MXPA02004477A - Edible fat blends - Google Patents

Abstract

Olive oil based products, based on the virgin olive oils, containing plant stanol and or sterol fatty acid ester blends and methods for preparing such olive oil based products.

Description

MIX THE EDIBLE GREASE This invention relates to products based on olive oil, based on especially higher grades of olive oils such as virgin olive oils, which contain vegetable stanol esters and / or plant sterol esters and methods for preparing such products to olive oil base, as well as certain esters of sterol and / or plant stanol used for the preparation of the product based on olive oil. Plant sterols are a group of compounds structurally very similar to cholesterol. The plant sterols that occur more frequently in nature are sitoesterol, campesterol and stigmaesterol. Vegetable fats and oils are the main source of vegetable sterols in our diet. In vegetable oils, most of the sterols exist as fatty acid esters. Saturated plant sterols such as sitostanol and campestanol are present in our diet in small amounts. The daily intake of total tin cans in the Finnish diet has been estimated at 30-80 mg / day. However, high oil sterols contain 1-20% of vegetable steels (mainly sitostanol and campestanol). Plant stenoles can also be produced by hydrogenation to remove the double bond in corresponding plant sterols. In recent years, much attention has been focused on properties that lower cholesterol from sterols and tin cans vegetables with already many products enriched with sterol and vegetable stanol such as margarines, salad dressings, bars and commercially available yogurts. Based on recent studies, a daily intake of 2-3 g of plant sterols and steels significantly reduces serum LDL cholesterol levels even when used as part of recommended, healthy diets. Enriched foods such as sterol and plant stanol provide an increased dietary approach to decrease elevated LDL and total serum levels. The enrichment of staple foods with sterols and / or vegetable steels in their fatty acid ester forms is possible without compromising the taste or mouthfeel. Based on the effectiveness of lowering cholesterol and the fact that vegetable steels are virtually non-absorbable, vegetable steels are more preferred, but also mixtures of plant sterols and stems or vegetable sterols can be used alone. The best benefit of using sterols and / or plant stanols to lower high levels of LDL cholesterol and total serum levels is obtained when basic foods are enriched. For example, in the northern part of Europe, margarine and marmalade are very suitable food products for such enrichment, but for the southern part of Europe they need to find other basic food candidates. In this region, olive oil is a staple food of greater importance. In addition, the consumption of olive oil is also increased in other parts of the world due to the health reputation and taste of higher grades of olive oils. Olive oil naturally contains very low levels of plant sterols (typically <0.2 g / 1000 g of oil). In addition, higher-grade olive oils, such as virgin olive oils, contain very high amounts of squalene, a cholesterol precursor. The squalene content varies, but extra virgin olive oil typically contains approximately 300 mg / 100 g of oil. It has been shown that dietary squalene increases serum cholesterol levels in man. Such an effect in LDL cholesterol and total serum levels can be counteracted by plant sterols and / or stanols. Virgin olive oils should remain clear when stored at 20 ° C for 24 hours. Typically, the highest grades of olive oils, such as virgin olive oils, they become cloudy with still clear crystallization that occurs when they are stored for a prolonged period at refrigerant temperatures. An olive oil enriched with plant sterols and / or stems should avoid haze. For the large-scale production of sterol esters and / or plant stanols, normally common vegetable oils or commercially available edible oils with modified fatty acid compositions are used. The enrichment of higher grades of olive oils, such as virgin olive oils, with sterol esters and / or plant stanols, with acid grades derived from such commercially available vegetable oils and their mixing further increases the precipitation of high melting lipids to ambient and lower temperatures. The crystals formed do not dissolve normally, even after prolonged storage at ambient temperatures. East The problem can not be solved, even when using ester conversion of sterol and / or stanol fatty acids derived from commercially available vegetable oils with high levels of polyunsaturated fatty acids and low levels of saturated fatty acids, such as soybean oil. saturated low (PUFA: 67% by weight, SAFA: 7.9% by weight), sunflower oil (PUFA: 64% by weight, SAFA: 12% by weight) or linoleum oil (PUFA: 70% by weight, SAFA: 11% by weight). The Patent of E. OR . 5,089, 139 discloses a method for treating virgin olive oil, in which the virgin olive oil is microfiltered on a microfilter at temperatures of 1 to 35 ° C to obtain a virgin olive oil that remains clear when subjected to a virgin olive oil. cold test at 0 ° C for 24 hours. US Patent 3,751, 569 discloses clear salad and cooking oils having hypocholesterolemic properties. In the liquid glyceride base oil, 0.5-1.0% by weight (calculated as free sterols) of a sterol fatty acid ester is mixed. The fatty acid portion is defined as a saturated C monocarboxylic acid moiety? 2 or an unsaturated fatty acid with up to 24 carbon atoms. In one embodiment, the sterol fatty acid ester is prepared by ester conversion catalyzed by perchloric acid from commercially available free sterols with monocarboxylic acid anhydrides. The sterol fatty acid ester is added in a small enough amount to avoid precipitation at cooling temperatures. In the embodiment exemplified, salad or cooking oil is prepared by dissolving a liquid glyceride base oil and an acid ester. monocarboxylic plant sterol in a mutual solvent (such as diethyl ester or hexane) and evaporate the solvent. The solubility of different fatty acid esters of plant sterol in triolein is also presented, showing very low solubility for vegetable sterol esters of saturated fatty acid C 6 (0. 1%) and Ci 2 (0.6%). The process and product described in the '569 patent suffer from at least two disadvantages. First, the use of free fatty acids prepared from commercially available individual sterols is neither practical nor economical, since these initial products are very expensive. Second, the ester conversion process catalyzed by perchloric acid used in the '569 patent is not a food grade process, since residual chloride remains in the product. In this way, the '569 patent is not suitable for commercial applications. GB Patent 1 405 346 teaches a process by which the free sterols normally contained in fats and oils are converted to fatty acid esters through an ester interconversion process. In addition, a method for producing vegetable oils with high contents of sterol ester is described in Example 2. However, the method taught is based on the ester interconversion of the complete oil mixture, which based on physical properties can not be executed for higher grades of commercial olive oils, such as virgin olive oils.

