JP5550147B2 - Deodorization and stabilization of marine oil - Google Patents

Description

Detailed Description of the Invention

  The present invention relates to a method for deodorizing and stabilizing marine oil and the marine oil thus obtained.

  Marine oils have attracted much attention as a source of polyunsaturated fatty acids (PUFA), especially eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) (PUFA esters in the ethyl ester form as well as the natural glyceride form). Including) has an important meaning in the diet. However, marine oils vary greatly in quality in terms of taste and stability depending on their origin, their degree of impurity removal, and the removal of degradation products in addition to natural by-products. Since PUFA contains some carbon-carbon double bonds, it is susceptible to oxidation under atmospheric conditions to cause fishy taste and fishy odor.

  Ingesting many of these compounds now has a beneficial health effect and can reduce mortality from coronary heart disease through blood pressure, atherosclerosis, and thrombus formation. There is a lot of solid evidence.

  With increasing interest in these compounds, the search for ways to stabilize marine oils against the occurrence of oxidation and off-flavors has become an urgent task.

  Recently, many improvements have been seen in the stabilization of marine oil and PUFA by adding stabilizing substances.

  By Hamilton et al. Am. Oil Chem. Soc. (JAOCS), Vol. 75, No. 7, pp. 813-822 (1998) discloses a very good ternary additive mixture (δ-tocopherol 2%, ascorbyl palmitate 0.1%, lecithin 0.5%) to prevent auto-oxidation of fish oil. Has been. Fish oil refined after the addition of this mixture does not show significant peroxidation even after a period of 6 months at 20 ° C., but this mixture is effective in preventing off-taste and off-smell. Not very successful. Unusual flavor occurred within 3 weeks.

  EP 340635A describes a process for treating oils containing EPA and DHA, in particular fish oil, under mild conditions (30 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 2 to 5 hours). Volatile flavor compounds with low boiling point and low polarity are reduced by performing vacuum steam distillation at low pressure, and volatile flavor compounds with high boiling point and high polarity are obtained by contacting the oil with an adsorbent, such as silica gel. A method by reducing is described. In certain embodiments, the oil thus decontaminated is mixed with an antioxidant that is a rosemary extract. However, such oils have greatly reduced fishy odor and odor generation, but are not suitable for many foods, especially dairy products, due to the taste and odor unique to rosemary extract.

  In accordance with the procedure described in European Patent Application No. 61346 (WO 93/10207), it is treated with silica, subjected to mild vacuum steam distillation (140-210 ° C.) and lecithin, ascorbyl palmitate ( (AP), and refined marine oils stabilized with a mixture of alpha tocopherol have improved rancimat stability (according to Examples 1-8 (4.9-14 hours at 100 ° C.)) and are primarily health supplements Applicability to is high. However, it has also been recognized that there are still unacceptable unpleasant tastes and unpleasant odors in dairy products such as yogurt and milk drinks that are particularly susceptible to smell.

  EP 999259 (U.S. Patent Application No. 2003 / 161918A1) treats marine oil with silica and optionally palmitic acid in the presence of rosemary or sage extract. The preparation and stabilization of PUFA-containing edible marine oils by a process comprising adding ascorbyl and mixed tocopherols and subjecting to batch vacuum steam deodorization for 2 hours at a temperature of 150 ° C. to 190 ° C. is described. This procedure results in a stabilized edible marine oil with excellent odor and taste characteristics and a rancimat induction time value of 4.1 to 6.2 hours. Since this oil has the highest quality ever obtained, it is suitable for various food applications including dairy products such as milk and yogurt.

  In view of the growing need for high quality edible oils containing PUFAs, production methods that are more efficient and run in a shorter time from a quantitative point of view are desirable. The present invention provides such a method and corresponding product.

  Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A10, p. According to 204-206 (1967), semi-continuous and continuous deodorizing systems are used instead of batch-type deodorizing devices because steam is saved by performing more efficient stripping and heat recovery. It's getting on. Examples of semi-continuous and continuous deodorizers consisting of iron barrels with stainless steel trays attached and examples of their suppliers are described. The Campro deodorizer has a continuous tray-in-shell design that combines the concept of plug flow and a unique thin-film stripping concept.

  For the development of commercial deodorization systems from the beginning to the early 90s, Bailey's Industrial Oil and Fat Products, Volume 4, Chapter 6 (Deodorization), YH High (Y H. Hui), John Wiley & Sons, New York, 1996, pp. 14-28. 339-390.

  U.S. Pat. No. 4,996,072 describes a method for deodorizing and / or reducing the amount of cholesterol of fats and oils, especially fish oils or marine oils, which oil of this kind is about 400-550 ° F. (204 Heating to a temperature of ˜288 ° C.) and flash-evaporating the heated oil to obtain a par-treated oil liquid phase, which is then treated with 1-7 mmHg countercurrent steam 1 Disclosed is a method by multi-stage treatment under reduced pressure comprising subjecting to thin film stripping with ˜15% by weight. The clean oil thus obtained has a reduced cholesterol content and contains at least 95% of the starting n-3 unsaturated fatty acid content and has no peculiar taste or odor. It is an oil from which unnecessary materials have been removed.

