CN101677600A - deodorization and stabilization of marine oils - Google Patents
deodorization and stabilization of marine oils Download PDFInfo
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- CN101677600A CN101677600A CN200880015614A CN200880015614A CN101677600A CN 101677600 A CN101677600 A CN 101677600A CN 200880015614 A CN200880015614 A CN 200880015614A CN 200880015614 A CN200880015614 A CN 200880015614A CN 101677600 A CN101677600 A CN 101677600A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
- C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
- C11B5/0035—Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/21—Removal of unwanted matter, e.g. deodorisation or detoxification by heating without chemical treatment, e.g. steam treatment, cooking
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/02—Antithrombotic agents; Anticoagulants; Platelet aggregation inhibitors
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
- A61P9/10—Drugs for disorders of the cardiovascular system for treating ischaemic or atherosclerotic diseases, e.g. antianginal drugs, coronary vasodilators, drugs for myocardial infarction, retinopathy, cerebrovascula insufficiency, renal arteriosclerosis
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
- C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
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Abstract
The invention relates to a process for the preparation of deodorized and stabilized food-grade marine oils by submitting marine oils to a counter-current steam distillation (CCSD) in a thin film column containing a structured packing and, if desired, adding antioxidant(s), to the food-grade marine oils thus obtained and to their uses in the food/feed, cosmetic and/or pharmaceutical industry.
Description
The present invention relates to a kind of marine oils deodorizing and stable method and marine oils that obtains thus of making.
Marine oils has very attracting benefit, because polyunsaturated fat oil (PUFA) (specifically being eicosapentaenoic acid (EPA) and DHA (DHA)) source has great meals meaning, it comprises the PUFA ester with its naturally occurring monoglyceride form and ethyl ester form.Yet according to the rejecting of its source, its degree of purification and naturally occurring accessory substance and denatured products, marine oils has different significantly at taste with quality aspect stable.Because PUFA comprises some carbon-carbon double bonds, so thereby they are easy to oxidation generation fishlike smell under environmental condition.
At present, exist a large amount of favourable evidences to prove: to increase the level of these compounds in meals health is had beneficial effect, thereby and can intervene blood pressure, atherosclerotic and thrombosis and reduce the death that causes by coronary heart disease.
A kind of stable method that avoids taking place oxidation and unfavorable development of fish oil that makes of exploitation is urged in the concern that these compounds increase day by day.
In recent years, stablizing and have some improvement aspect fish oil and the PUFA by adding stable material.
People such as Hamilton are at J.Am.Oil Chem.Soc. (JAOCS), 75 (7), a kind of extraordinary ternary additive agent mixture (2% Delta-Tocopherol, 0.1% ascorbyl palmitate, 0.5% lecithin) that is used to prevent the fish oil oxidation is disclosed among the 813-822 (1998).Although the fish oil of refining does not have remarkable peroxidating in 20 ℃ of following time periods of 6 months after adding said mixture, this mixture can not successfully suppress peculiar smell (off-taste and off-smell).Peculiar smell appears in 3 week.
EP 340 635 A have described a kind of like this method: at temperate condition (between 30 ℃ and 150 ℃, preferred 60-100 ℃, 2-5 hour) under by vacuum steam distillation the oil (especially fish oil) that contains EPA and DHA is handled, thereby the minimizing boiling point is low and the volatile flavor compound of low polarity, described oil is contacted with adsorbent (for example silica gel), thereby reduce the volatile flavor compound of boiling point height and high polarity.In the specific embodiment, the oil of purifying and Rosmarinus officinalis extract antioxidant combination thus.Yet the oil that this fish off-flavors is reduced to a great extent has following feature: the taste of rosemary extract and smell make it be unsuitable for numerous food product and use, and especially are unsuitable for dairy products.
According to european patent application 612346 (=WO93/10207) described in process, make the refining marine oils that adopts treatment of silica carry out soft vacuum steam distillation (140-210 ℃) and adopt the mixture of lecithin, ascorbyl palmitate (AP) and alpha-tocopherol to stablize to make Rancimat improved stability (according to embodiment 1-8: at 100 ℃ of following 4.9-14 hours) and make the application performance that is mainly used in the healthy food replenishers good.Yet, in to the responsive especially dairy applications (such as yogurt and milk beverage) of smell, observe and it is to occur in some cases unacceptable, undesirable aroma and flavor.
EP 999 259 (=US 2003/161918A1) has described preparation by the following method and the stable food-grade marine oils that contains PUFA, described method comprises: use the treatment of silica marine oils, carry out 2 hours batch (-type) vacuum steam deodorizings under the temperature that makes it 150 ℃ and 190 ℃ in the presence of rosemary, or the Salvia japonica extract (adding ascorbyl palmitate and mixed tocopherol if desired).This process obtains stable food-grade marine oils, and it has the Rancimat induction period of useful aroma and flavor feature and 4.1 to 6.2 hours.These oily quality are best up to now, and they are suitable for various food applications, comprise dairy products, for example milk and yogurt.
Consider containing the ever-increasing demand of high-quality food-grade oil of PUFA, need a kind of in more effective production method aspect output and short time.The invention provides such method and corresponding product.
According to Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th plate, A 10 volumes, 204-206 page or leaf (1967), substitute intermittently deodoriser with semicontinuous and continuous deodoration system, this is because more effective stripping and heat recovery can be saved steam.The example of mentioned semicontinuous and continuous deodorizer is made up of the iron-clad that stainless steel tower tray (tray) and supply thereof are installed.The Campro deodoriser has tower tray (tray-in-shell) design in the continuous shell, and it is combined with unique film stripping notion with plug flow.
At Bailee ' s Industrial Oil and Fat Products, people such as Y.H.Hui edit, JohnWiley ﹠amp; Sons, New York has summarized commercial deodorization system from beginning to the development history of the nineties in last century in 1996 (339-390 page or leaf) the 4th volume the 6th chapter (deodorizing).