BRIEF DESCRIPTION OF I NVENTION Saturation of a mixture of plant sterol to a corresponding plant stanol mixture causes marked differences in the fusion properties of the corresponding sterol / stanol esters with the same fatty acid composition. For example, vegetable oil based on sterol ester with low erucic acid rapeseed oil fatty acids and corresponding stanol fatty acid ester showed the following amounts of solid fat contents (% by weight of total fat) at different temperatures as measured by the NMR technique. 1 0 ° C 20 ° C 30 ° C 35 ° C 40 ° C Plant sterol 40.5 1 1 .6 3.5 1 .7 1 .1 Vegetable Stanol 82.3 70.2 34.9 9.4 5.2 The physical properties of sterol and / or stanol fatty esters can be made to order by changing the fatty acid composition of the fatty acid ester or by using different proportions of plant sterols and steels in the ester. In the present invention the problem with precipitation / crystallization of higher melting lipids in higher grade olive oils is overcome by dissolving fatty acid esters of sterol and / or stanol with fatty acids derived from the so-called PU vegetable oils FA high in higher grade olive oils, such as virgin olive oils, and crystallize any higher melting lipid of olive oil at temperatures in the range of refrigerant temperatures to ambient temperatures to obtain a mixture of fatty acid ester of sterol and / or plant stanol with a content Very low saturated fatty acid esters contained in olive oil. The crystallization temperature and time required depends on the amount and type of sterol fatty acid ester and / or stanol used. By choosing the crystallization temperature and time appropriately, the virgin olive oils either remain clear at refrigerating temperatures or become clear when the oil is removed from the refrigeration and maintained at ambient temperatures for a short period of time. Compared to US Patent 3,751,569 which shows a very limited solubility for, for example, vegetable sterol palmitate in a liquid glyceride base oil (0. 1%), the presence of an acid ester mixture Sterol and / or stanol fatty acid with a high level of unsaturated fatty acids clearly increases the solubility of sterol and / or stanol esters. In addition, the present invention teaches sterol ester and / or plant stanol compositions usable for the direct enrichment of virgin olive oils. In this way, an oil according to the invention can also be obtained by adding the appropriate amount of a sterol ester and / or plant stanol with a fatty acid composition containing more than 60%, preferably more than 65%, of acids polyunsaturated fatty acids, and less than 5% saturated fatty acids. When olive oils that are clear at refrigerating temperatures are desired, a sterol ester and / or plant stanol is used with a fatty acid composition containing more than 60%, preferably more than 65%, of polyunsaturated fatty acids, and less than 5% saturated fatty acids, preferably less than 3%, less than 2%, or more preferably less than 1.5% saturated fatty acids, such as stannic acid. Such sterol and / or stanol fatty acid esters can be obtained by any ester conversion method known in the art. material, such as by ester conversion of a fatty acid mixture or a fatty acid alcohol ester mixture having the appropriate, predetermined fatty acid composition. All values in percent and throughout the specification are% by weight, unless otherwise indicated.

DESCRIPTION OF THE PREFERRED MODALITIES The term "virgin olive oils" means to include extra virgin olive oil, virgin olive oil, ordinary olive oil and virgin olive oil lampanato, all defined according to the Official Journal of the European Community No. L 39/2 (1 5.2.1992). In addition, any blend of virgin olive oils with lower grades of olive oils as defined by the Official Journal of the European Community is covered by this definition. Preferably, such a mixture contains at least 25% more preferably at least 50%, and more preferably at least 75% virgin olive oils. The term "olive oil based product" means to include virgin olive oils, according to the above definition, enriched with a mixture of fatty acid esters of sterol and / or plant stanol. Approximately 0.3-25% by weight, preferably about 0.3-1.0% by weight, more preferably about 1.5-1.0% by weight, and more preferably about 3-1.0% by weight of sterol fatty acid esters and / or stanol (calculated as free stanols) can be included in the product based on olive oil.