  Similarly, U.S. Pat. No. 5,436,018, which is closely related to this, describes a method for reducing the cholesterol level of an oil, especially fish oil or marine oil, wherein such oil is at least 400 ° F. ( 204 ° C.) and a pressure of at least 1 mmHg is introduced into the top of a counter-current thin-film steam stripper and at the same time is deodorized by a method comprising introducing water vapor from the bottom of the counter-current thin-film steam stripper. In addition, it is disclosed that an oil with reduced cholesterol and a good flavor can be obtained. This method is advantageous over conventional deodorization techniques because the degradation of beneficial n-3 unsaturated fatty acids is minimized, considering the short oil residence time of 5 minutes or less. It has been broken.

  U.S. Pat. No. 4,810,330 describes high boiling liquids with relatively low charge (fatty acids, edible oils, fats, glycerides, other high boiling esters, etc.), in particular light acids in addition to fatty acid glycerides. Palm oil and other vegetable oils containing about 5% by weight of light ends (free fatty acids, water, pigments, odor and / or flavor compounds) are continuously stroked through a fallinf liquid film in a countercurrent tower. A specific embodiment of a continuous deodorization method by contacting with a ripping stem is described.

  Similar methods and apparatus for removal / deodorization / physical refining of volatile impurities in high boiling edible oils, fats and esters, especially vegetable and hardened fish oils, by countercurrent steam stripping in the falling film tower For example, U.S. Pat. No. 4,394,221, U.S. Pat. No. 4,599,143, and British Patent Application No. 2176713A (German Patent Application Publication No. 3522897A1). Is well known.

Japanese Patent Application Laid-Open No. 2007-014263A describes edible oils and fats derived from plants and animals such as fish oil (unrefined, deoxidized, decolorized, deodorized, hydrogenated) having a trans fatty acid content of 1% by mass or less. Further, it is described that purification is performed by combining a thin-film column containing a stacked filler and a tray-type apparatus. The column internal temperature is 225 to 252 ° C., the pressure is 18 hPa or less, the oil load value is 12 to 28 m ³ / m ² · hr, and the moving unit height of the regular packing is 1 to 7 m. The internal temperature of the tray type apparatus is 210 to 247 ° C., and the pressure is 18 hPa or less. The purification treatment time is 15 to 120 minutes.

  Xu et al. (JAOCS, Vol. 78, No. 7, pp. 715-718 (July 2001)) distill certain structured lipids in a conventional batch deodorizer using stripping steam. Therefore, the cause and the influence of acyl transfer when impurities are removed are investigated. The results suggest that more efficient separation techniques should be used to improve the quality of the structured lipids from which impurities have been removed, and the vacuum should be as low as possible to lower the distillation temperature. In order to shorten the distillation time, it has been concluded that the thin film principle should be used in the packed column.

  Ahrens, Fett / Lipid, Vol. 101, No. 7, pp. 230-234 (1999), WILEY-VCH Verlag GmbH, Weinheim, review the history of thin-film deodorization of seed oil. Development of a thin film deodorization apparatus was started in the 1970s and has been used industrially since the mid 1980s. The latest model is SoftColumn ™, a deodorizing device with regular packing, specially developed to treat seed oils, especially sunflower, soy, and rapeseed oil, at a mild and low cost . By stripping free fatty acids very effectively, the total oil retention time under high temperature reduced pressure is further reduced and the consumption of water vapor is reduced to one-third that required by conventional deodorizers. Is done. The resulting oil has low acidity, light color, good taste and stability, and low trans fatty acid content. Due to the excellent distillation efficiency of the ordered packing, it is possible to tune the deodorizer to either tocopherol removal or tocopherol retention by simply adjusting the stripping steam. In thin-film deodorization of edible seed oil, on the one hand, thin-film stripping using packed towers is superior to tray-type stripping systems, and on the other hand, regular packing is superior to packing with irregular loading. Have already been found by Stemberg et al. (INFO, Vol. 7, No. 12, pp. 1296-1304, December 1996).

  In WO 2006/1185518, in a tower having one or more trays, a fluid is introduced, preferably an aerated gas (which may be water vapor) introduced from the height of the tray bottom. Semi-continuous or continuous processes are described for deodorizing organic or inorganic fluids by contact.

  Sulzer Company is a regular filler on the homepage (www.sulzerchemtech.com) for preparing edible fats and deodorizing oils by removing free fatty acids from vegetable oils at a very low vacuum A factory with a packed tower containing goods is proposed. Sulzer has also proposed various types of ordered packings using different materials useful for this type of column.

  These ordered packings for towers distribute the oil liquid phase uniformly as a thin film over a large surface so that mass exchange is achieved in high contact with the gas phase. This is why the deodorization process using this type of tower in reduced countercurrent steam is much more efficient than the corresponding batch process.

  The contact time of the oil phase and the gas phase in the batch deodorization method is usually several hours, but in the countercurrent steam distillation (CCSD) method, it is in the range of several minutes. On the other hand, as shown in EP 999259, in batch-type deodorization in the presence of herbal extracts such as rosemary and sage extract, the deodorizing and stabilizing active ingredient of this type of extract is While not removed, not only the herbal odor and taste components but also the components responsible for the generation of fish odor and fish taste are removed from the marine oil. The same will happen under CCSD conditions where the efficiency is much higher, i.e. under the CCSD conditions, from the marine oils to which the herbal extract deodorant and optionally antioxidants have been added, It was unexpected that the stabilizing component would not be removed along with the herbal odor and taste components and the fish odor and fish flavor components. Surprisingly, by subjecting this kind of oil or marine oil to CCSD in the presence of herbal extract deodorant, it is very good in quality, i.e. in terms of odor and taste, has a long rancimat induction time, and It has been found that edible oils characterized by a low FAST index are obtained.