United States Patent (USP) 4,996,072 disclose a kind of by the deodorizing and/or reduce fat and the method for the cholesterol levels of oily (being specially fish oil or marine oils) under vacuum of the rapid technology of multistep, described method comprises: the temperature that above-mentioned oil is heated to about 400-500 (204-288 ℃), the described heated oil of flash distillation forms pretreated fluid phase, adopts 1-15% (by weight) adverse current steam under 1-7mmHg this oil to be carried out the film stripping then.Thereby the oil that obtains having following feature: the content of n-3 unrighted acid is at least 95% in the low and raw material of taste gentleness, the cholesterol level of clean fish oil.
Similarly, approaching related U.S. patent 5,436,018 discloses by being used for reducing the method for oil (concrete fish oil or marine oils) cholesterol levels, obtain cholesterol lower, by deodorizing and oil with good taste, described method comprises: introduce above-mentioned oil on the top of adverse current film steam stripping device under the pressure of 1mmHg under the temperature of at least 400 (204 ℃) and at least, introduce steam simultaneously in its underpart.Consider oil retention time lack (5 minutes or shorter), think this method compare with traditional deodorization technology favourable because the degraded minimum of useful n-3 unrighted acid.
United States Patent (USP) 4,810,330 have described a kind of liquid by making falling liquid film contacts the specific embodiment that the high boiling liquid that relatively small amount is added carries out continuous deodorization process with continuous stripped vapor in countercurrent tower, described high boiling liquid is such as being aliphatic acid, edible oil, fat, glyceride and other high boiling ester, specifically be palm oil and other vegetable oil, it also comprises the liquid condensate (compound of free fatty, water, pigment, scent of and/or taste) of about 5wt% except fat oil glyceride.
Similar approach and device are from for example US 4,394,221, US 4,599,143 and GB 2 176 713 A (=DE 35 22 897 A1) in know, these method and apparatus are by carrying out the adverse current steam stripping in falling-film tower, concise to remove its deodorizing of volatile impurity/make/it is carried out physics from higher boiling edible oil, fat and ester (being specially vegetable oil and hydrogenated fish oil).
JP 2,007 014263 A have described a kind of film tower and tower tray type device by will containing stacked packing material and have made up purifying plant-derived and the edible fat of animal and the method for oil, this edible fat and oil comprise content of trans fatty acids be no more than the fish oil of 1 quality % (be not purified, by depickling, that decoloured, by deodorizing, be hydrogenated).Temperature in this tower is 225 to 252 ℃, and pressure is no more than 18hPa, and oily heap(ed) capacity is 12 to 28m
3/ m
2, the height of transfer unit of regular packing is 1-7m.Temperature in the tray apparatus is 210 to 247 ℃, and pressure is no more than 18hPa.The purification process time is 15 to 120 minutes.
People such as Xu (JAOCS, 78 (7), 715-718[2001 July]) studied traditional intermittence of adopting stripped vapor in the deodoriser lipid by the distillation purifying ad hoc structure during, cause and influence that acyl group shifts.The result shows the quality that should use the Structured lipid that more effective isolation technics is purified with improvement, and draw: in order to reduce vapo(u)rizing temperature as drawing a conclusion, vacuum should be low as much as possible, and in order to shorten distillation time, should use the film principle in packed column.
Ahrens is at Fett/Lipid 101. (7), 230-234 (1999), and WILEY-VCH VerlagGmbH has summarized the history of seed oil being carried out the film deodorizing among the Weinheim.The film deodoriser develops into 20 reagent the mid-80s since the seventies in 20th century and is used in the commercial Application.Latest type be SoftColumn
TM, a kind of deodoriser that is used for moderate, low-cost processing seed oil (being specially sunflower oil, soybean oil and rapeseed oil) that is developed especially, it comprises structurized filler.To free fatty carry out very effective stripping can cause oil in vacuum, improve total retention time under the temperature and shorten and steam consumption can be reduced to 1/3rd of traditional deodoriser aequum.Low acid, low colour that gained oil has, good taste and stability and lower trans-fatty acid level.By the outstanding distillation efficiency of structuring filling, can also be simply adjust deodoriser by regulating stripped vapor, thereby be used to remove tocopherol or keep tocopherol the two.People such as Stenberg (INFORM, 7 (12), 1296-1304 Dec.1996) has been found that: on the one hand packed column is used for the tower tray stripping system and carries out the film stripping and have advantage; Filler with the alternative random placement of structurized filler has advantage in the film deodorizing of edible seed oil on the other hand.
WO2006/1185518 has described a kind of by the following semicontinuous or continuation method that makes the deodorizing of organic or inorganic fluid in having the tower of one or more tower trays: described fluid is contacted with gas jet, described gas jet can be a water vapour, preferably introduces in the bottom of tower tray.
Sulzer company provides a kind of equipment that comprises the packed column that contains structure shape filler on its website (www.sulzerchemtech.com), it prepares edible fat and be used for oily deodorizing by remove free fatty from vegetable oil under low-down vacuum.Sulzer also provides the various dissimilar structuring fillings that formed by different materials that can be used in the above-mentioned tower.
These structurized tower packings evenly distribute the liquid oil phase on the big surface of film, thereby realize contacting and the material exchange with the extensive of gas phase.Here it is adopts the deodorization process of above-mentioned tower under the vacuum and steam counter-current condition than the more effective reason of corresponding batch technology.
In the intermittence deodorization process, be generally some hrs the time of contact of oil phase and gas phase, and in adverse current steam distillation (CCSD) technology in its scope at some minutes.Yet, shown in EP 999259, at intermittence that has herb extracts (for example rosemary, or Sage extract) in the deodorisation process, the active deodorizing and the stable component of said extracted thing can not be removed, and herbal medicine flavor component and cause that the component of fishlike smell is removed from marine oils.What do not reckon with is, following situation takes place under the condition of highly effective CCSD, promptly from herb extracts deodorant and optional antioxidant had added wherein marine oils, deodorizing and stable component can not removed with herbal medicine flavor component and fishlike smell component under the CCSD condition yet.Find surprisingly, make above-mentioned oil or marine oils in the presence of herb extracts deodorant, carry out CCSD, thereby form high-quality food-grade oil, promptly have the oil of following feature: the aroma and flavor quality is very good, Rancimat induction period long and the FAST index is less.