The term "high PUFA olive oils" means to include vegetable oils or vegetable oil blends containing more than 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, linole oil or mixtures thereof. The amount of saturated fatty acids in the fatty acid composition is typically about 7.5-4.9%, more preferably about 8-25% and more preferably about 10-20%. The term "phytosterol" means including 4-demethyl steels, 4-monomethyl stearols and 4-methyl sterols., 4, -dimethyl (triterpene alcohols) or their mixtures. The term "phytostanol" means to include 4-demethyl steels, 4-monomethyl steels and 4,4-dimethyl stenols, and is preferably obtained by hydrogenation of the corresponding phytosterol. Typical 4-demethyl steels include sitosterol, campesterol, stigmaterol, brasicaesterol, 22-dehydrobraesterol,? 5-oatsterol. The 4,4-dimethyl sterols include cycloartenol, 24-methylenecycloartanol and cyclobranol. Typical phytostanols include sitostanol, campestanol and its 24-epimers, cycloartanol and saturated forms obtained by saturation of triterpene alcohols (cycloartenol, 24-methylenecycloartenol and cyclobranol). The terms phytosterol and phytostanol also include all possible natural mixtures of tin steels and 4-demethyl steels, tin steels and 4-monomethyl stearols and stenoles and 4,4-dimethyl steels and mixtures of natural mixtures. The The terms phytosterol and phytostanol also include any individual 4-desmethyl sterol, 4-monomethyl sterol or 4,4-dimethyl sterol or their corresponding (stanol) saturated forms. The terms "plant sterol" and "plant stanol" are proposed as synonyms for the terms "phytosterol" and "phytostanol", respectively. "Sterol" and "stanol" must also mean "phytosterol" and "phytostanol", respectively. The "polyunsaturated fatty acids" are defined herein as fatty acids containing two or more double bonds. Preferably, the double bonds have a cis configuration, but one or more double bonds can be in the trans configuration. It is known that many vegetable oils commercially available due to thermal isomerization in the deodorization process contain a percentage level of polyunsaturated fatty acids containing one or more double bonds with trans configuration. In addition, the double bonds can be either the so-called conjugates or interrupted by methylene. The typical vegetable oil derived from polyunsaturated fatty acids are linoleic,? -leoleic and linoleic acid, but polyunsaturated fatty acids from fish oils such as docosahexaenoic acid and eicosapentanoic acid can also be used. The term "saturated fatty acids" is understood to mean fatty acids with 4-24 carbon atoms that have no double bond, thus including both straight and branched chain fatty acids, by the term "sterol esters and / or stanols PUFA. elevated "sterol and / or stanol esters are preferably produced with fatty acids of elevated PUFA vegetable oils, but fish oil derived from polyunsaturated fatty acids or mixtures of fish oil or vegetable derived polyunsaturated fatty acids can also be used. The sterol and / or stanol fatty acid esters used in the present invention are preferably produced using a food grade process. A "food grade process" as defined herein includes any process by which the sterol and / or stanol fatty acid ester product is free of residual chemicals that are (1) undesirable in the final product since affect one or more of the qualities of the sterol and / or stanol fatty acid esters, or (2) harmful to a consumer from a food safety point of view (eg, solvents or chlorine-containing catalysts). There are a number of food grade processes known in the art, any of which may be suitable for producing the sterol and / or stanol fatty acid esters used in the present invention. Preferably, the food grade process is a food-grade process-free solvent. The sterol and / or stanol fatty acid esters can be produced by the method described in the E. OR . 5,502,045, for example by transesterification of fatty acid alcohol esters obtained from high PUFA vegetable oils or mixtures thereof. Another suitable method for producing esters of sterol and / or stanol fatty acid is by esterification of the sterol and / or free stanol with high vegetable oils PUFA in the presence of a catalyst of trans- or interconversion in ester. Direct, preferably catalytic, ester conversion methods such as those described in U.S. Patent 5,892,068 or enzymatic ester conversion methods such as those described in EP 195 31 1 can be used. Another possibility to produce sterol and / or stanol fatty acid esters is to use the excess of elevated PUFA alcohol esters present in the oily phase obtained after conversion to high stanol ester and / or sterol PUFA ester according to the method described in U.S. Patent 5,502,045. This mixture of high PUFA alcohol ester and stanol and / or sterol ester can as such be subjected to a fractionation step to remove higher stanol and / or sterol ester from fusion and then used for conversion to stanol ester and / or sterol. Esters of stanol, esters of sterol or their mixtures can preferably be produced by the method indicated in the patent of US Pat. No. 5,502,045 using esters of fatty acid alcohol with a predetermined fatty acid composition according to the present invention. The fatty acid alcohol esters can be produced by any