KR20020061612A - Edible fat blends - Google Patents

Abstract

The present invention provides an olive oil base product containing a plant stanol and / or sterol fatty acid ester mixture based on virgin olive oil and a method for providing such olive oil base products.

Description

Edible fat blends

Plant sterols are a group of compounds that are structurally very similar to cholesterol. Plant sterols most commonly present in nature are sito sterols, campe sterols and stigma sterols. Vegetable oils and fats are the main sources of plant sterols in our diet. The main part of sterols in vegetable oils exists as fatty acid esters. Saturated plant sterols such as cytostolol and camphortanol are present in small amounts in our diet. For a Finnish diet, the total daily intake of stanol is 30 to 80 mg. However, tall oil stanols contain from 10 to 20% of plant stanols (primarily cytostanol and camphortanol). Plant stanols can also be prepared by hydrogenation to remove the double bonds of the corresponding phytosterols.

Recently, attention has been focused on the cholesterol-lowering properties of phytostanols and sterols and already phytostanol or sterol enrichment products such as margarine, salad dressings, bars and yogurt have been sold. Recent studies show that eating 2-3 g of plant stanols daily significantly reduces serum LDL cholesterol levels even when used as part of a recommended health diet. Plant stanol and sterol fortified foods are effective in reducing elevated serum total and LDL cholesterol levels. Increasing the nutritional value of staple foods with fatty acid form plant stanols and / or sterols is possible without compromising taste or texture. Based on the cholesterol lowering effect and the fact that plant stanol is hardly absorbed, plant stanol is preferred, but a mixture of plant stanol and sterol or plant sterol may also be used.

The best advantage of using plant stanols and / or sterols to reduce elevated serum total and LDL cholesterol levels is obtained when fortifying stocks. For example, margarine or spread is a very suitable food for this enhancer in the north of Europe, but other stock candidates will have to be found in the south of Europe. Olive oil is a staple in this region. And olive oil consumption is also increasing in other parts of the world, due to its good taste and good health. Olive oil naturally contains very low levels of plant sterols (typically less than 0.2 g per 100 g of oil). Higher olive oils, such as virgin olive oil, contain large amounts of squalene, a precursor to cholesterol. Although the content of squalene varies, the special virgin olive oil typically contains about 300 mg per 100 g of oil. Edible squalene increases serum cholesterol levels in the human body. This effect on serum total and LDL cholesterol levels is also neutralized by plant stanols and / or sterols. Therefore, it is necessary to fortify the high quality olive oil with plant stanols and / or sterols and to have properties similar to those of ordinary olive oils.

Virgin olive oil should remain clear when stored 24 hours to 20 degrees Celsius. Typically, higher olive oils, such as virgin olive oil, are also turbid as crystals that occur when stored for a long time at refrigerated temperatures. Olive oil fortified with plant stanols and / or sterols should be avoided in turbidity.

For mass production of plant stanols and / or sterol esters, ordinary cooking oils or ordinary vegetable oils with controlled fatty acid components are used. Strengthening higher olive oils such as virgin olive oil with plant stanol and / or sterol esters having fatty acids from these ordinary vegetable oils or mixtures thereof promotes precipitation of higher dissolved lipids at room temperature and below. Crystals formed do not usually dissolve even after prolonged storage at room temperature. The problem is low saturated soybean oil (PUFA: 67 wt%, SAFA: 7,9 wt%), sunflower oil (PUFA: 64 wt%, SAFA: 12 wt%) or linola oil (PUFA: 70 wt% Esterification of stanol and / or sterol fatty acids from ordinary vegetable oils with low levels of saturated fatty acids and high levels of polyunsaturated fatty acids such as%, SAFA: 11% by weight) is not solved.

U.S. Patent No. 5,089,139 discloses a method for purifying virgin olive oil, where the virgin olive oil is traced by a microfilter at 15 degrees to 35 degrees Celsius to obtain virgin olive oil that remains clear even in tests maintained at 0 degrees Celsius for 24 hours. Filtered.

U. S. Patent No. 3,751, 569 discloses clear cooking and salad oils having hypocholesterolemic properties. The liquid is mixed with 0.5 to 10% by weight of sterol fatty acid ester (calculated as free sterol) of the glyceride base oil. Fatty acid residues are defined as C _1-12 saturated monocarboxylic acid residues or unsaturated fatty acid residues having up to 24 carbon atoms. In one embodiment the sterol fatty acid ester is prepared by perchloric acid catalytic esterification of carboxylic anhydride and usually free sterol. Sterol fatty acid esters are added in an amount small enough to prevent precipitation at refrigeration temperatures. In the illustrated embodiment, cooking and salad oils are prepared by dissolving the liquid glyceride base oil and the plant sterol monocarboxylic acid ester in a mutual solvent (such as hexane or diethyl ether) and evaporating the solvent. The solubility of the different fatty acid esters of the plant sterols of triolein is also shown, showing very low solubility for the C ₁₂ (0.6%) and C ₁₆ (0.1%) saturated fatty acid plant sterol esters. The methods and products described in U.S. Patent No. 3,751,569 described above have at least two defects. First, the use of fatty acids, usually made from free sterols, is neither practical nor economical because the starting articles are quite expensive. Second, the perchloric acid catalytic esterification method used in this patent is not suitable as a food manufacturing method because residual chlorine remains in the product. Thus, this method is not suitable for commercial applications.