  Accordingly, the present invention is a process for preparing a deodorized and stabilized edible marine oil (composition), wherein the marine oil is preferably optionally in the presence of a herbal extract deodorant, optionally with an antioxidant, such as It relates to a process comprising adding ascorbyl palmitate and / or tocopherol and / or citric acid and subjecting to countercurrent steam distillation (CCSD) in a thin film column containing ordered packing. The term “marine oils in the presence of herbal extract deodorants” includes marine oils containing herbal extract deodorants or herbal extracts and marine oils with added herbal extract deodorants or herbal extracts. Is done.

  The invention also provides deodorized and stabilized edible marine oils (compositions) obtained or obtainable by this method, their use as dietary or health supplements, and their food applications In addition to its use for producing preparations such as fortified foods (functional foods), it also relates to diets and health supplements fortified with these marine oils and the food itself.

  As used herein, the term “marine oil” is to be interpreted broadly and includes marine organisms, including algae, plankton, fish, preferably cold water fish and seals, including at least one long chain (LC) PUFA. In addition to oils derived from (including genetically modified / transformed organisms), parts or fractions and components of such marine oils are included. The broadest term "marine oil" includes aldehydes and ketones that can be obtained from any organism and that are associated with the development of a "fishy odor" or other unpleasant odor and taste Possible oils are included. Such organisms include animals, microorganisms (eg, yeast), and plants, as well as some of those described above (eg, seeds).

  The term “polyunsaturated fatty acid (PUFA)” refers to n-3, n-6, and n-9 (or omega-3, omega-6, and omega) having at least two C—C double bonds. -9) related to fatty acids, preferably n-3 fatty acids and their esters with glycerol or alkanols, preferably lower alkanols (such as ethanol). Examples of LCn-6PUFA include linoleic acid (C18: 2), γ-linolenic acid (GLA, C18: 3), dihomo-γ-linolenic acid (DGLA, C20: 3), and arachidonic acid (ARA, C20: 4). Examples of LCn-3PUFA include α-linolenic acid (C18: 3), octadecatetraenoic acid (C18: 4; 6, 9, 12, 15), eicosapentaenoic acid (EPA, C20: 5; 5, 8 , 11, 14, 17), docosapentaenoic acid (DPA, C22: 5; 7, 10, 13, 16, 19), and docosahexaenoic acid (DHA, C22: 6; 4, 7, 10, 13, 16, 19). In particular, EPA and DHA have recently attracted attention from the food industry, and marine oils containing them in glyceryl or alkyl (eg, methyl or ethyl) ester forms, particularly concentrated forms, are preferred and interesting for the present invention. . The glycerol esters of PUFA (which may be natural or reconstituted) include mono-, di-, and triglycerides, with particular interest in the latter. Methyl or ethyl esters are obtained by transesterification of marine oils.

  The marine oil or fraction thereof used as a starting material in the method of the present invention is a crude, degummed, deacidified, neutralized, herbal extract deodorant such as rosemary or sage extract. It may be a marine oil that has been partially oxidized, partially purified, refined, decolorized, and / or deodorized. Preferred starting materials are those that have been subjected to pre-purification such as silica adsorption (with or without carbon) and / or short path distillation. The amount of herbal extract added before CCSD varies depending on its quality. The chemical nature of the components involved in the deodorizing power of herbal extracts and the mechanism by which they act have not been elucidated at present. Very good results can be obtained when the deodorized rosemary or sage extract is used in an amount ranging from 0.1 to 0.4% (w / w). However, it is not limited to this range. The optimum amount may be determined based on the principle according to individual cases. In the case of PUFA ethyl ester, for example, even when Herbarox is 250 ppm, a good rancimat value is still obtained.

  Deodorized and stabilized edible marine oils have low FAST index (trademark) values, ie, less than 2 or 1.5, preferably 1-2, 1-1.5, 1-1.3 More preferably between 1 and 1.1, most preferably the numerical value is 1.0. This index correlates precisely with the fish odor measure exhibited by trained tasting panels. The acronym “FAST” stands for “Fatty Acid Smell and Teste”. This method combines automated solid phase microextraction (SPME) of odor molecules and ammonia negative chemical ionization mass spectrometry detection. This makes it possible to measure the concentration of three specific molecules (4-heptenal, 2,6-nonadienal, and 3,6-nonadienal) that impart fish taste and fish odor. This data is converted to a score that reflects these concentrations using an algorithm. The FAST index (trademark) is calibrated to a human tasting panel so that the ratings 1-7 correspond to the range of taste sensitivity perceived by human subjects. Grade 1 has no fishy taste (ie, “None”), Grade 2 is “Slightly”, Grade 3 is “Slight”, Grade 4 is “Medium”, Grade 5 is “Strong”, Grade 6 is “ A rating of 7 indicates an extremely strong fish taste. Although human taste saturates at or slightly above a rating of 7, the FAST Index ™ can measure taste and odor molecules up to a few hundred ratings. In the American Oil Chemist's Society magazine INFORMATION (Volume 12, pp. 244-249, March 2001), N. McFarlane et al. Quantified fish flavor. The FAST index (TM) technique is described and an algorithm for converting analytical data into scores is disclosed. The following algorithm has been developed: Fish taste index = 1 + (0.312 × A) + (0.11 × B) + (0.03 × C), where A = 2.6-nonadienal (ppb), B = 4-heptenal (ppb), C = 3.6-nonadienal (ppb)).