Therefore, the present invention relates to a kind ofly be used to prepare by the method for deodorizing and the food-grade marine oils (composition) that is stabilized, described method comprises: make marine oils preferably carry out adverse current steam distillation (CCSD) under the existence of herb extracts deodorant (adding antioxidant if desired, for example ascorbyl palmitate and/or tocopherol and/or citric acid) in containing the film tower of structuring filling.Term " marine oils is in the presence of herb extracts deodorant " comprises marine oils that contains herb extracts deodorant or herb extracts and the marine oils that has added herb extracts deodorant and herb extracts.
The invention still further relates to a kind of that obtain by this method or can obtain by this method by deodorizing and the food-grade marine oils (composition) that is stabilized, relate to them as meals or healthy replenishers be used for making such as the purposes of food, condensed food (functional food) preparation and relate to meals and healthy replenishers and by the food of these marine oils reinforcement itself.
Term used herein " marine oils " should broadly be explained, it comprises the component that is obtained oil and contained the above-mentioned marine oils of at least a long-chain (LC) PUFA by marine organism, described marine organism comprises marine alga, planktonic organism, fish, preferred cold water fish and sea dog, comprise genetic modification/genetically modified organism, and part of organism or fragment.On the broad sense, term " marine oils " comprises the oil that can obtain from any organism, thereby this oil can be degraded and produced aldehydes and the ketone that causes " fishlike smell " or other unhappy taste.Above-mentioned organism comprises animal, microorganism (for example yeast) and plant and part (for example seed) thereof.
Term " polyunsaturated fatty acid (PUFA) " refer to have n-3, the n-6 of the two keys of at least two C-C and n-9 (or Ω-3, Ω-6 and Ω-9) aliphatic acid and with the ester of glycerine or alkanol (preferred low-grade alkane alcohol is such as ethanol), preferred n-3 aliphatic acid.The example of LC n-6PUFA be linoleic acid (C18:2), gamma-Linolenic acid (GLA, C18:3), two height (dihomo)-gamma-Linolenic acid (DGLA, C20:3) and arachidonic acid (ARA, C20:4).The example of LC n-3PUFA is alpha-linolenic acid (C18:3), parinaric acid (C18:4; 6,9,12,15), eicosapentaenoic acid (EPA, C20:5; 5,8,11,14,17), clupanodonic acid (DPA, C22:5; 7,10,13,16,19) and DHA (DHA, C22:6; 4,7,10,13,16,19).In recent years, especially EPA and DHA have caused showing great attention to of food industry, and especially pay close attention to glyceride and Arrcostab (for example methyl esters or ethyl ester) the above-mentioned EPA of form and the marine oils of DHA, particularly its conc forms of containing related to the present invention.PUFA glyceride (it can be natural or reconstruct) comprises monoglyceride, diester and three esters, the special concern latter.Methyl esters and ethyl ester are obtained by ester exchange by marine oils.
In the method for the invention as the marine oils of raw material or its fraction can be to wherein add herb extracts (such as rosemary, or Sage extract) deodorant not concise, do not come unstuck, unacidified, be neutralized, by partial oxidation, concise, concise by part, bleached and/or by the marine oils of deodorizing.Preferred raw material has carried out concise in advance, such as adsorbing on carbon containing or carbon-free silica gel and/or carrying out short-path distillation.Amount with the herb extracts that adds before the CCSD depends on its quality.It is not immediately clear and make herb extracts have the chemical property and the mechanism of action thereof of the component of odor removal efficient.In the scope of 0.1-0.4% (w/w), can be obtained excellent result by the amount of the rosemary, of deodorizing or Sage extract.Yet this scope does not have restricted.Optimum amount can be determined according to each case.Have at the PUFA ethyl ester under the situation of 250pppm Herbalox for example, still obtain good rancimat numerical value.
Had following feature by deodorizing and the food-grade marine oils that is stabilized: the FAST index
TMLittle, promptly less than 2 or 1.5, preferably between between 1 and 2, between 1 and 1.5, between 1 and 1.3; More preferably, most preferably be numerical value 1.0 based between 1 and 1.1.This index is definitely relevant with the trial test panel of undergoing training that is the fishlike smell classification.Abbreviation " FAST " expression " aliphatic acid aroma and flavor ".This method makes up the scent molecule solid phase extractions and the ammonia anion chemistry source-mass spectrography of automation.This makes it possible to measure the concentration of three kinds of concrete molecules (4-heptenal, 2,6-nonadienal and 3,6-nonadienal) of giving fishlike smell.Algorithm becomes this data transaction the scoring of reaction density.The FAST index
TMTaste panel's standardization by the mankind, make the score of 1-7 reflect the scope of human subjects the taste sensitivity.Score 1 expression does not have fishlike smell (promptly not having) fully; Score 2 expressions " very slight "; Score 3 expressions " slightly "; Score 4 expressions " medium "; Score 5 expressions " weight "; Score 6 expressions " very heavy "; And the extremely heavy fishlike smell of score 7 expressions.Although the human sense of taste for 7 or higher again score saturated, the FAST index
TMCan measure taste and the scent molecule of score up to hundreds of.In the magazine INFORM (12,244-249, March calendar year 2001) of American Oil Chemists ' Society, people such as N.Macfarlane propose a kind of test that fishiness is quantized, and have wherein described the FAST index
TMTechnology and disclose and to analyze the algorithm that data conversion becomes score.Fishiness index=1+ (0.312 * A)+(0.11 * B)+(0.03 * C), wherein, A=2,6-nonadienal (ppb); B=4-heptenal (ppb); C=3,6-nonadienal (ppb).