British Patent 1 405 346 teaches how free sterols contained in cooking oils and fats are converted to fatty acid esters via interesterification. In addition, a method for producing vegetable oil with an increased sterol ester content in Example 2 is disclosed. However, the method is based on the interesterification of the entire oil mixture, but it cannot be performed for higher olive oils such as virgin olive oil because of its physical properties.

FIELD OF THE INVENTION The present invention relates to edible fat mixtures, and in particular to olive oil base products and such olive oil base products, based on higher olive oils such as virgin olive oil containing plant stanol esters and / or plant sterol esters. And to plant stanols and / or sterol esters used to make olive oil base products.

Saturation of the plant sterol mixture into the corresponding plant stanol mixture causes a significant difference in the solubility of the corresponding sterol / stanol ester with the same fatty acid component. Vegetable oil base sterol esters having low erucic acid rapeseed oil fatty acids and corresponding stanol fatty acid esters exhibit the following amounts of solid fat content at different temperatures as determined by NMR techniques.

10 ℃ 20 ℃ 30 ℃ 35 ℃ 40 ℃

Plant Sterols 40.5 11.6 3.5 1.7 1.1

Plant Stanol 82.3 70.2 34.9 9.4 5.2

The physical properties of stanol and / or sterol fatty acid esters can be tailored by altering the fatty acid component of the fatty acid ester or by varying the ratio of plant stanol and sterol of the ester.

In the present invention, the problem of precipitation / crystallization of higher soluble lipids of higher olive oil is to dissolve plant stanol and / or sterol fatty acid esters with fatty acids from so-called high PUFA vegetable oils of higher olive oils such as virgin olive oil, and from refrigeration temperatures. It is solved by crystallizing higher soluble lipids from olive oil at temperatures ranging up to room temperature to obtain plant stanol and / or sterol fatty acid ester mixtures with very small amounts of saturated fatty acid esters contained in olive oil. The required crystallization temperature and time depends on the amount and type of stanol and / or sterol fatty acid esters used. By appropriately selecting the crystallization temperature and time, the virgin olive oil is kept clear at the refrigeration temperature or cleared when the oil is removed from the refrigeration and kept for a short time at room temperature. The presence of plant stanol and / or sterol fatty acid ester mixtures having high levels of unsaturated fatty acids, for example, as compared to US Pat. No. 3,751,569 which shows very limited solubility (0.1%) in phytosterol palmitate of liquid glyceride base oils. Obviously enhances the solubility of stanols and / or sterol esters.

In addition, the present invention teaches plant stanol and / or sterol ester compositions that can be used for direct fortification of virgin olive oil. Thus, oils according to the invention can be obtained by adding an appropriate amount of plant stanol and / or sterol esters having a fatty acid composition containing at least 60%, preferably at least 65% polyunsaturated fatty acids and less than 5% saturated fatty acids. . When clear olive oil is needed at refrigeration temperatures, such as at least 60%, preferably at least 65% polyunsaturated fatty acids and less than 5%, preferably less than 3%, less than 2%, or most preferably less than 1.5% stearic acid Plant stanols and / or sterol esters with fatty acid compositions containing saturated fatty acids are used. Such stanol and / or sterol fatty acid esters can be obtained by esterification of the known art, such as esterification of fatty acid mixtures or fatty alcohol ester mixtures with suitable predetermined fatty acid compositions.

The term “virgin olive oil” is meant to include special virgin olive oil, virgin olive oil, ordinary olive oil, lampante virgin olive oil, as defined in accordance with the European Community Official Journal No. L 39/2 (1992.2.15). And any mixture of lower olive and virgin olive oil, as defined by the European Community Official Journal, is covered by this definition. Preferably, this mixture contains at least 25%, preferably 50% and most preferably 75% virgin olive oil.

The term "olive oil base product" is meant to include virgin olive oil according to the above definition, fortified with a mixture of plant stanols and / or sterol fatty acid esters. From about 0.3 to 25% by weight, preferably from 0.3 to 10% by weight, more preferably from 1.5 to 10% by weight, most preferably from 3 to 10% by weight of plant stanol and / or sterol orthotropic esters (as free sterols). Calculated) may be included in olive oil base products.