  In particular, 2,6-nonadienal, 3,6-nonadienal, and 4-heptenal are molecules that are inevitably involved in reducing the undesirable odor and / or stability of marine oils and are measured by the FAST index. Removal (completely or highly) of this compound is a specific embodiment achieved by the present invention. By this method, it is possible to obtain marine oil having a FAST index of 1.0, which symbolizes quality that has not been achieved so far.

  Accordingly, a further embodiment of the invention is to remove or reduce these molecules to a concentration where the FAST index ™ is 1.0, where 1.0 is less than 1.1. 1.01 should be understood to be included.

  In addition to the three molecules mentioned in the FAST test, there are other aldehydes and ketones that have different flavor attributes and can contribute to a different flavor when present in amounts that can be confirmed by analysis. Such molecules include alkanals (pentanal-blue cheese; hexanal-sayanugususa; heptanal-chemical, unpleasant; octanal-chemical, plastic; nonanal-chemical, plastic), alkenals (2-hexenal-bitter 2-heptenal-bitter; 2-octenal-nutty flavor; 2-nonenal-chemical, unpleasant), alkadienals (2,4-heptadienal-acid deodorant; 2,4-nonadienal-acid deodorant), and Ketones (1-penten-3-one-chemical, plastic; 1-octen-3-one-mushroom; 3,5-octadien-2-one-metal). Reducing these to below the perceptual limit is important for the production of oils with no peculiar taste or peculiar odor, and quantitatively determining whether these compounds are present is the deodorizing and stabilizing of the present invention. Will help differentiate the marinated oil from the prior art stabilized / deodorized marine oil. In the edible marine oil, these components are reduced to the detection limit.

  On the other hand, the stability of marine oils is given by the Rancimat induction time (RIT) value. This value represents the time interval in hours until the oil reaches the onset of rancidity. This value is measured at 100 ° C. using a Rancimat RTM apparatus (Metrohm Ltd., CH-9101 Herisau, Switzerland). From this value measured at high temperatures, the stability of the oil at lower temperatures, for example 20 ° C. or 10 ° C., can be extrapolated. The marine oils of the present invention have a rancimat stability at 100 ° C. of greater than 2, preferably greater than 3.8, more preferably greater than 5.2, 6, or 6.2, most preferably 10.15-20. It is in the range of time.

  In further embodiments of the present invention, the marine oils of the present invention are in accordance with well-known techniques, powders, premixes, granules, beadlets, supplement forms, tablets, pills, lotions, solutions, or emulsions. Further processed.

  Compositions and preparations or formulations comprising / based on the marine oils of the present invention may further comprise organic carrier molecules common in food, animal feed, cosmetic or pharmaceutical formulations.

  As mentioned above, the stabilization of marine oils by adding stabilizers / antioxidants is a state-of-the-art method and, when combined with the present invention, is a preferred embodiment of the present invention. Specific examples of stabilizers include ascorbic acid, ascorbyl palmitate, BHT, t-butyl-hydroquinone (TBHQ), rosemary extract, such as Calsec, Inc. (Kalsec, Inc., Kalamazoo, Michigan, Michigan). ), Sage extract, tocopherol, lecithin, and citric acid.

  The present invention also represents a significant advance in industrial processes for preparing stabilized and deodorized marine oils. By using the thin film countercurrent technique, the amount of oil produced per unit time is significantly increased. Depending on the dimensions of the tower used, it is possible to achieve amounts exceeding 10 kg per hour. Preferably, the product yield is greater than 100 kg per hour or even 1000 kg per hour, which corresponds to an industrially meaningful amount for marine oil or marine oil fractions. Preferred package sizes include those where the sample exceeds 4 kg, preferably exceeds 19 kg, more preferably exceeds 170 kg, and most preferably exceeds 900 kg.

  Implementation of the present invention for all kinds of thin film towers, including ordered packings, in particular highly efficient ordered packings, which produce a thin film of marine oil to be deodorized and stabilized, thereby being in high contact with the gas phase (water vapor) Can be used for Many ordered packings using different materials for this type of thin film column are well known. In one particular embodiment, corrugated metal sheet packing provides very good results. Among the many commercially available packed towers useful in the process of the present invention, the following packings are specifically exemplified: Sulzer Melapak, Sulzer Melapak Plus, Sulzer Wire Mesh Type BX, BX Plus, or CY, Sulzer Melagrid, Nutter grid, Künene Rombopak, or Zehua Sepak. These uses are representative of preferred embodiments of the invention.

  Contact with water vapor may be carried out in various ways. However, in one particularly effective method, marine oil or a marine oil fraction is added from the top or top of the tower and water vapor is added from the bottom or bottom, thus operating the tower in a countercurrent manner.

  The present invention may be practiced in a batch or semi-continuous manner, but this method is preferably practiced in a continuous manner. In one particularly preferred embodiment of the invention, the column is operated as a continuous countercurrent steam tower, the process being countercurrent steam distillation (CCSD).