Because 2,6-nonadienal, 3,6-nonadienal and 4-heptenal are the main molecules that causes that undesirable taste and/or marine oils hang down stability and measure in the FAST index, so the removal of these compounds (removing fully or the very removal of high level) is the specific embodiment that realizes by the present invention.Can obtain the FAST index by this method is 1.0 marine oils, the quality that this expression never reached in the past.
Therefore, another embodiment of the present invention is that the FAST index is removed or be reduced to above-mentioned molecule
TMBe 1.0 concentration,, wherein 1.0 should be understood to less than 1.1 but comprise 1.01.
Except three kinds of molecules in FAST test, describing, exist other to have different taste profile and can cause the peculiar smell aldehyde and the ketone of (if existence) to analyze confirmable amount.These molecules comprise alkanal (valeral-blue cheese flavor; Hexanal-quilt flavor of mowing; Heptane-chemicals, unhappy; Octanal-chemicals, the plastics flavor; Aldehyde C-9-chemicals, the plastics flavor); Olefine aldehydr (2-hexenoic aldehyde-bitter taste; 2-heptenal-bitter taste; 2-octenal-nut astringent taste; 2-nonenyl aldehyde-chemicals, unhappy); Two olefine aldehydrs (2,4-heptadienal-putrefactive odor; 2,4-nonadienal-putrefactive odor) and ketone (1-penten-3-one-chemicals, plastics flavor; 1-octene-3-ketone-mushroom taste; 3,5-octadiene-2-ketone-metallic taste).It is following very important for producing soft oil that they are reduced to the sensation limit, quantitatively determine these compounds whether exist help to distinguish of the present invention by deodorizing and be stabilized marine oils and prior art be stabilized/by the marine oils of deodorizing.In this food-grade marine oils, these components are reduced to detectable limit.
On the other hand, the numerical value of the Rancimat induction period (RIT) by marine oils is determined its stability.Rancid time interval appears in this numeric representation oil, in hour.This numerical value utilizes Rancimat RTM device, and (Metrohm Ltd., CH-9101 Herisau Switzerland) measure down at 100 ℃.By the numerical value of at high temperature the measuring stability of this oil under lower temperature (for example 20 ℃ or 10 ℃) of to extrapolate.Marine oils of the present invention has following feature: the Rancimat stability under 100 ℃ is preferably greater than 3.8 greater than 2, more preferably greater than 5.2,6 or 6.2, most preferably in 10.15-20 hour scope.
In another embodiment of the present invention, marine oils of the present invention is further processed into powder, pre-composition, particle, bead (beadlet), replenishers form, tablet, pill, emulsion, solution or emulsion according to known technology.
Comprise/can further comprise the organic supporting agent that is commonly used in food, animal feed, cosmetics or the pharmaceutical preparation based on the composition of marine oils of the present invention and preparation or preparation.
As mentioned above, it is the method that this area existing level adopts that/antioxidant stable by adding makes marine oils stable, and itself and the present composition are preferred implementations of the present invention.The instantiation of stabilizing agent comprises ascorbic acid, ascorbyl palmitate, BHT, the tert-butyl group-hydroquinones (TBHQ), Rosmarinus officinalis extract (for example from Kalsec Inc Herbalox " O "), Kalamazoo, Michigan, Sage extract, tocopherol, lecithin and citric acid.
The present invention be preparation is stabilized and by the breakthrough of the commercial run of the marine oils of deodorizing.By using the film reverse flow technique, improved the oil mass of unit interval production to a large extent.According to used Sopwith staff cun, per hour can realize output greater than 10kg.Preferably, the output of product is greater than 100kg/ hour, even is 1000kg/ hour, and this is illustrated in industrial significant marine oils amount or marine oils fraction.Preferred Package size comprises, greater than 4kg, is preferably greater than 19kg, more preferably greater than 170kg, most preferably greater than the sample of 900kg.
In practice of the present invention, can use the film tower that contains structuring filling (being specially the efficient configuration filler) of all kinds, form the film for the treatment of deodorizing and treating stable marine oils by this tower, thereby it is fully contacted with gas phase (steam).There are many structuring fillings that form by the different materials that becomes known for above-mentioned film tower.In a specific embodiment, corrugated sheet metal filler obtains excellent result.In a plurality of available commercial packed columns in the methods of the invention, specifically mention following filler as an example: Sulzer Mellapak, Sulzer Mellapak Plus, Sulzer gauze model BX, BX Plus or CY, Sulzer Mellagrid, Nutter grid,
Rombopak or Zehua Sepak, the purposes of above-mentioned filler is represented preferred implementation of the present invention.
Can contact with steam in every way.Yet, in a concrete effective and efficient manner, marine oils or part marine oils are added the top or the top of tower, in the bottom or the bottom add steam, thereby move with counter-flow pattern.
Although the present invention can carry out in the mode of batch technology or half-continuous process, preferably carry out this method in a continuous manner.In an especially preferred embodiment, tower is with the formal operations of continuous flow upstream turret, and technology is adverse current steam distillation (CCSD).
The inventor infers that the theoretical stage in the film tower has influence to the quality of this technology.One preferred embodiment in, contain highly the effective film tower of structuring filling adopt greater than 10, be preferably greater than 50, more preferably from about 60 or the NTS (theoretical stage) between 60 and 100 operate.Particularly preferably be, this tower does not have physics dividing plate (physical plate) at all, but currently thinks that 1 physics dividing plate can not reduce the advantage of the inventive method, even 2 dividing plates also are acceptable.
Observe, at the bottom of cat head and the tower between bottom pressure poor (pressure drop) have influence for composition at the bottom of institute's production in some embodiments.Therefore, in preferred implementation of the present invention, the pressure drop at the bottom of the tower and between the cat head less than 2mbar/m, preferably between 0.01 and 1mbar/m between, more preferably between 0.8 and 1.0mbar/m between.
