Deg C for

60 minutes 16 hours

N lO 6.08 6.70 N 20 3.12 3.60 N 25 2.50 2.95 N 30 1.60 1.85 N 35 0.60 0.50

EXAMPLE -2

Hard Stock -B

Palm oil was fractioned using standard melt crystallization process method to produce Palm stearin fraction as given in the Example 1. This stearin fraction was then subjected to another melt crystalization step and the slurry was filtered at a higher temperature of 52 Deg C through a high-pressure membrane filter as per example 1. (Netzch type) After filtration of each batch, the hard fractionation collected in the chamber of the filter was subjected to progressive squeezing pressure to remove the occluded olein in the crystal matrix of the hard fraction. The squeezing pressure was increased up to 30 bar and then held at this pressure for 10 minutes. There after the filter was core blowed to remove all the feed slurry from the core of the press and the cake were discharged in to the Stearin tank. The hard stearin fraction was tested to contain 86.53 % of C-16 fatty acid residues and 7.47% unsaturated fatty acid residues.

This hard palm fraction was then blend in the ratio of approx. 70%/30% with extra palm kernel fraction obtained by hard setting and fractionation of Palm Kernel oil and having a C-12 level of 56.71%, and unsaturated fatty acid residue level of 6.73 %. The resultant mixture was randomly interesterified with 0.15% sodium methoxide catalyst. The interesterified mixture was washed with citric acid solution and bleached and deodorized. The resultant hard structural fat was found to have the desired characteristics required in a hard structural fat. The details are given in the Table 7 below.

Table 7A

TABLE 7-B Fatty Acid profile of interesterified fat

TABLE 7-C

TABLE 7-D

The resulting trans free interesterified hard fat was blended with fully refined

sunflower oil at various ratios and the solid fat was analyzed to find the best blend level for

the manufacture of Margarine. The blending was done from 1 % level to 15 % level and the

SFC profile is shown in Table 8.

Table 8

This hard stock and blended with fully refined sunflower oil in a ratio of 7:93 to give a margarine fat blend. The SAFA content of the blend was 18%, the content of trans unsaturated fatty acid residues .was negligible. From this blend a spread was manufactured with a composition as described in Example I.

The mixture was processed through a pilot plant supplied by Schroder Kombinator a through a conventional A-A-C sequence with a throughput of 10 Kg per hour. Exit temperature of A unit was 17 Deg C and that of second A unit was 12 deg C. The exit temperature of the product was 8.8 deg C. The rpm of the pin worker was maintained at 200.

The margarine produced was found to be soft, shining, of good spreadability and imparted good salt release. The solid fat profile of the blend after tempering for 1 hour as well as 16 hours at 0 Deg C is given as below:

Table-9

Tempering 1 hour 16 hours

NlO 7.0 7.6 N20 4.2 4.7 N30 1.6 1.9 N35 1.0 1.0

The product showed good spread ability properties, plasticity and exhibited excellent melting behavior. It was soft and shiny with good salt release.

It could be seen from the above Examples that the hard structural fat of the current invention had the similar properties in the margarine formulation compared to the hard fat as described in prior art. Example -3

Hard Stock C

Hard structural fat of Example 1 was subject to panning and pressing after hard setting at a temperature of 28-29 Deg C. The hard-set fat was then covered in filter cloth and

subjected to a very high pressure of 50 Kg/Cm2 in a commercial Sperry hydraulic press specially developed for this application. The Pressing was applied gradually to max level in

90-minute period. The olein fraction was collected in drip tray. The Hard stearin fraction was

removed from the press and melted. This resulted in a yield of 81% very hard structural fat stearin fraction.

The analytical values of the extra hard stearin fraction ( extra hard trans free structural fat) are given in the table- 10 below:

Table- 10

Fractionation of Interesterified Hard Structural fat

It could be seen from the above example that the panning and pressing of our novel

Hard Interesterified structural fat resulted in an yield of 81 % Extra hard stearin fraction

which matches with example Xl of US 6,156,370 at the same time resulting in much higher yield ratios The olein fraction obtained had lower solid fat profile compared to prior art.

For the purpose of comparison with respect to the functionalities of this novel structural fat ( hardϋstock A,B and various examples of solid fat content of the fat blend as

given in the prior art US 6,156,370 product, ( structural fat in blend with sunflower oil ) is summarized below in Table 11. The example numbers given in this table refers to the

examples as given in the prior art patent.

Table 11

Ex-I to Ex-Xl 1 are the Solid fat content (SFC)profiles as given in the US Patent

No 6,156,370. Hard stock A and Hard stock B ,hard stock C relates to the trans free hard

structural fat obtained under Example 1 and example 2 and example 3 of this invention.

It could be seen, that through the current invention, we could produce a hard

structural fat of similar qualities as prior art product, but the process involved in the new art is much more economical and yield of the structural fat was much higher for commercial

exploitation. The margarine produced by using the structural fat of current invention with similar in quality compared to prior art products.