The inventors believe that the number of theoretical plates in the thin film tower affects the quality of the process. In the present invention , a thin film column containing very efficient ordered packing is operated with an NTS (theoretical plate number) of more than 10, preferably more than 50, more preferably between about 60 or 60-100. A column that does not contain any physical trays is particularly preferred, but at present it is believed that one physical shelf will not reduce the advantages of the method of the present invention, and two physical shelves Even steps are allowed.

  It has been recognized that the pressure difference (pressure loss) between the tower top and the tower bottom may affect the composition produced. Therefore, in a preferred embodiment of the present invention, the pressure loss between the tower bottom and the tower top is less than 2 mbar / m, preferably 0.01-1 mbar / m, more preferably 0.8-1.0 m. Bar / m.

It has also been observed that the results of this method vary depending on the ratio of marine oil and water vapor. At the present time, in the present invention, the ratio of marine oil versus water vapor (w / w) is 5 00: 1 to 20: 1, more preferably 200: 1 to 50: 1, most preferably from 160: 1 to 70: 1 in you driving a thin film tower. In fact, very good results are obtained with a ratio of 120: 1.8.

  This method provides an effective use of raw materials. This has been shown to significantly reduce waste. Of course, it is clear that the nature and quality of the raw material affects the mass balance. In a preferred embodiment, for example, when starting from already refined marine oil, the mass balance of the marine oil, i.e. the difference before and after contact with water vapor, is less than 5% by weight.

  The measured dimensions of the tower affect the economics of this method. It is preferred to use a column containing an active ordered packing of 0.5 to 20 m, preferably 1 to 12 m, more preferably 2 to 10 m, most preferably more than 7 m. It is a very important advantage of the present invention that the average contact time between the marine oil and water vapor is relatively short and, as a result, the deodorization by the process and the production time per unit seafood oil stabilized is greatly reduced. is there.

  One reason is that the residence time of marine oil in the thin film tower is relatively short. The residence time of the liquid phase in the tower in a preferred embodiment of the present invention is 0.5 to 60 minutes, more preferably 5 to 30 minutes, 2 to 20 minutes, or 5 to 10 minutes. Particularly preferably, the residence time in the gas phase tower is 0.5 to 10 seconds.

  There are a variety of marine oils that can be stabilized by subjecting them to the process of the present invention. Preferred marine oils are: herringen, sardines, anchovy, pilchard, tuna, hake, catfish, capeio, capeio (Red fish), white fish, mackerel, jack mackerel, sand eel, sand eel, bib (pout), salmon, pollock, cod, halibut (Halibut), trout, trout, capelin, blue whitening, sp Ttoiwashi (Sprat), an oil and mixtures of such oils from fish such as a small shark (dogfish).

  The present invention relates not only to the stabilization and deodorization of intact whole fractions obtained from marine organisms, but also to the stabilization and deodorization of fractions of marine oils. It will be apparent to those skilled in the art that there are various qualities of marine oil available as feedstock for the process, the quality of which depends on the age. It may have already been subjected to one or more impurity removal steps before being processed according to the method of the present invention. Thus, starting materials or raw materials for use in the method of the present invention include unrefined unpurified marine oil, degummed marine oil, deacidified marine oil, decolorized, partially and fully refined Marine oils, neutralized marine oils, decolorized marine oils, stabilized and / or deodorized marine oils, and mixtures thereof are included. In the most preferred embodiment of the method, the raw material is silica adsorbed and already contains a herbal extract deodorant or the herb extract deodorant of this type is added almost immediately before being subjected to the method. Has been.

  In one particular embodiment of the invention, the marine oil is an edible oil and comprises polyunsaturated fatty acids in the form of their natural or reconstituted glycerides, primarily triglycerides. The oil is supplied and processed at a temperature of 80 ° C to 250 ° C, preferably 100 ° C to 230 ° C, more preferably 180 ° C to 220 ° C.

  In another embodiment of the present invention, the marine oil comprises a polyunsaturated fatty acid in the form of an alkyl ester, preferably a methyl or ethyl ester, and is preferably from 60 ° C to 200 ° C, preferably from 80 ° C to 180 ° C. Is supplied and processed at a temperature of 105 ° C to 150 ° C or 120 ° C to 160 ° C.

The temperature of the water vapor is 140 ° C to 160 ° C.

  The method may be carried out under normal pressure, but it is clear that it works best under reduced pressure. Thus, in a preferred embodiment, the thin film column is operated at a pressure of 0.1 to 10 hPa, preferably 0.5 to 10 hPa, more preferably 1 to 5 hPa.

In connection with the implementation of the method of the invention, various further conventional process steps may be performed. One preferred step is defoaming. In a special embodiment of the present invention, the process is preferably carried out before the marine oil is contacted with water vapor, preferably until the O ₂ is less than 1 ppm (depending on the volume of the marine oil), preferably less than 0.5 ppm. Including foaming.

  Another special preferred means is to evaporate the moisture. The improvement consists in evaporating the marine oil, preferably just before contacting with water vapor, until the water content is below 50 ppm (based on the weight of the marine oil), preferably 1-50 ppm.

Steam, it is necessary not to include oxidizing components, such as O _2. It has been found that steam from ordinary tap water is sufficient.

  In certain embodiments of the invention, stabilizers such as antioxidants and / or additional deodorants such as herbal extracts may be added after the deodorization step.