Also observe, the ratio between marine oils and the steam makes the difference as a result of this method.Preferably current, with following marine oils steam is operated the film tower than (w/w) in some embodiments, described marine oils than between 1000: 1 and 10: 1, is preferably 500: 1 to 20: 1 to steam, more preferably 200: 1 to 50: 1, most preferably be 160: 1 to 70: 1.In fact, under 120: 1.8 ratio, obtain extraordinary result.
This method can effectively be utilized raw material.Observe, it can reduce waste material on sizable degree.Certainly, obviously raw material properties and quality have influence for mass balance.In preferred embodiment, for example when when being set out by concise marine oils, the mass balance of marine oils (difference before and after promptly contacting with steam) is less than 5 weight %.
The metric size of tower has influence for the economy of this technology.The preferred tower that uses comprise 0.5 to 20 meter, preferred 1 to 12 meter, more preferably 2-10 rice, most preferably greater than 7 meters active structure filler.Essential advantage of the present invention is that marine oils is relative short with the average contact time of steam, thereby has been shortened to a great extent by the production of units time of deodorizing and marine oils that be stabilized according to this method.
A reason is: the retention time of marine oils in the film tower is short relatively.In preferred implementation of the present invention, the retention time of liquid phase in tower is between 0.5 and 60 minute, more preferably between 5 and 30 minutes, between 2 and 20 minutes or between 5 and 10 minutes.Especially preferred is that the retention time of gas phase in tower is between 0.5 and 10 second.
Various marine oils can be stabilized by making it carry out method of the present invention.Preferred marine oils is oil and these the oily mixtures that obtained by following fish, and described fish comprises catfish, black carp, sardine, long tail anchovy, Pacific sardine (pilchard), tuna, catfish, squama fish, snapper, whitefish, mackerel, Chilean mackerel (jack mackerel), husky eel, bullhead, salmon, cod, cod, halibut, salmon, sweetfish, blue whitefish, westerly wind, dog shark or the like.
The present invention not only relates to the stable and deodorization process of the full oil that is directly obtained by marine organism, also relates to the stable and deodorization process of marine oils fraction.For a person skilled in the art, the marine oils that obviously has various qualities can be used for this technology as raw material, and its quality depends on the age of organism.Some have carried out one or more purification steps before the method according to this invention is handled.Therefore, be used for that rising of the inventive method expected or raw material comprise be not purified, not by concise marine oils, the marine oils that is come unstuck, by the depickling marine oils, decoloured and quilt part and complete concise marine oils, the marine oils that is neutralized, by the marine oils bleached, be stabilized and/or by marine oils of deodorizing and composition thereof.In most preferred embodiment of the present invention, raw material has carried out absorption and has comprised herb extracts deodorant on silica, perhaps almost makes raw material add above-mentioned herb extracts deodorant before carrying out the present invention.
In a specific embodiment of the present invention, marine oils is a food oil, and it comprises the polyunsaturated fatty acid of glyceride form, mainly is naturally occurring or the triglyceride of reconstruct.This oil is between under the temperature between 80 ℃ and 250 ℃, preferably between under the temperature between 100 ℃ and 230 ℃, more preferably be fed under the temperature of 180 ℃ and 220 ℃ and processed.
In another embodiment of the present invention, marine oils comprises the polyunsaturated fatty acid of Arrcostab (preferred methyl esters or ethyl ester) form, and it is between under the temperature between 60 ℃ and 200 ℃, preferably between under the temperature between 80 ℃ and 180 ℃, more preferably be fed between 105 ℃ and 150 ℃ or under the temperature of 120 ℃ and 160 ℃ and processed.
The temperature of described steam is between 100 ℃ and 290 ℃, preferably between 140 ℃ and 160 ℃.
Although method of the present invention can be operated under normal pressure, obvious is that this method is under reduced pressure operated the best.Therefore, in preferred embodiment, the film tower between 0.1 and 10hPa between pressure under, preferably between 0.5 and 10hPa between pressure under, more preferably between 1 and the pressure of 5hPa under move.
Various extra common process steps can be carried out in conjunction with the execution of the inventive method.A preferred step is the degassing.In specific implementations of the present invention, this method comprises makes the marine oils degassing, preferably makes its degassing before making marine oils and steam contacts, to O
2Less than 1ppm (with the stereometer of marine oils), preferably less than 0.5ppm,
Another kind of particularly advantageous measure is an evaporation water.Improvement is, the evaporation marine oils preferably not long ago evaporates marine oils in that marine oils is contacted with steam, to water less than 50ppm (based on the weight of marine oils), preferably between 1 and 50ppm between.
Described steam should oxygen-free component, for example O
2Find that the steam that derives from normal running water is just enough.
In specific implementations of the present invention, stabilizing agent (for example antioxidant) and/or extra deodorant (for example herb extracts) can add behind deodorization process.
Consider organoleptic quality and high stability that marine oils of the present invention is favourable, it can advantageously substitute and contain PUFA marine oils itself and contain the PUFA marine oils in this area in existing and commercial composite and preparation or preparation, nutritious supplementary pharmaceutical and meals or the reinforcement/functional food.The present invention is a food products market by the staple market of deodorizing and the marine oils that is stabilized.But also may there be interesting application facet in feed market.In the context of the present invention, also interested in pet food market.Be expected at cosmetics and medical market and also have some application.In preferred implementation of the present invention, the composition that the method according to this invention obtains can be used as healthy replenishers, can be included in the food applications.To the interested especially field of pure and stable marine oils is dairy products, infant nutrition product or baby food.Instantiation comprises beverage or cereal.Described composition can be advantageously utilised in milk, yogurt and the fruit juice, and these products change the most responsive to taste and the smell that oxidation and degraded owing to the marine oils component take place.