The term “high PUFA vegetable oil” is meant to include vegetable oil and vegetable oil mixtures containing at least 50% polyunsaturated fatty acids and at least 7% saturated fatty acids in fatty acid composition. Typical high PUFA vegetable oils include sunflower oil, corn oil, soybean oil, low saturated soybean oil, safflower oil, cottonseed oil, linola oil, or mixtures thereof. The amount of saturated fatty acid in the fatty acid composition is typically about 7.5-49%, preferably about 8-25%, most preferably about 10-20%.

The term "phytosterol" is meant to include 4-desmethyl sterols, 4-monomethyl sterols, and 4,4-dimethyl sterols (triterpene alcohols) or mixtures thereof. The term “phyto stanol” is meant to include 4-desmethyl stanol, 4-monomethyl stanol and 4,4-dimethyl stanol, preferably obtainable by hydrogenation of the corresponding phytosterol. Typical 4-desmethyl sterols include cytosterol, camphorsterol, stigmasterol, brassicasterol, 22-dehydrated brassikasterol, Δ5-avenasterol. Typical 4,4-dimethyl sterols include cycloartenol, 24-methylenecycloartenol and cyclobradol. Typical phytostanols include the saturated forms (cycloarthenol, 24-methylenecycloartanol and cyclobradol) obtained by saturation of cytosethanol, camphortanol and its 24-epimer, cycloarthenol and triterpene alcohols. do. The terms phytosterol and phytostanol also include 4-desmethyl sterol and stanol, 4-monomethyl sterol and stanol, 4,4-dimethyl sterol and stanol and all natural mixtures thereof. The terms phytosterol and phytostanol also include individual 4-desmethyl sterols, 4-monomethyl sterols or 4,4-dimethyl sterols or their corresponding saturated (stanol) forms.

The terms "plant sterol" and "plant stanol" are intended to be synonymous with the terms "phytosterol" and "phytostanol", respectively. "Sterol" and "stanol" also mean "phytosterol" and "phytostanol", respectively.

"Poly unsaturated fatty acids" are defined herein as fatty acids having two or more double bonds. Preferably, the double bond has a cis shape, but one or more double bonds may be trans. Due to the thermal isomerization of the deodorization process, it is known that many common vegetable oils contain 1 percent level of polyunsaturated fatty acids with one or more double bonds in the trans form. And, the double bond may be so-called conjugated or blocked methylene. Typical vegetable oil derived polyunsaturated fatty acids are linoleic acid and ??-linoleic acid, but unsaturated fatty acids from fish oil such as eicosapentaenoic acid and docosahexaenoic acid may be used.

The term "saturated fatty acid" is meant to include straight chains and branched fatty acids by having 4 to 24 carbon atoms and no double bonds.

The term "high PUFA stanol and / or sterol ester" preferably refers to stanol and / or sterol ester made from fatty acids from high PUFA vegetable oil, but also to fish oil derived polyunsaturated fatty acids or vegetable oils and fish oil derivatives. Mixtures of polyunsaturated fatty acids may also be used.

The stanol and / or sterol fatty acid esters used in the present invention are preferably prepared using a food grade process. A "food grade method" is not preferred for the final product, where the stanol and / or sterol fatty acid ester products (1) affect the quality of one or more of the stanol and / or sterol fatty acid esters, and (2) Food safety standards are defined to include methods for freeing residual chemicals (eg, solvents or catalysts containing chlorine) that are harmful to consumers. Many food grade methods are known and any of them may be suitable for preparing the stanol and / or sterol fatty acid esters used in the present invention. Preferably, the food grade method is a solvent free food grade method. Stanol and / or sterol fatty acid esters may also be prepared by the methods disclosed in US Pat. No. 5,502,045, for example by transesterification of fatty alcohol esters obtained from high PUFA vegetable oils or mixtures thereof.

Another suitable method for preparing stanol and / or sterol fatty acid esters is to esterify free stanol and / or sterol with high PUFA vegetable oil in the presence of a trans- or interesterification catalyst. Alternatively, direct, preferably catalytic esterification methods, such as those disclosed in US Pat. No. 5,892,068, or enzyme esterification methods, such as those disclosed in EP 195 311, can be used.

Another possibility for preparing stanol and / or sterol fatty acid esters is the high PUFA alcohol ester present in the oily phase obtained after esterification of high PUFA sterols and / or stanol esters according to the method disclosed in US Pat. No. 5,502,045. Is to take advantage of This mixture of high PUFA alcohol esters and sterols and / or stanol esters can be used for the esterification of stanols and / or sterols after removal of the higher dissolved sterols and / or stanol esters.