process known in the art, such as fractionation of detergent or solvent of fatty acid esters of alcohol obtained from a high PUFA liquid vegetable oil or mixtures of elevated PUFA oils. The corresponding mixtures of fatty acid alcohol esters can also be obtained by distillation processes under reduced pressure. Such distillation procedures can be preferably used to remove saturated fatty acids with 16 or less carbon atoms. The fatty acid alcohol esters with the defined fatty acid compositions can also be obtained by alcoholysis of vegetable oils or oil mixtures with reduced contents of saturated fatty acids, obtained for example, according to the Patent of US Pat. No. 5,670,348. Sterol and / or stanol esters with the desired fatty acid composition can also be produced by direct catalytic ester conversion methods, for example, US Pat. No. 5,892,068, between free fatty acids or fatty acid mixtures of the composition and stanol and / or sterol. Conversion to ester of stanol and / or sterol with a triglyceride having the desired fatty acid composition using an ester transconversion or interconversion catalyst is also a suitable method for producing the sterol and / or stanol esters. In addition, sterol and / or stanol esters can also be produced by conversion to enzymatic ester, for example, as indicated in EP 1 95 31 1. In addition, mixtures of polyunsaturated fatty acids can be used to obtain sterol and / or stanol esters with the desired composition. The stanol esters and / or sterol esters with the desired fatty acid compositions can also be obtained by commercially applied fractionation processes, such as wet, detergent and dry fractionation of sterol and / or stanol fatty acid esters obtained by conversion into ester of high PUFA fatty acids derived from mixtures of vegetable oil or vegetable oil m M l < ethodes based on, for example, the ester transconversion process set forth in US Pat. No. 5,502,045, any direct catalytic ester conversion process, direct or by the use of an enzymatic ester conversion process, for example, as indicated in EP 1 95 31 1. Especially the fractionation of solvents can be used to prepare desired stanol ester and / or sterol compositions. When enzymatic ester conversion processes are used as indicated in EP 1 95 31 1, the fractionation can preferably be carried out directly in the reaction solvent used in the esterification process after removing the enzyme and the phase of possible water. The processes discussed above are only a few of the food grade processes that can be used to make the fatty acid esters of sterol and / or stanol according to the invention. In a preferred embodiment the virgin olive oils, preferably an extra virgin olive oil containing a predetermined mixture of sterol and / or stanol fatty acid esters can be obtained by dissolving 5-50% by weight (preferably 5-25%) of esters of fatty acid of sterol and / or ethanol obtained by an ester conversion process such as that described in the Patent of E. U. 5,502,045, for example when using a high PUFA vegetable oil or a mixture of high PUFA vegetable oils as a source for the fatty acids. This can be carried out preferentially as part of the regular refining process of virgin olive oils. The olive oil mixture of sterol ester and / or stanol thus obtained is heated and mixed to completely dissolve the sterol and / or stanol esters in the olive oil, after which a conventional "conditioning for winter" stage or any fractionation process as known in the art takes place. For example, a type of dry fractionation process by groups or conditioning for winter can be carried out at 0-30 ° C, preferably at 5-25 ° C resulting in products based on olive oil that are clear at some point in the temperature range of 4-25 ° C, more preferably at some point in the temperature range of 4-8 ° C. All products based on olive oil made according to the invention can be clarified, in the cases that nebulosity is shown at refrigerating temperatures, when they are removed from the refrigeration and stored at room temperature, that is, at some point in the temperature range of 18-30 ° C, more preferably at some point in the temperature range of 1 8-25 ° C. This means that the olive oil-based product of the invention is clear at 30 ° C or more, preferably at 25 ° C or more, more preferably at 20 ° C or more, even more preferably at 1 8 ° C or more . If the product is stored at refrigerating temperatures (i.e., about 2-12 ° C, preferably about 2-8 ° C), it is preferably clear at 4 ° C. Since most European consumers are accustomed to storing the oil at ambient temperatures, the olive oil-based product may preferably be clear at 25 ° C or more, more preferably at 20 ° C or more, and more preferably at 1 8 ° C or more. The crystallization temperature and time can be altered depending on the amount and type of stanol ester and / or sterol ester used and the desired final product. After removing the solid part mainly made of saturated fatty acids from the stanol and / or stanol ester by, for example, vacuum filtration, the olive oil-based product obtained can be used as such or diluted with virgin olive oils without process to obtain the desired content of sterol and / or plant stanol in the product based on olive oil. Depending on the quality