  In view of the fact that the marine oils of the present invention exhibit advantageous sensory properties and high stability, they can advantageously be replaced directly with PUFA-containing marine oils in compositions and preparations or formulations according to the state of the art on the market. , In nutritional supplements, and in dietary or fortified / functional foods. The primary market for the deodorized and stabilized marine oils of the present invention is the food market. However, it is expected that there will be interesting aspects of its use in the feed market. In the context of the present invention, the pet food market is also of interest. Similarly, there are several anticipated uses in the cosmetic and pharmaceutical markets. In a preferred embodiment of the present invention, the composition obtained by the method of the present invention can be used as a health supplement, which may be included in food applications. An interesting limited field of stable marine oils free of impurities is dairy products, infant nutrition products, or baby food products. Specific examples include beverages or cereals. The composition can be advantageously applied to milk, yogurt, and 100% juice juice, products most sensitive to changes in taste and odor due to oxidation and degradation of marine oil components.

  The invention therefore also relates to a method for preparing fortified or functional foods as well as dietary or health supplements containing deodorized and stabilized edible marine oils according to the invention and products of this type rich in n-3 PUFA. .

  The marine oils rich in PUFAs, in particular n-3 or ω-3 PUFAs, in particular EPA and DHA, according to the invention are advantageously used in dietary, health or nutritional supplements or foods enriched with n-3 fatty acids (functional May be used in accordance with well-known methods such as those described in US Patent Application No. 2007/0298079, for example. According to such a method, a fortified food is produced from the intermediate food or its ingredients, which is added to the intermediate food or its ingredients in the desired amount (usually 5 to 5000 mg, preferably at least 16 mg per food serving) of n-. A quantity of marine oil containing 3 fatty acids is added in neat liquid form or in emulsion or gel form or in dry form (eg powder encapsulated in a matrix) and dispersed by high speed mixing, optionally obtained in this way. By obtaining a desired product by subjecting the substantially homogeneous blend to further processing and post-processing. This intermediate food can be fruit juice (FC or NFC), such as citrus juice, non-citrus juice, milk drink, energy supplement drink, sports drink, enhanced / enhanced water drink, soy drink, fermented drink, carbonated drink, etc. It may be a mixture of fresh fruit juices and beverages, yogurt, oatmeal, cereal, cake, snack bar, pudding, cheese, and combinations thereof. Further processing and post-processing is performed according to methods well known in the art, including, for example, pasteurization and cooling or filling containers and packages, respectively.

  In another particular embodiment, the marine oil of the present invention is a liquid preparation for nutritional and refreshing of the kind described in WO0147377 and EP1241955, For example, it may be used in a method for producing 100% orange juice and the contents of this document are incorporated herein as part of the present invention. The qualitative and quantitative composition of the vitality-recovery preparations and the like described herein is a representative example of the food use of the marine oil of the present invention.

  This marine oil is described in addition to this type of oil, for example, in U.S. Patent Application No. 2007/0010480, the contents of which are incorporated herein as part of the present invention. For diet containing at least one dietary fiber (indigestible starch, fructooligosaccharide, oligofructoside, inulin, etc.) in the context of a low fat diet for weight loss or weight management It may be part of the composition and food preparation and may be useful in its manufacture. Dietary compositions and food preparations thereof in which at least one n-3 fatty acid component is the marine oil and food preparations thereof are also representative examples of dietary or health supplements and fortified / functional foods of the present invention.

  Finally, another specific embodiment of the present invention is a nutritional supplement as described in WO 2006/117164, the contents of which are incorporated herein as part of the present invention. And n-3 fatty acids, which are functional foods, are marine oils of the present invention, such as salad dressings, further comprising at least one nut oil and a flavor carrier.

  It is worth mentioning that there are various uses in the industry to add citrus flavors to counter the off-flavors and tastes of marine oils and / or marine oil fractions and / or PUFAs and PUFA (alkyl) esters and (tri) glycerides. . The final product obtainable by the present invention does not require this type of additive, but it is included to combine citrus flavors such as citric acid. In fact, it is preferable not to add citrus flavor since it may interfere with the body's original defense mechanism for detecting damaged food.

  Finally, the marine oils of the present invention may be used in the preparation of galenical formulations according to methods well known in the cosmetic and pharmaceutical industries.

  The invention is further illustrated by the following examples without however being limited thereto.

[Example 1]
Distilled marine oil ethyl ester concentrate was subjected to countercurrent steam distillation in a thin film column (8 m long, 250 mm diameter, stainless steel column with Sulzer BX wire mesh packing) under the following operating conditions:
Temperature: 150C, pressure: 1-2 mbar, oil supply rate: 100 kg / h, steam supply: 1.8 kg / h.

  Various marine oil ethyl ester concentrates treated under these conditions show very good sensory properties and rancimat stability (see Table 1), which includes the addition of stabilizers including antioxidants. Can be further improved.

  As is common in the industry, the stability of the oil obtained was evaluated at 100 ° C. using a Rancimat RTM device (Metrohm Limited, Helisau CH-9101, Switzerland). The measured value represents the time interval (time) until the oil reaches the onset of rancidity.