Starol esters, sterol esters or mixtures thereof may be prepared using fatty alcohol esters having a predetermined fatty acid composition according to the invention by the method disclosed in US Pat. No. 5,502,045. Fatty acid alcohol esters may be prepared by known techniques such as solvent or detergent fractionation of alcohol fatty acid esters obtained from mixtures of high PUFA liquid vegetable oils or high PUFA oils. The corresponding mixture of fatty acid esters can also be obtained by distillation under reduced pressure. Such distillation may also be used to remove saturated fatty acids having 16 or fewer carbon atoms. Fatty acid alcohol esters having a defined fatty acid composition can also be obtained by the alcohol-decomposition of vegetable oils or oil mixtures with reduced amounts of saturated fatty acids obtained according to US Pat. No. 5,670,348, for example.

Stanols and / or sterol esters with the desired fatty acid composition are for example directly or preferably by catalytic esterification according to US Pat. No. 5,892,068, between stanols and / or sterols and fatty acid mixtures or free fatty acids of their composition. It may also be prepared. The esterification of stanols and / or sterols with triglycerides having the desired fatty acid composition using trans- or interesterification catalysts is also a suitable method for preparing stanol and / or sterol esters. And stanol and / or sterol esters may also be prepared by enzymatic esterification methods, for example as disclosed in EP 195 311.

In addition, mixtures of polyunsaturated fatty acids can also be used to obtain stanol and / or sterol fatty acid esters having the desired composition. Stanol esters and / or sterol esters having the desired fatty acid composition can also be prepared, for example, by the method based on the trans esterification method as disclosed in US Pat. No. 5,502,045, for example of high PUFA fatty acids from vegetable oils or oil mixtures. Such as dry, detergent and wet fractionation of stanol and / or sterol fatty acid esters obtained by esterification, directly preferably by catalytic esterification or by enzymatic esterification, for example as disclosed in EP 195 311. It may also be prepared by conventional classification. In particular, classification from solvents can be used to produce the desired stanol and / or sterol ester compositions. When using an enzyme esterification method as disclosed in EP 195 311, the fractionation can preferably be carried out directly in the reaction solvent used in the esterification method after removing the enzyme and possible aqueous state.

The aforementioned methods are several food grade methods used to prepare stanol and / or sterol fatty acid esters in accordance with the present invention.

In one preferred embodiment, virgin olive oil, preferably a special virgin olive oil containing a predetermined mixture of stanols and / or sterol fatty acid esters, uses, for example, a mixture of high PUFA vegetable oils or high PUFA vegetable oils as a source of fatty acids. Can be obtained by dissolving 5-50% by weight (preferably 5-25%) of stanol and / or sterol fatty acid esters obtained by the esterification method as disclosed in US Pat. No. 5,502,045. This may preferably be done as part of the regular purification process of virgin olive oil. The stanol and / or sterol ester olive oil thus obtained is heated and mixed to completely dissolve the stanol and / or sterol ester of the olive oil, followed by a known conventional “winterizing” step or fractionation process. For example, a process of winterizing or batch dry classification can be carried out at 0-30 ° C. (preferably 5-25 ° C.) so that olive oil base products have a point in the range of 4-25 ° C. Preferably it becomes clear at any point in the range of 4-8 degreeC). The olive oil base products prepared according to the invention are clear when stored at refrigerated temperatures and stored at room temperature, ie at some point in the range 18-18 ° C., preferably in the range 18-18 ° C., when cloudy at refrigeration temperatures. Can lose. This means that the olive oil base product of the invention is clear at 30 ° C. or higher, preferably 25 ° C. or higher, more preferably 20 ° C. or higher, even more preferably 18 ° C. or higher. If the product is stored at a refrigeration temperature (ie about 2-12 ° C., preferably about 2-8 ° C.) it will preferably be clear at 8 ° C., more preferably 4 ° C. Since many European consumers store oils at room temperature, olive oil base products should be clear at 25 ° C. or above, preferably 20 ° C. or above, and most preferably 18 ° C. or above.

The crystallization temperature and time may vary depending on the type of stanol ester and / or sterol ester used and the desired final product. After removal of the solid portion made mainly of saturated fatty acids of stanols and / or stanol esters, for example by vacuum filtration, the resulting olive oil base products can be diluted with virgin olive oil, used as such or not treated, and thus olive oil base products. The desired content of plant stanols and / or sterols can be obtained. Depending on the quality of the virgin olive oil, some of the higher dissolved lipid components naturally contained in the olive oil will be removed simultaneously by filtration, so this process may have a refrigeration temperature (ie, about 2-12 ° C., preferably about 2-8 ° C.). Improve the clarity of olive oil. In addition to the method of winterizing or batch dry classification, certain types of classification methods are stanols and / or sterols with higher melting points, for example stanol and / or sterol fatty acid esters based on saturated fatty acids. It is apparent to one of ordinary skill in the art that it can be used to crystallize and remove fatty acid esters. It is also apparent to them that any known filtration method may be used.