Therefore, the invention still further relates to comprise of the present invention by the meals of deodorizing and the food-grade marine oils that is stabilized and healthy replenishers and reinforcement or functional food, and relate to a kind of method that is used to prepare the product of the above-mentioned n-3PUFA of being rich in.
Marine oils of the present invention is rich in PUFA, especially be rich in n-3 or ω-3PUFA, specifically be rich in EPA and DHA, it can be advantageously used in according to known method (for example described in the US2007/0298079) preparation meals, health or nutritious supplementary pharmaceutical or the food (functional food) strengthened by n-3 aliphatic acid.According to said method, condensed food is made by intermediate food or its component by following: add being embedded in a certain amount of marine oils in the matrix, liquid form, former state, emulsion or gel form or dried forms (for example powder) in described intermediate food or its component, the n-3 aliphatic acid (be generally every part of food 5-5000mg, preferably 16mg) at least that wherein contains aequum; Make its dispersion by violent mixing; What will obtain thus if desired is processed into required product after the further processing also of blend uniformly basically.Intermediate food can be juice (FC or NFC), for example mixture, yogurt, oat, cereal, cake, fast food, patch, cheese and the combination thereof of citrus juice, non-citrus juice, milk beverage, energy drink, sports drinks, reinforcement/enhancing water drink, soymilk, fermented beverage, carbonic acid drink, above-mentioned fruit juice and drink.Further processing and back processing adopt means known in the art to realize, it comprises for example pasteurize and cooling respectively; The container of perhaps packing into is packing also.
In another specific implementations, marine oils of the present invention can be used in the manufacture method of the nutrition of the liquid of type described in WO 0147377 and the EP1 241 955, the preparation of refreshing oneself (for example orange juice), and the content of above-mentioned patent documentation is inserted in this specification by reference.Wherein said refresh oneself preparation and component in nature and quantitatively similarly preparation be the example of marine oils of the present invention in food applications.
Marine oils of the present invention can also be the part of dietary composition and food formulation and can be used in its manufacturing, described dietary composition and food formulation also comprise at least a dietary fiber except above-mentioned oil, such as for example described in the United States Patent (USP) 2007/0010480 for resistant starch (resistant starch), FOS, FOS glycosides and inulin in the fat reducing meals of purpose that reduce body weight or control body weight, the content of above-mentioned patent documentation is inserted in this specification by reference.Dietary composition and food formulation thereof with at least a n-3 fatty acid component (for marine oils of the present invention) also are the examples of meals of the present invention or healthy replenishers and reinforcement/functional food.
At last, the example of another specific implementations of the present invention is nutritious supplementary pharmaceutical described in the WO2006/117164 and functional food, the content of above-mentioned patent documentation is inserted in this specification by reference, wherein, described n-3 fatty acid source is a marine oils of the present invention, and it also comprises at least a macadamia nut oil and flavor enhancement, such as mayonnaise.
It should be noted that to have application known in the various industry, wherein, add the Citrus local flavor to hide marine oils and/or the fraction of marine oils and/or the peculiar smell of PUFA and PUFA (alkyl) ester and glycerine (three) acid esters.Although the final products that can obtain according to the present invention do not need above-mentioned additive, the combination that comprises Citrus local flavor (comprising citric acid) also is included among the present invention.In fact, preferably do not add the Citrus local flavor, because they can hinder the people to find the natural defensive enginery of rotten food.
At last, marine oils of the present invention can be used to prepare galenica in cosmetics and the medical industry according to known method.
Further set forth the present invention by following examples, but the present invention is not limited thereto.
Embodiment 1
The ethyl ester concentrate that makes the marine oils that is distilled at the film tower (highly: 8m; Diameter: 250mm; Stainless head tower with Sulzer BX gauze packing) under following operating condition, carry out the adverse current steam distillation in:
Temperature: 150 ℃; Pressure: 1-2mbar; Oil feed rate: 100kg/h; Steam feed speed: 1.8kg/h.
The various ethyl ester concentrates of the marine oils of Chu Liing have excellent sensory qualities and Rancimat stability (referring to table 1) under these conditions, and it can further improve by the stabilizing agent that interpolation contains antioxidant.
As common in the industry, in Rancimat RTM device (Metrohm Ltd.CH-9101Herisau, the stability of the oil that obtains thus 100 ℃ of following assessments in Switzerland).The rancid time interval should oil appears in measured numeric representation, in hour.
Some kinds of table 1 expressions are purchased n-3PUFA ester product and the oxidation stability of the product that obtains according to embodiment 1
| Sample | Rancimat stability under 100 ℃ (hour) | The airborne stability (hour/day) under 20 ℃ of prediction | The airborne stability under 20 ℃ of prediction (my god) |
| ??Croda?3322EE | ??0.4 | ??102.4/4.3 | ??8.6 |
| ??Triomega | ??0.8 | ??204.8/8.6 | ??17.2 |
| ??Esapent | ??0.5 | ??128/5.3 | ??10.6 |
| ??Croda?4020EE | ??1.1 | ??281.6/11.7 | ??23.4 |
| ONC 4020EE-is without stable | ??0.4 | ??102.4/4.3 | ??8.6 |
| ??EPAX?6000EE??(4020) | ??0.9 | ??230.4/9.6 | ??19.2 |
| ONC4020EE-is through stable | ??1.1 | ??281.6/11.7 | ??23.4 |
| ??Ropufa?75EE | ??1.8 | ??460.8/19.2 | ??38.4 |
| Embodiment 1 | ??4.0 | ??1022/42.7 | ??85.3 |
Embodiment 2
Will preheating in thin film evaporator under of the decompression of the concise marine oils of part at 150 ℃ and 30mbar.After this make this oil immediately (highly: 8m at the film tower; Diameter: 250mm; Stainless head tower with Sulzer BX filler) under following operating condition, carry out the adverse current steam distillation in:
Temperature: 210 ℃; Pressure: 1-2mbar; Oil feed rate: 100kg/h; Steam feed speed: 1.8kg/h.