[Example 2]
The partially refined marine oil was preheated to 150 ° C. in a thin film evaporator under a reduced pressure of 30 mbar. Immediately thereafter, the oil was subjected to countercurrent steam distillation under the following conditions in a thin film column (a stainless steel column with a length of 8 m, a diameter of 250 mm and a sulzer BX packing):
Temperature: 210 ° C., pressure: 1-2 mbar, oil supply rate: 100 kg / h, water vapor supply rate: 1.8 kg / h.

  After the steam treatment, the oil was cooled and the FAST index value was measured (see Table 2). The formula used is as follows: Fish Taste (FAST) index = 1 + (0.31A) + (0.11B) + (0.03C) (A = 2,6-nonadienal, B = 4- Heptenal, C = 3,6-nonadienal (ppb)).

  By using this model, a sensory image of samples prepared according to the method of the present invention and several commercial products can be successfully drawn. Commercial oils (glycerides) that are more stable than (alkyl) ester concentrates have FAST index values in the range of 20-100, and ester concentrate values in the range of 60-2500. This means that all of these products can be fishy even if the oxidation may not exceed a few ppm. This explains why the “aftertaste” phenomenon is common with n-3 supplements and why many problems occur in the processing and consumption of these products.

  Further experiments were performed to improve the oxidative stability of these products by mixing the material from Example 2 with an antioxidant. Some of the results are described below. It will be apparent to those skilled in the art that this choice does not limit the scope of the invention.

  It has long been known that TBHQ is a powerful antioxidant. Unexpectedly, the inventors have found that this is a strong synergist for rosemary oil. The Rupima® edible oil containing 0.2% rosemary extract, 200 ppm ascorbyl palmitate and 1000 ppm mixed tocopherol has a rancimat induction time of 5.4 hours at 100 ° C. When tocopherol is replaced with 200 ppm TBHQ, the induction time increases and exceeds 10 hours at 100 ° C. The oxidative stability results of Loffa® edible oil containing different combinations of herb-derived phenols and TBHQ are shown in Table 3 below. In all cases, the Rancimat induction time (RIT) is over 4 hours.

[Example 3]
(A) Marine oil-based DHA from Smit & Zon, the Netherlands, for Lopfa “30” n-3 edible oil has the following specifications:
Appearance: Yellow oil Color number (Gardner): 11 or less Taste: Acceptable odor: Very slight fish odor Acid value: 0.5 or less (mg KOH / g oil)
Peroxide value: 5.0 or less (mEq / kg oil)
p-anisidine value: 30 or less Unsaponified product: 2.0% or less DPA content: 1.0% or less EPA content: 10.5% or more DHA content: 16.0% or more Total n-3 fatty acids: 30.0% or more Total n-3 long chain PUFA (DPA + EPA + DHA): 25.0% or more Vitamin A: 100 IU / ml or less Vitamin D3: 50 IU / ml or less Cholesterol: 0.5% or less

  (B) The marine oil above has been fully refined (degummed, decolorized and deodorized by standard oil refining procedures). However, if the goal is to produce a stabilized marine oil without the peculiar taste or odor for human consumption, this is called crude refining and is a further step to make it suitable for food applications. Have to go through.

[(C1) Silica adsorption]
500 kg of raw marine oil was supplied to a 1000 L tank in nitrogen. Silica 5% (w / w) was added thereto and stirring was started. The inside of the tank was depressurized to 40 hPa. As soon as 100 hPa was reached, the contents of the vessel were heated to 70 ° C. Stirring, temperature, and pressure were maintained for 5 hours. The vessel contents were then cooled to 40 ° C. and filtered first with a 10 microbag filter followed by a 1 microcandle filter. 2000 ppm of Herbarox was added to half of the filtered oil.

[(C2) Silica and carbon adsorption]
500 kg of raw marine oil was supplied to a 1000 L tank in nitrogen. Silica 5% (w / w) was added thereto and stirring was started. The inside of the tank was depressurized to 40 hPa. As soon as 100 hPa was reached, the contents of the vessel were heated to 70 ° C. Stirring, temperature, and pressure were maintained for 2 hours. Subsequently, the pressure was set to normal pressure and 2% of activated carbon was added. The inside of the tank was again decompressed to 40 hPa. Stirring, a temperature of 70 ° C., and pressure were maintained for an additional 3 hours. The vessel contents were then cooled to 40 ° C. and first filtered through a 10 microbag filter followed by a 1 microcandle filter. Herbarox 2000 ppm was added to half of the filtered oil.

[(D) Countercurrent deodorization]
The PUFA oil was deodorized by continuous countercurrent steam distillation (CCSD). Before supplying the oil to the deodorizing tower, the oil was defoamed with a defoaming device having a temperature of 140 ° C. and a pressure of 40 hPa. After defoaming, the oil was further preheated to a temperature of 210 ° C. with a heat exchanger and then fed to the top of the deodorization tower. The deodorization tower had an inner diameter of 50 mm and was provided with a regular packing (model: Kuehni, Lombopack S6M). The length of the regular packing in the tower was 4 m. Water vapor from a standard water vapor generator was continuously fed below the packing in the column. The water vapor pressure was about 4 bar (4000 hPa) and the temperature was about 144 ° C. The interior of the tower itself was maintained at a very low vacuum using a three-stage vacuum pump device. The pressure at the top of the column was adjusted to 2 hPa. The odorous components were removed from the oil by countercurrent flow of the oil liquid phase and water vapor gas phase. The mass flow of oil was 11 kg / h overall, and the mass flow rate of water vapor was 0.1 kg / h overall. The deodorized oil was cooled to 80 ° C. and finally three different antioxidants were added (tocopherol: 1000 ppm, ascorbyl palmitate: 250 ppm, citric acid: 25 ppm).