To prepare stanol and / or sterol esters having the desired fatty acid composition

Another method is transesterification as disclosed in US Pat. No. 5,502,045.

Excess fatty acids of high PUFA stanol and / or sterol ester mixtures obtained after fluorination

It is to utilize a methyl ester. After the drying step, the prepared stanols and / or sterols

Depending on the composition of the steanol and / or sterol ester fatty acid alcohol ester horn

The mixture is cooled to 5-25 [deg.] C., and the higher dissolved portions are allowed to crystallize for 4 to 24 hours. Optionally, additional fatty alcohol esters are added to facilitate classification. After filtration, the clear oily state is preferably deodorized to remove excess fatty alcohol esters and to yield tasteless stanol and / or sterol esters. The stanol and / or sterol fatty acid esters thus obtained may be preferably mixed with virgin olive oil.

Plant stanols and / or sterol fatty acid esters having the desired fatty acid composition can also be prepared from fatty acids or fatty alcohol esters having the appropriate composition. The plant stanols and / or sterol fatty acid esters thus obtained can be added directly to virgin olive oil to obtain olive oil base products by the present invention.

In addition, the stanol and / or sterol ester compositions according to the invention are for example "fatty acids, such as fatty acids, fatty alcohol esters or oils obtained by methods involving the utilization of new breeding of microorganisms, enzymes or oil producing plants. Starting material ". The sterol and / or starol moiety can be obtained, for example, from sterol and / or stanol sources from the pulping pulp industry or from treatment of vegetable oils. New breeds that produce elevated amounts or more attractive compositions of suitable sterols and / or stanols generated by conventional methods or genetic modifications may also be included as possible raw materials for the production of stanols and / or sterols. Preferably, stanol and / or sterols are then utilized in food grade methods to prepare the olive oil base products of the present invention.

In one preferred embodiment of the invention, virgin olive oil is fortified with plant stanol fatty acid esters having a predetermined fatty acid composition. In addition, mixtures of plant stanols and sterol fatty acid esters or plant sterol fatty acid esters may be used.

The following examples are presented to illustrate the invention in more detail.

[Yes]

Example 1 Preparation of Stanol Fatty Acid Esters Based on Low Saturated Soybean Oil Fatty Acids (Low SatSoy)

Plant stanol fatty acid esters were prepared on a pilot scale. 6 kg of plant stanol (composition: 68.2% cytostanol, 28.3% camphortanol, 1.1% cytosterol and traces of other unsaturated sterols), usually obtained by hydrogenation of plant sterols, is mixed with 8.6 kg of LowSatSoy methyl ester mixture and 110 It dried at -120 degreeC. The temperature of the dry mixture was reduced to 90-95 ° C. and methyl sodium catalyst (73 g) was added. The temperature of the dry mixture was increased to 120 ° C. and the reaction was carried out under vacuum (40 mmHg) for 4 hours. The conversion was monitored by GC analysis. Once the> 98% conversion was achieved, the temperature was reduced to 100 ° C. and 30 wt% hot high temperature> 90 ° C. water was added to destroy the catalyst. The water phase was removed and the oil phase was rewashed to give a soap content <1000 ppm. The oil phase was dried at 95 ° C. and the dry material was bleached at 95 ° C. under vacuum using 1 wt% bleach (Trisil, Grace, Germany) for 20 minutes. After removing the deodorant by filtration, a standard pilot scale deodorization (batch deodorizer, capacity 9 kg) was performed to remove excess soybean oil methyl ester and to yield a tasteless stanol ester product.

The fatty acid composition of the obtained plant stanol ester is as follows: SAFA: 8.7%, MUFA: 27.5% and PUFA: 63.8%. The contents of C16: 0 and C18: 0 are both 3.6%. The stanol content is 57.6% by weight with high esterification conversion (1.5% by weight of free stanol).

Example 2: Preparation of vegetable oil base stanol fatty acids with fatty acids from linola oil.

Stanol fatty acid mixtures with fatty acids from linola oil are prepared by plant stanol mixtures and methods such as those listed in Example 1. The fatty acid composition of the obtained plant stanol ester is as follows: SAFA: 10.6%, MUFA: 17.7% and PUFA: 71.8%. The contents of C16: 0 and C18: 0 are 6.2% and 3.9%, respectively. The stanol content is 57.9% by weight with high esterification conversion (0.13% by weight of free stanol).