of the virgin olive oils, some of the higher melting lipid components naturally contained in the olive oil will be removed simultaneously by the filtration process, and in this way the process improves the clarity of the olive oil at cooling temperatures (ie, about 2-12 ° C, preferably about 2-8 ° C). It is obvious to those skilled in the art that any type of fractional process in addition to dry fraction fractionation processes by groups can be used to crystallize and remove fatty acid esters of sterol and / or ethanol with higher melting points, for example , esters of stanol fatty acid and / or sterol based on saturated degrees acids. It is also clear to those skilled in the art that any filtration method known in the art can be used. Another way to produce sterol and / or stanol esters with the desired fatty acid compositions is to use the excess methyl ester of fatty acid of the mixture of stanol ester and / or high sterol PUFA obtained after the ester transconversion described in the Patent of E. U. 5, 502, 045. After drying, the mixture of ester alcohol fatty acid ester of sterol and / or stanol is cooled to -25 ° C, depending on the composition of the sterol ester and / or stanol produced, and the higher melting components are allowed to crystallize for 4-24 hours. Optionally, the additional fatty acid alcohol ester is added to facilitate the fractionation process. Any ester of fatty acid alcohol can be used, but the use of elevated PUFA alcohol ester is preferred. After filtration, the clear oil phase is preferably deodorized to remove the excess alcohol fatty acid esters and obtain an unflavored sterol and / or stanol ester. The sterol and / or ethanol esters obtained as such can be preferably mixed in the virgin olive oils. The fatty acid esters of sterol and / or plant stanol with the desired fatty acid composition can be produced in addition to fatty acids or esters of fatty acid alcohol with appropriate composition. The sterol and / or vegetable stanol fatty acid esters thus obtained can be added directly to virgin olive oils to obtain olive oil-based products taught by this invention. In addition, the sterol and / or stanol ester compositions according to the invention can be produced using "fatty acid starting materials" such as fatty acids, fatty acid alcohol esters or oils obtained by processes including, for example, the use of microorganisms, enzymes or new species of plants that produce oil. The part of stanol and / or sterol can be obtained from any source of stanol and / or sterol, for example, from the pulp industry or from the processing of vegetable oils. New species that produce high quantities or more attractive compositions of Suitable steels and / or sterols produced by conventional methods or genetic modifications are also included as possible raw materials for the production of tin and / or sterols. Preferably, stanol and / or sterols are used hereafter in a food grade process to produce the olive oil based product of the invention. In a preferred embodiment of this invention, virgin olive oil is enriched with vegetable stanol fatty acid esters with a predetermined fatty acid composition. As well, mixtures of sterol fatty acids and vegetable stanol or fatty esters of vegetable sterol can be used. The following examples are presented in order to describe the present invention in more detail. All percentages given are% by weight. EXAMPLES Example 1: Preparation of stanol fatty acid esters based on low saturated soybean oil fatty acids (LowSatSoy) Vegetable stanol fatty acid esters are produced on a pilot scale. 6 kg of vegetable steels (composition: 68.2% sitostanol, 28.3% campestanol, 1.1% sitosterol and indicative quantities of other unsaturated sterols) obtained by hydrogenation of commercially available vegetable sterols are mixed with 8.6 kg of methyl ester mixture LowSatSoy and dry at 1 1 0-1 20 ° C. The temperature of the dry mixture is reduced to 90-95 ° C and the sodium methylate catalyst (73 g) is added. The temperature increases to 120 ° C and the reaction takes performed vacuum (40 mmHg) for 4 hours. The conversion is monitored by GC analysis. Once it is achieved > 98% of the conversion, the temperature is reduced to 1 00 ° C and 30% by weight of water to > 90 ° C, hot are added to destroy the catalyst. The aqueous phase is removed and the oily phase is rinsed again to provide < 1000 rpm. The oily phase is dried at 95 ° C and the dried material is bleached using 1% by weight of bleaching aid (Trisyl, Grace, Germany) for 20 minutes at 95 ° C under vacuum. After removal of the bleaching aid by filtration, a standard pilot scale deodorization (group deodorizer, 9 kg capacity) is carried out to remove excess methyl esters from soybean oil and obtain an unflavored 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 content of C16: 0 and C18: 0 was 3.6% for both. The stanol content was 57.6% by weight with a high esterification conversion (amount of free stanol 1.5% by weight). Example 2: Preparation of stanol fatty acid ester based on vegetable oil with fatty acids derived from linone oil A mixture of stanol fatty acid ester with fatty acids derived from linola oil is prepared with the same mixture of plant stanol and method as indicated in Example 1. The fatty