This oil cools off after steam treatment, measures FAST index (referring to table 2) then.Used equation is as follows: fishiness index=1+ (0.31A)+(0.11B)+(0.03C), wherein, A=2,6-nonadienal; The B=4-heptenal; C=3, the 6-nonadienal.
Adopt this model, can obtain sample and the some kinds of sense organ figure that are purchased product (sensory picture) that good the inventive method is made.It is more stable than (alkyl) ester concentrate to be purchased oil (glyceride), and the numerical value of its FAST index is in the scope of 20-100, and the numerical value of ester concentrate is in the scope of 60-2500.This means: all these products all have fishlike smell although oxidation is no more than several ppm.This has explained that " repetition " sign relevant with the n-3 replenishers why is common and why some problems can occurs in the processing of these products and consumption.
Table 2 expression is purchased ester concentrate and reconstruct triglycerides and the FAST exponential number of the sample that obtains according to the present invention.
| Sample | FAST numerical value |
| ?EPAX?6000EE(4020) | ??2068 |
| ?EPAX?6000TG | ??2396 |
| ?EPAX?4510TG | ??1997 |
| ?EPAX?1050TG | ??1531 |
| ?Croda?332EE | ??111 |
| ?ONC?4020EE | ??125 |
| ?Croda?TG3322 | ??82 |
| ?Croda?TG0525 | ??1073 |
| ?Ropufa?75EE | ??2-3 |
| Embodiment 1 | ??1.5-2 |
| ?Ropufa?Food?oil | ??1.5 |
| Embodiment 2 | ??1-1.3 |
Thereby the material of embodiment 2 mixed with antioxidant further test the oxidation stability of improving these products, some the results are shown in following.Those of ordinary skills know that this selection not delimit the scope of the invention.
TBHQ is considered to a kind of effective anti-oxidants for a long time.Unexpectedly, we find that it and rosemary oil have strong synergy.Contain 0.2% Rosmarinus officinalis extract, 200ppm ascorbyl palmitate and 1000ppm mixed tocopherol
Food oil has 5.4 hours Rancimat induction period under 100 ℃.If substitute tocopherol with 200ppm TBHQ, extend to more than 10 hours in the induction period under 100 ℃ so.
Contain the herbal medicine phenol of various combination and TBHQ
The results are shown in the table 3 of food oil oxidation stability.The Rancimat of every kind of situation surpasses 4 hours induction period.
Table 3: the PUFA oil that is stabilized and the Rancimat stability of ester
Embodiment 3
(A) from Smit ﹠amp; Zoon, the marine oils type DHA that is used for ROPUFA ' 30 ' n-3 food oil of NL has following specification:
Outward appearance: yellow oil
Color (Gardner): maximum 11
Taste: can accept
Smell: very light fishlike smell
Acid number: maximum 0.5 (mg KOH/g oil)
Peroxide number: maximum 5.0 (mEq/kg oil)
P-Anisidin value: maximum 30
Saponifiable matter not: maximum 2.0%
DPA content: maximum 1.0%
EPA content: minimum 10.5%
DHA content: minimum 16.0%
N-3 fatty acid total amount: minimum 30.0%
N-3 long-chain PUFA (DPA+EPA+DHA) total amount: minimum 25.0%
Vitamin A: maximum 100IU/ml
Cholecalciferol: maximum 50IU/ml
Cholesterol: maximum 0.5%
(B) above-mentioned marine oils is by concise fully (come unstuck, bleach and deodorizing by the standard oil refinery practice).Yet in order to produce human consumption's gentle and stable marine oils, it is considered to rough, must carry out extra step so that it adapts to food applications.
(C1) on silica, adsorb
Under blanket of nitrogen, the thick marine oils of 500kg is added in the 1000l container.To wherein adding 5% (w/w) silica, begin then to stir.The pressure of container is reduced to 40hPa.In case reach 100hPa, just container contents be heated to 70 ℃.Kept stirring, temperature and pressure 5 hours.Then, the content in the container is cooled to 40 ℃, and successively on the tubular filter of 10 microns bag filter and 1 micron, filters.To be filtered oil half in add the Herbalox of 2000ppm.
(C2) on silica and carbon, adsorb
Under blanket of nitrogen, the thick marine oils of 500kg is added in the 1000l container.To wherein adding 5% (w/w) silica, begin then to stir.The pressure of container is reduced to 40hPa.In case reach 100hPa, just container contents be heated to 70 ℃.Kept stirring, temperature and pressure 2 hours.Then, pressure is set at normally, adds 2% active carbon then.Make the pressure of container reach 40hPa once more.Kept stirring, temperature and pressure other 3 hours.Content in the container is cooled to 40 ℃, and successively on the tubular filter of 10 microns bag filter and 1 micron, filters.To be filtered oil half in add the Herbalox of 2000ppm.
(D) adverse current deodorizing
Make the deodorizing of PUFA oil by continuous flow upstream steam distillation (CCSD).Oil is being added before the deodorizing tower, oil is being outgased in degas module under 140 ℃ the temperature and under the pressure of 40hPa.After the degassing, oil further is preheated to 210 ℃ temperature in heat exchanger, is fed to the top of deodorizing tower then.The tower of deodoriser has the internal diameter of 50mm, and structuring filling (model is installed
Rombopak S6M).The length of structuring filling is 4m in the tower.Below filler, the steam that derives from the equivalent steam generating unit is added in the tower continuously.The pressure of steam is about 4bar (4000hPa), and temperature is about 144 ℃.In tower itself, keep low-down vacuum by 3-level vacuum pump unit.At the top of tower, pressure is adjusted to 2hPa.By the counter-current flow of liquid oil phase and steam gas phase, from oil, take away the taste component.The mass flow of oil adds up to 11kg/h, and the mass flow of steam adds up to 0.1kg/h.The oil of deodorizing is cooled to 80 ℃, adds three kinds of different antioxidants (tocopherols: 1000ppm at last; Ascorbyl palmitate: 250ppm; Citric acid: 25ppm).