Example 3: Distillation from sunflower oil Preparation of plant stanol fatty acids based on high PUFA fatty acids.

High PUFA plant stanol esters are prepared in a manner analogous to that described in Example 1 with methyl fatty acid esters obtained after distillation of sunflower oil base methyl esters. The combined distillation cuts contained 5.6% SAFA (0.3% C16: 0, 5.0% C18: 0), 26.5% MUFA and 67.9% PUFA. The total sterol of the plant stanol ester (plant sterol + plant stanol) was 59.5%, and the plant stanol content was 58.4% by weight. The amount of free stanol was 0.86 wt%.

Example 4: Plant stanol ester fortified virgin olive oil was prepared by crystallization at +7 ° C.

7% by weight of plant stanol esters (equivalent to 4.0% by weight of plant stanols and 0.05% by weight of plant sterols) with fatty acids from low saturated soybean oil obtained according to Example 1 heated the oil to 60 ° C. and normal pressure It was dissolved in a special virgin olive oil (Kalsham Megeri, Sweden) by stirring at. When all plant stanol esters are dissolved the mixture crystallizes with agitation at + 7 ° C. for 21 hours. The oil was filtered using thick (carbon) filtration paper commonly used in winterizing and vacuum (40 mm Hg). The weight of the filtrate was 1.1% by weight of the original special virgin olive oil plant stanol ester mixture. The olive oil base product obtained contained 3.7 wt% plant stanol and 0.12 wt% plant stanol was in free form. Fatty acids of plant stanol esters contain 4.9% saturated fatty acids (2.4% C16: 0 and 1.5% C18: 0), and compared to 8.7% saturated fatty acids of added plant stanol esters, the crystallized is mainly saturated plants It is clearly shown to be a stanol ester. The plant stanol content of the filtrate was 19.3% by weight and only 0.18% by weight of plant stanol was free form. The obtained plant stanol ester-enriched virgin olive oil was kept clear at 5 ° C. for at least 5 days, but clear crystallization of the glass walls of the bottles in the controlled special virgin olive oil was visible after 3 days.

Example 5: Preparation of plant stanol ester fortified olive oil by crystallization at 16 ° C.

The plant stanol ester fortified virgin olive oil was prepared similarly as in Example 4, with the exception that crystallization was performed at 16 ° C. for 21 hours. The olive oil base product obtained contained 3.7 wt% plant stanol and 0.11 wt% plant stanol was in free form. The fatty acid composition of the plant stanol esters was 4.5% SAFA (2.3% C16: 0, 1.4% C18: 0), 29.0% MUFA and 66.6% PUFA. The weight of the filtrate was 1.5% by weight of the original special virgin olive oil plant stanol ester mixture. The plant stanol content of the filtrate was 10.7% by weight and only 0.1% by weight of plant stanol was free form. The fatty acid composition of the plant stanol ester of the filtrate was 36.9% SAFA (18.9% C16: 0 and 15.4% C18: 0), 19.7% MUFA and 43.4% PUFA. This data shows that mainly saturated fatty acid plant stanol esters crystallize. The obtained plant stanol ester-enriched virgin olive oil was kept clear at 5 ° C. for at least 5 days, but clear crystallization of the glass walls of the bottles in the controlled special virgin olive oil was visible after 3 days.

Example 6: Preparation of plant stanol ester fortified virgin olive oil.

7% by weight of plant stanol esters obtained according to example 2 were dissolved according to example 4 in a special virgin olive oil (Kalsham Megeri, Sweden) and crystallized at 16 ° C. for 20 hours. The oil sample obtained after filtration was found to be cleared after being stored in the refrigerator at 7 ° C. for 24 hours. The sample cleared at room temperature, but began to turbid after 1 day at room temperature and clear crystal formation began after 2 days at room temperature. The olive oil base product obtained contained 3.3% by weight of plant stanol. The fatty acid composition of the plant stanol ester is 6.0% SAFA, 19.4% MUFA and 74.6% PUFA compared to the original linola stanol ester 10.6% SAFA, 17.7% MUFA and 71.8% PUFA. Based on this data it is clear that the 6% SAFA content of the fatty acids of the plant stanol esters is too high to obtain olive oil base products of the desired properties.

Example 7: Preparation of plant stanol ester fortified virgin olive oil.