acid composition of the obtained plant stanol ester was as follows: SAFA: 1 0.6%, MU FA: 1 7.7% and PUFA: 71.8%. The content of C 1 6: 0 and C 1 8: 0 was 6.2% and 3.9%, respectively. The stanol content was 57.9% by weight with a high ester conversion (amount of stanol free 0.1 3% by weight). Example 3: Preparation of vegetable stanol fatty acid ester based on high PUFA fatty acids, distillates derived from sunflower oil. The PU FA plant stanol esters raised with similar procedures as described in Example 1 with methyl fatty acid esters after the distillation of methyl esters based on sunflower oil. The combined distillation cuts contained 5.6% SAFA (0.3% C1 6: 0, 5.0% C1 8: 0), 26.5% MU FA and 67.9% PUFA. The total sterol content (plant sterol + plant stanol) of the plant stanol ester was 59.5%, while the plant stanol content was 58.4% by weight. The amount of free tin cans was 0.86% by weight. Example 4: Preparation of plant stanol ester enriched with olive oil by crystallization at + 7 ° C. 7% by weight of the vegetable stanol ester (equivalent to 4.0% by weight of vegetable stems and 0.05% by weight of plant sterols) with fatty acids derived from low saturated soybean oil produced according to Example 1, are dissolved in oil Extra virgin olive tree (Carlshamm Mejeri, Sweden) by heating the oil to 60 ° C and stirring at normal pressure. When all the plant stanol ester has dissolved, the mixture is allowed to crystallize under slow stirring at + 7 ° C for 21 hours. The oil is filtered by using vacuum (40 mmHg) and thick (charcoal) filtration paper conventionally used in winter conditioning processes. The filtrate weight was 1. 1% by weight of the plant stanol ester mixture of extra virgin olive oil. The product based on olive oil obtained contains 3.7% by weight of plant stanol with 0. 1 2% by weight of vegetable steels in the free form. Vegetable stanol ester fatty acids contain 4.9% saturated fatty acid (2.4%, C 16: 0 and 1.5% C 18: 0), compared to 8.7% saturated fatty acids in the added plant stanol ester , showing clearly that stanol esters, mainly saturated, are what crystallize. The plant stanol content of the filtrate was 19.3% by weight with only 0.18% by weight of plant stanol in the free form. The stanol ester obtained enriched with olive oil remained clear at 5 ° C for at least 5 days, while the clear crystallization of the glass wall of the bottle could be observed after 3 days in the extra virgin olive tree of control. Example 5: Preparation of plant stanol ester enriched with virgin olive oil by crystallization at 16 ° C. An olive oil enriched for plant stanol ester is prepared in a similar manner as in Example 4, except that the crystallization is carried out at 16 ° C for 21 hours. The olive oil-based product obtained contains 3.7% by weight of vegetable stanol with 0.1% by weight of vegetable steels in the free form. The fatty acid composition of the plant stanol ester was 4.5% SAFA (2.3% C 1 6: 0 and 1.4% C 1 8: 0), 29.0% MU FA and 66.6% PUFA. The weight of the filtrate was 1.5% by weight of the stanol ester mixture of virgin olive oil initially. The plant stanol content of the filtrate was 0.7% by weight with only 0.1% by weight as free plant stanol. The fatty acid composition of the plant stanol ester of the filtrate was 36.9% SAFA (1 8.9%) C 1 6: 0 t 1 5.4% C 1 8: 0); 1 9.7% MU FA and 43.4% PU FA.

These data clearly show that the mainly saturated vegetable fatty acid stanol esters crystallize. The virgin olive oil enriched with vegetable stanol ester obtained remained clear at 5 ° C for at least 5 days, while the clear crystallization of the glass wall of the bottle could be observed after 3 days in the extra virgin olive oil of control. Example 6. Preparation of virgin olive oils enriched with vegetable stanol ester 7% by weight of plant stanol ester produced according to Example 2 is dissolved in extra virgin olive oil (Carishamm Mejeri, Sweden) according to Example 4 and crystallizes at 1 6 ° C for 20 hours. The oil sample obtained after filtration is stored in the refrigerator at 7 ° C for 24 hours and is found to become cloudy. The sample becomes clear at room temperature, but begins to become cloudy after one day at room temperature with crystal clear formation after 2 days at room temperature. The product based on olive oil obtained contains 3.3% by weight of plant stanol. The fatty acid composition of the plant stanol ester was 6.0% SAFA, 19.4% MUFA and 74.6% PUFA, as compared to the stanol ester of linole source 10.6% SAFA, 17.7 & MUFA and 71.8% PUFA. Based on these data it is clear that a SAFA content of 6% of the vegetable stanol ester fatty acids is very high to obtain the desired properties of the olive oil based product. Example 7: Preparation of virgin olive oils enriched with plant stanol ester. 