[(E) Application of cooking oil to milk (0.2%)]
[Preparation]
-Dissolve sodium ascorbate in part of milk-Add edible oil to milk-Homogenize (twice, 150 and 50 bar)
-Filling a 200ml bottle with milk-Pasteurization (80 ° C, 1 minute in kernel)
-Store in refrigerator for 2 weeks

[Application of edible oil to (F) Natural Yogurt (stirring type)]
[Preparation]
-Heat milk to 30 ° C-Add skim milk powder, stabilizer and sugar mixture-Mix-Heat to 65 ° C-Add edible oil-Homogenize (65 ° C, 200 kg / cm ² , 2 minutes)
-Pasteurization (90 ° C, 15 minutes)
-Cool to 15 ° C-Add natural yogurt and mix-Fermentation at 45 ° C for 3-4 hours (pH 4.3)-Cool and stir vigorously in a short time-Fill the cup with the whole amount and seal-Temperature below 5 ° C Keep in

[sensory evaluation]
A profile test was performed as a sensory method. A sensory test provides the most important information related to whether a consumer accepts the food based on smell and taste. This method is very sensitive and provides information on the stability of the flavor.

  All samples were subjected to a trained tasting panel. Sensory analysis was performed by descriptive analysis using an internal scale from the viewpoint of different attributes. The internal scale consists of 6 intervals, starting from level 1 belonging to “I don't feel” and up to level 7 which is “very strong”. Analysis of variance (ANOVA) was performed to see if there was a significant difference. Multiple comparisons were performed using the least significant difference test (LSD) with a significance level of 5%.

[Example 4]
In a manner similar to that described in Example 3, transesterified marine fish oil from Ocean Nutrition, Canada (ONC), Canada, was deodorized. The specification for EE75 fish oil ethyl ester from ONC is shown below:
Appearance: Yellow oil color number (Lobibond red 5 1/4 inch): 0.5 or less Acid value: 3.0 or less (mgKOH / g oil)
Peroxide value: 5.0 or less (mEq / kg oil)
p-anisidine value: 20 or less EPA content: 42.0% or more DHA content: 22.0% or more Total n-3 fatty acid: 75.0% or more

Claims (20)

A method for preparing deodorized and stabilized edible marine oils, comprising:
Subjecting the marine oil to countercurrent steam distillation (CCSD) in a thin film column containing ordered packing,
The thin film column containing the highly efficient ordered packing is operated with more than 10 NTS (theoretical plate number);
The temperature of the water vapor is 140 ° C to 160 ° C,
The marine oil to water vapor weight ratio is 500: 1 to 20: 1;
Method.   The method of claim 1, comprising adding an antioxidant to the marine product oil. The process according to claim 1 or 2 , which is continuous countercurrent steam distillation. 4. A method according to claim 2 or 3 , wherein the antioxidant comprises ascorbyl palmitate and / or tocopherol and optionally citric acid. The marine oil comprises at least one PUFA (polyunsaturated fatty acids) The method according to any one of claims 1-4. The method according to any one of claims 1 to 5 , wherein the marine product oil is an edible oil containing PUFA or an alkyl ester or ethyl ester concentrate. The method according to claim 1, wherein the distillation is performed under a reduced pressure of 0.1 to 10 hPa, 0.5 to 10 hPa, or 1 to 5 hPa. Deodorized and stabilized edible marine oil obtained by the method according to any one of claims 1 to 7 . Claim 1-7 deodorized and stabilized edible marine oils can be obtained by the method according to any one of.   Deodorized and stabilized edible marine oil, characterized in that the FAST index (trademark) is less than 1.5, 1.3-1, 1.1-1, or 1.0. The marine oil according to any one of claims 8 to 10 , characterized in that the rancimat induction time value exceeds 6.2 hours. The marine oil according to any one of claims 8 to 10 , characterized in that the ransimat induction time is in the range of 10.15 to 20 hours. Health aids, reinforcing foods, functionality of food, animal feed, of in the manufacture of cosmetics or pharmaceutical formulations, the use of edible marine oil which has been deodorized and stabilized according to any one of claims 8 to 12 . Including health supplements the deodorized and stabilized edible marine oil according to any one of claims 8-12. A fortified food or a functional food comprising the deodorized and stabilized edible marine oil according to any one of claims 8 to 12 . A cosmetic comprising the deodorized and stabilized edible marine oil according to any one of claims 8-12 . A pharmaceutical formulation comprising a deodorized and stabilized edible marine oil according to any one of claims 8-12 . Use of a thin-film distillation column packed with ordered packings in the production of a deodorized and stabilized edible marine product oil according to any one of claims 8-12 . Health supplements rich in n-3 PUFAs according to claim 14 and 15, a fortified food or functional food, a process for producing the intermediate food product or components thereof, it or them, a desired amount of n-3 fatty acids A product obtained by adding an amount of the marine oil in a liquid form, an emulsion or a gel form or a dry form, and dispersing it by high-speed mixing into a product. . 20. A method according to claim 19 , characterized in that the blend is subjected to further processing and post-processing to make the product.