11 and 16% by weight of plant stanol esters obtained according to example 3 were dissolved in special virgin olive oil (Kalsham Megeri, Sweden) and treated according to example 4. The crystal temperatures are + 7 ° C. (20 hours) and + 23 ° C. (7 days) for 16 wt% samples and + 23 ° C. (7 days) for 11 wt% samples. The 16 wt% sample crystallized at 7 ° C. is kept clear at 7 ° C. for at least one week. The total stanol content of this olive oil base product was 8.9% by weight and the fatty acid composition of the plant stanol esters contained in this olive oil base product was 1.7% SAFA (0.65% C16: 0 and 0.34% C18: 0), 26.8% MUFA and 71.5% was PUFA. This olive oil base product can be diluted with untreated virgin olive oil to obtain an olive oil base product of the desired plant stanol content for commercialization.

Crystallized samples at 23 ° C. for 7 days become cloudy at 7 ° C. but clear at room temperature. The stanol content of the two olive oil base products was 6.3 and 8.9 wt% for the 11% and 16% samples, respectively.

Example 8: Preparation of plant stanol ester fortified virgin olive oil.

4.5% by weight of plant stanol esters obtained in Examples 1, 2 and 3 were dissolved in a special virgin olive oil (Kalsham Megeri, Sweden) and stored at 7 ° C. for 11 hours. Based on sunflower methyl ester cuts (SAFA: 5.6%, C16: 0 0.3%, C18: 0 5.0%), olive oil base products with enhanced plant stanol esters show crystal clear crystals at + 7 ° C and these samples at room temperature. It is not clear that the olive oil base products clearly indicate that the amount of C18: 0 stanol ester is too high. All three mixtures crystallized because of too much SAFA content (8.7%, 10.6% and 5.6%).

Example 9 Preparation of Plant Stanol Fatty Acid Esters Having Desired Fatty Acid Compositions by Solvent Classification.

10 g of the plant stanol ester obtained by the method disclosed in Example 1 was dissolved in 90 ml of hexane in a 200 ml centrifuge tube. The mixture was maintained at + 7 ° C. for 24 hours and then centrifuged in a temperature programmable centrifuge. The hexane phase was removed and the hexane was evaporated. The obtained plant stanol esters contained 4.6% SAFA (2.4% C16: 0 and 1.8% C18: 0), 27.2% MUFA and 68.25% PUFA.

Example 10: Production of an olive oil product using plant stanol esters having the desired fatty acid composition.

7 wt% of plant stanol esters obtained in Example 9 were dissolved in special virgin olive oil and stored at 7 ° C. according to a method similar to that described in Example 4. The oil was kept clear for at least 7 days.

Example 11: Preparation of olive oil base products fortified with stanol fatty acid esters.

Two batches of fatty acid methyl esters were prepared by distillation in a similar manner as described in Example 3, but the following fatty acid compositions were obtained: 4.9% SAFA, 34.1% MUFA and 61% and the other 2.5% SAFA, 36.5% and It contained 61% PUFA. The fatty acid methyl esters obtained were used for esterification of plant stanol using the method disclosed in Example 1. 0.3 g of stanol fatty acid ester was dissolved in 10 g of special virgin olive oil. Both oils remained clear for at least 1 week at room temperature.

Example 12 Preparation of Olive Oil Base Products fortified with Sterol Fatty Acid Esters.

As prepared and used in Example 11, the same fatty acid methyl ester consisting of 4.9% SAFA, 44.1% MUFA and 61% PUFA was used for esterification of plant sterols. 0.6 g of sterol fatty acid ester was dissolved in 10 g of special virgin olive oil. The oil was kept clear for at least 1 week at room temperature.

The stanol and / or sterol fatty acid esters used in the present invention are preferably prepared using a food grade process.

Plant stanols and / or sterol fatty acid esters having the desired fatty acid composition can also be prepared from fatty acids or fatty alcohol esters having the appropriate composition. The plant stanols and / or sterol fatty acid esters thus obtained can be added directly to virgin olive oil to obtain olive oil base products by the present invention.

Claims (37)