11 and 16% by weight of the plant stanol ester obtained in Example 3 is dissolved in extra virgin olive oil (Carishamm Mejeri, Sweden) and processed according to Example 4. The crystallization temperatures were + 7 ° C ( 20 hours) and + 23 ° C (7 days) for the samples of 16% by weight and + 23 ° C (7 days) for the sample of 11% by weight. The sample of 16% by weight crystallized at 7 ° C remained clear at 7 ° C for at least 1 week. The total stanol content of this olive oil based product was 8.9% by weight and the fatty acid composition of the plant stanol ester contained in the olive oil based product was 1.7% SAFA (0.65% C) 16: 0 and 0.34% C 1 8: 0), 26.8% MUFA and 71.5% PUFA. This product based on olive oil can be diluted with virgin olive oils without processing to obtain the desired vegetable stanol content of the olive oil based product to be commercialized. Samples crystallized at 23 ° C for 7 days become cloudy at 7 ° C, but both samples become clear at room temperature. The stanol content of the two products based on olive oil was 6.3 and 8.9% by weight for the 1 1% and 16% samples, respectively. Example 8: Preparation of virgin olive oils enriched with vegetable stanol ester 4.5% by weight of the vegetable stanol esters obtained in Examples 1, 2 and 3 are dissolved in extra virgin olive oil (Carishamm Mejeri, Sweden) and stored at 7 ° C for 1 1 h. Olive oil-based products enriched with vegetable stanol ester based on sunflower methyl ester cuts (SAFA: 5.6%, C16: 0.3%, C18: 0 . 0%) showed clear crystallization at + 7 ° C and these samples do not become clear at room temperature, clearly indicating that the amount of stanol ester C 1 8: 0 is too high in this product based on olive oil. All three mixtures were also crystallized because the SAFA content was too high (8.7%, 0.6% and 5.6%). Example 9: Preparation of vegetable stanol fatty acid ester with desired fatty acid composition by solvent fractionation. 1 0 g of the plant stanol ester obtained by the procedure set forth in Example 1 are dissolved in 90 ml of n-hexane in a 200 ml centrifuge tube. The mixture is maintained at + 7C for 24 hours, after which the mixture is centrifuged in a programmable temperature centrifugation. The hexane phase is removed and the hexane evaporated. The obtained plant stanol ester contains 4.6% SAFA (2.4% C 1 6: 0 and 1.8% C 1 8: 0), 27.2% MU FA and 68.2% PU FA. Example 1: Preparation of a product based on olive oil using vegetable stanol ester with desired fatty acid composition 7% by weight of the plant stanol ester obtained from example 9 is dissolved in extra virgin olive oil according to a similar procedure as indicated in Example 4 and stored at + 7 ° C. The oil remained clear for at least 7 days. Example 1 1: Preparation of a product based on olive oil enriched with stanol fatty acid esters Two groups of methyl esters of fatty acid are prepared by distillation in a similar manner as described in Example 3, but with the following fatty acid compositions obtained: 4.9% SAFA, 34.1% MU FA and 61% PUFA and the other 2.5% SAFA, 36.5% MUFA and 61% PUFA . The methyl esters of fatty acid obtained were used for the esterification of plant stanol using the method described in Example 1. 0.3 g of stanol fatty acid esters are dissolved in 10 g of extra virgin olive oils. Both oils remained clear at room temperature for at least a week. Example 1 2: Preparation of a product based on olive oil enriched with sterol fatty acid ester. The same methyl ester of fatty acid comprising 4.9% SAFA, 44.1% MUFA and 61% PU FA as prepared and used in Example 1 1, is used for the conversion to vegetable sterol ester. 0.6 g of the sterol fatty acid ester are dissolved in 1 g of extra virgin olive oil. The oil remained clear at room temperature for at least a week.

Claims (37)

1. REIVI NDICATIONS 1. A product based on olive oil, comprising (1) at least one of the virgin olive oils and (2) a mixture of fatty acid esters of sterol and / or stanol, wherein the fatty acid portion of the The mixture contains less than 5% by weight of saturated fatty acids and more than 60% by weight of polyunsaturated fatty acids. 2. The product based on olive oil according to claim 1, characterized in that the fatty acid portion of the mixture contains more than 65% by weight of polyunsaturated fatty acids. 3. The olive oil-based product according to claim 1 or 2, characterized in that the fatty acid portion of the mixture contains less than 3% by weight of saturated fatty acids. 4. The olive oil-based product according to any of claims 1 -3, characterized in that the fatty acid portion of the mixture contains less than 2% by weight of stearic acid. The product based on olive oil according to any of claims 1 - 3, characterized in that the fatty acid portion of the mixture contains less than 1.5% by weight of stearic acid. 6. The product based on olive oil according to any of claims 1-5, characterized in that the product is clear to 30 ° C. 7. The product based on olive oil according to any of claims 1-5, characterized in that the product is clear at 25 ° C. 8. The product based on olive oil according to any of claims 1-5, characterized in that the product is clear at 20 ° C. 9. The olive oil-based product according to any of claims 1-5, characterized in that the product is clear at 18 ° C. 1 0. The product based on olive oil according to any of claims 1-5, characterized in that the product is clear at 8 ° C. eleven . The product based on olive oil according to any of claims 1-5, characterized in that the product is clear to 4 ° C.
2. 2. The product based on olive oil according to any of claims 1 to 5, characterized in that the product becomes clear after being removed from the refrigerator and brought to room temperature.