(1) a mixture of at least one virgin olive oil and (2) a sterol and / or stanol fatty acid ester, wherein the fatty acid portion of the mixture contains less than 5% by weight of saturated fatty acids and at least 60% by weight of polyunsaturated fatty acids Olive oil base product. The olive oil base product of claim 1, wherein the fatty acid portion of the mixture contains at least 65% by weight of polyunsaturated fatty acids. 3. The olive oil base product of claim 1 or 2, wherein the fatty acid portion of the mixture contains less than 3 weight percent saturated fatty acids. The olive oil base product of claim 1, wherein the fatty acid portion of the mixture contains less than 2% by weight stearic acid. The olive oil base product of claim 1, wherein the fatty acid portion of the mixture contains less than 1.5% by weight stearic acid. The olive oil base product according to claim 1, wherein the product is clear at 30 ° C. 7. The olive oil base product of claim 1, wherein the product is clear at 25 ° C. 7. The olive oil base product of claim 1, wherein the product is clear at 20 ° C. 7. The olive oil base product of claim 1, wherein the product is clear at 18 ° C. 7. The olive oil base product of claim 1, wherein the product is clear at 8 ° C. 7. The olive oil base product of claim 1, wherein the product is clear at 4 ° C. 7. The olive oil base product of claim 1, wherein the product is removed from the refrigerator and cleared after reaching room temperature. The olive oil base product of claim 1, wherein the at least one virgin olive oil consists of virgin olive oil. The olive oil base product of claim 1, wherein the at least one virgin olive oil consists of a special virgin olive oil. The olive oil base product according to claim 1, wherein said sterol and / or stanol fatty acid esters consist mainly of stanol fatty acid esters. The olive oil base product according to claim 1, wherein the stanol portion of the stanol fatty acid ester consists of cytostolol and optionally camphortanol. The olive oil base product according to claim 1, wherein the mixture (2) is present at 0.3-10% by weight, calculated as free sterols and / or stanols. 18. The olive oil base product of any of claims 1 to 17, wherein the mixture is prepared using a food grade method. (1) a mixture of at least one virgin olive oil and (2) a sterol and / or stanol fatty acid ester, wherein the fatty acid portion of the mixture contains less than 5% by weight of saturated fatty acids and at least 60% by weight of polyunsaturated fatty acids A process for preparing an olive oil base product, comprising: (a) esterifying sterols and / or stanols with a source of fatty acids containing less than 5% by weight of saturated fatty acids and at least 60% by weight of polyunsaturated fatty acids; A process for producing an olive oil base product by preparing a mixture of phenol fatty acid esters, and (b) dissolving the mixture in at least one virgin olive oil. 20. The method of claim 19, wherein the source of fatty acid contains at least 65% by weight polyunsaturated fatty acid. 21. The method of claim 19 or 20, wherein the source of fatty acid contains less than 2% by weight stearic acid. 22. The process according to any of claims 19 to 21, wherein the esterification step consists in interesterifying sterols and / or stanols with excess alcohol fatty acid esters and performing esterification in the presence of an interesterification catalyst. Way. 23. The method of any of claims 19 to 22, wherein the sterols and / or stanol fatty acid esters consist primarily of stanol fatty acid esters. 24. The method of any of claims 19-23, wherein the esterification step is performed using a food grade method. (1) a mixture of at least one virgin olive oil and (2) a sterol and / or stanol fatty acid ester, wherein the fatty acid portion of the mixture contains less than 5% by weight of saturated fatty acids and at least 60% by weight of polyunsaturated fatty acids A process for producing an olive oil base product, comprising: (a) dissolving plant stanols and / or sterol fatty acid esters having fatty acids from the high PUFA vegetable oil of at least one virgin olive oil, and (b) between 0 and 30 ° C. A process for producing an olive oil base product consisting of crystallizing higher dissolved lipids from oil obtained from the dissolution step at temperature. The method of claim 25, wherein at least 65% by weight of the fatty acid residues are comprised of polyunsaturated fatty acids. 27. The method of claim 25 or 26, wherein less than 2% by weight of the fatty acid residue consists of stearic acid. 28. The method of any one of claims 25 to 27, wherein the crystallization step is performed at a temperature between 5 and 25 ° C. 29. The method of any of claims 25 to 28, wherein the sterols and / or stanol fatty acid esters consist primarily of stanol fatty acid esters. 30. The method of any one of claims 25 to 29, wherein the mixture is prepared using a food grade method. A plant sterol and / or stanol fatty acid ester mixture, wherein the fatty acid portion of the mixture consists of at least 60% by weight polyunsaturated fatty acids and less than 5% by weight saturated fatty acids, and less than 2% by weight of the mixture consists of stearic acid. 32. The sterol and / or stanol fatty acid ester mixture of claim 31, wherein the fatty acid portion of the mixture consists of at least 65 weight percent polyunsaturated fatty acids. 33. The sterol and / or stanol fatty acid ester mixture of claim 31 or 32, wherein less than 2% by weight of the mixture consists of stearic acid. 34. The sterol and / or stanol fatty acid ester mixture of any one of claims 31 to 33, wherein the fatty acid portion of the mixture consists of less than 3 wt% saturated fatty acids. 35. A sterol and / or stanol fatty acid ester mixture according to any one of claims 31 to 34, wherein said fatty acid residues each contain 4 to 24 carbon atoms. 36. The sterol and / or stanol fatty acid ester mixture of any one of claims 31 to 35, wherein the mixture contains stanol fatty acid esters and the stanol moiety consists of cytostanol and optionally camphortanol. 37. The plant sterol and / or stanol fatty acid ester mixture of any one of claims 31 to 36, wherein said mixture is prepared using a food grade method.