3. 3. The product based on olive oil according to any of claims 1 to 12, characterized in that at least one of the virgin olive oils comprises virgin olive oil. 14. The olive oil-based product according to claim 1, characterized in that at least one of the virgin olive oils comprises extra virgin olive oil. The product based on olive oil according to any of claims 1-14, characterized in that the stanol and / or sterol fatty acid ester comprises mainly stanol fatty acid esters. The product based on olive oil according to any of claims 1 - 1, characterized in that the stanol part of the stanol fatty acid ester comprises sitostanol and optionally campestanol. 7. The product based on olive oil according to any of claims 1-16, characterized in that the mixture (2) is present in an amount of 0.3-1 0% by weight, calculated as tin and / or free sterols. . 8. The olive oil-based product according to claim 1, characterized in that the mixture is prepared using a food-grade process. 9. A method for preparing a product based on olive oil, comprising (1) at least one of the virgin olive oils and (2) a mixture of stanol fatty acid esters and / or sterol wherein the The fatty acid portion of the mixture contains less than 5% by weight of saturated fatty acids and more than 60% by weight of polyunsaturated fatty acids, the method comprising (a) converting into ester a sterol and / or stanol with an acid source fatty acids containing less than 5% by weight of saturated fatty acids and more than 60% by weight of polyunsaturated fatty acids, to produce a mixture of stanol fatty acids and / or sterol and (b) dissolving the mixture in at least one of the virgin olive oils. The method according to claim 1, characterized in that the source of fatty acids contains more than 65% by weight of polyunsaturated fatty acids. twenty-one . The method according to claim 1 9 or 20, characterized in that the source of fatty acids contains less than 2% by weight of stearic acid. 22. The method according to any of claims 1 9-21, characterized in that the step of conversion into ester comprises interconverting in ester the sterol and / or stanol using an excess of esters of fatty acid of alcohol, and performing the conversion step in ester in the presence of an ester interconversion catalyst. 23. The method according to any of claims 1-22, characterized in that the stanol and / or sterol fatty acid esters comprise mainly stanol fatty acid esters. The method according to any of claims 1-23, characterized in that the step of ester conversion is conducted using a food grade process. 25. A method for preparing a product based on olive oil, comprising (1) at least one of the virgin olive oils and (2) a mixture of stanol fatty acid esters and / or sterol wherein the The fatty acid portion of the mixture contains less than 5% by weight of saturated fatty acids and more than 60% by weight of polyunsaturated fatty acids, the method comprising (a) dissolving the fatty acid esters of sterol and / or plant stanol which have fatty acids derived from PUFA vegetable oils elevated in at least one of the virgin olive oils and (b) crystallize high melting lipids from the oil obtained from the dissolution stage at a temperature between 0-30 ° C, to obtain the product a olive oil base. The method according to claim 25, characterized in that more than 65% by weight of the fatty acid portions comprise polyunsaturated fatty acids. The method according to claim 25 or 26, characterized in that less than 2% by weight of the fatty acid portions comprise stearic acid. 28. The method according to any of claims 25-27, characterized in that the crystallization step is carried out at a temperature between 5-25 ° C. 29. The method according to any of claims 25-28, characterized in that the stanol and / or sterol fatty acid esters comprise mainly stanol fatty acid esters. 30. The method according to any of claims 25-29, characterized in that the mixture is prepared using a food grade process. 31 A mixture of stanol fatty acid ester and / or plant sterol, wherein the fatty acid portion of the mixture comprises more than 60% by weight of polyunsaturated fatty acids and less than 5% by weight of saturated fatty acids, wherein less than 2% by weight of the mixture comprises stearic acid. 32. The mixture of stanol and / or sterol fatty acid ester according to claim 31, characterized in that the fatty acid portion of the mixture comprises more than 65% by weight of polyunsaturated fatty acids. 33. The mixture of stanol fatty acid ester and / or sterol according to claim 31 or 32, characterized in that less than 1.5% by weight of the mixture comprises stearic acid. 34. The mixture of stanol and / or sterol fatty acid ester according to any of claims 31-33, characterized in that the fatty acid portion of the mixture comprises less than 3% by weight of saturated fatty acids. 35. The mixture of stanol fatty acid ester and / or sterol according to any of claims 31-34, characterized in that the fatty acid portions each contain 4-24 carbon atoms. 36. The mixture of stanol and / or sterol fatty acid ester according to any of claims 31-35, characterized in that the mixture contains stanol fatty acid ester and the stanol part comprises sitostanol and optionally campestanol. 37. The mixture of stanol fatty acid ester and / or sterol according to any of claims 31 -36, characterized in that the mixture is prepared using a food grade process. RESU ME N Products based on olive oil, based on virgin olive oils, containing mixtures of sterol fatty acid and / or plant stanol and methods for preparing such products based on olive oil.