(E) application (0.2%) of food oil in milk
Preparation
-sodium ascorbate is dissolved in the part milk
-food oil is added in the milk
-homogenizing (2 *, 150 and 50bar under)
-milk is packed in the 200ml bottle
-pasteurization (in core 80 ℃ following 1 minute)
-be stored in 2 weeks in the refrigerator
Raw material control food oil is used
Full milk (3.8% fat) (g) 450 398
Defatted milk (0% fat) (g) 550 600
PUFA oil (g)-2.00
Sodium ascorbate (g) 0.25 0.25
Amount to 1,000 1000
Fat content 1.71 1.71
(E) application (agitating type) of food oil in natural acid cheese
Preparation
-milk is heated to 30 ℃
The mixture of-interpolation defatted milk powder, stabilizing agent and sugar
-mix
-be heated to 65 ℃
-interpolation food oil
-homogenize (60 ℃, 200kg/cm
2, 2 minutes)
-pasteurize (90 ℃, 15 minutes)
-be cooled to 15 ℃
-adding natural acid cheese also mixes
-at 45 ℃ of bottom fermentation 3-4 hour (pH4.3)
-cooling and vigorous stirring immediately
-with also sealing in the block device cup
-be stored under the highest 5 ℃ temperature
Raw material contrast (g) food oil is used (g)
Full milk (3.8% fat) 390 10
Defatted milk (0% fat) 507 879
Defatted milk powder (maximum 1.5% fat) 20 20
Sugar 50 50
Stabilizing agent 33
Inulin 55
Natural acid cheese (0.1% fat) 25 25
Food oil-8
Amount to 1,000 1000
The sense organ assessment:
Tested as the sense organ method.Sense organ test provides Useful Information, because it relates to the acceptance level of consumer to the aroma and flavor of food.This method is very responsive, and the information about flavor stability is provided.
All samples is given the trial test panel of undergoing training.Adopt inner grade (according to different qualities) to carry out the sense organ analysis by descriptive analysis.Inner grade is formed 1 grade of characterization " not detectable " at interval by 6; 7 grades of expressions " extremely strong ".Implement variable analysis (ANOVA) to determine whether to exist significant difference.Adopt least significant difference test (L.S.D) under 5% level of signifiance, repeatedly to compare.
The quality of deodorizing marine oils:
Silica/carbon
The silica silica
Silica/carbon
Do not contain
Do not contain Herbalox and contain Herbalox
Contain Herbalox
Herbalox
Fast index 1.5 1.0 1.0 1.0
Rancimat
100℃/h?2.6?????5.4?????2.8?????6.4
Milk is used
Smell 1.67 1.33 1.42 1.08
Taste 2.33 1.83 2.42 1.08
Yogurt is used
Smell 1.00 1.17 1.00 1.00
Taste 1.75 1.42 1.25 1.17
Embodiment 4
Similar with method described in the embodiment 3, make from Ocean Nutrition the deodorizing of the ester exchange ocean fish of Canada (ONC) oil.EE75 fish oil ethyl ester from ONC has following specification:
Outward appearance: yellow oil
(Lovibond red 5 for color
1/
4"): maximum 0.5
Acid number: maximum 3.0 (mg KOH/g oil)
Peroxide number: maximum 5.0 (mEq/kg oil)
P-Anisidin value: maximum 20
EPA content: minimum 42.0%
DHA content: minimum 22.0%
N-3 fatty acid total amount: minimum 75.0%
Claims (20)
1. one kind is used to prepare by the method for deodorizing and the food-grade fish oil that is stabilized, and described method comprises: make marine oils carry out adverse current steam distillation (CCSD) in containing the film tower of structuring filling, add antioxidant if desired.
2. the method for claim 1, wherein make described marine oils in the presence of herb extracts deodorant, carry out described adverse current steam distillation.
3. as claim 1 or the described method of claim 2, described method is the continuous flow upstream steam distillation.
4. as claim 2 or the described method of claim 3, wherein, described herb extracts deodorant is rosemary, and/or Sage extract.
5. as any described method in the claim 1 to 4, wherein, described antioxidant comprises ascorbyl palmitate and/or tocopherol and optional citric acid.
6. as any described method in the claim 1 to 5, wherein, described marine oils comprises at least a PUFA (polyunsaturated fatty acid).
7. as any described method in the claim 1 to 6, wherein, described marine oils is food oil or the Arrcostab that contains PUFA, preferred ethyl ester concentrate.
8. as any described method in the claim 1 to 7, wherein, described distillation between 0.1 and the low pressure of 10hPa under, preferably between 0.5 and the low pressure of 10hPa under, more preferably between 1 and the low pressure of 5hPa under carry out.
By any described method in the claim 1 to 8 obtain by food-grade marine oils deodorizing and that be stabilized.
Can by any described method in the claim 1 to 8 obtain by food-grade marine oils deodorizing and that be stabilized.
11. one kind by food-grade marine oils deodorizing and that be stabilized, it is characterized in that FAST index TM is lower than 1.5, preferably between 1.3 and 1, more preferably between 1.1 and 1, most preferably is 1.0.
12., it is characterized in that Rancimat induction period was greater than 6.2 hours as any described marine oils in the claim 9 to 11.
13., it is characterized in that Rancimat induction period is in 10.15-20 hour scope as any described marine oils in the claim 9 to 11.
14. as in the claim 9 to 13 any one described by the purposes of food-grade marine oils deodorizing and that be stabilized in making meals or healthy replenishers, condensed food and feed (functional food/feed) and cosmetics or pharmaceutical preparation.
15. meals or healthy replenishers, its comprise in the claim 9 to 13 any one described by food-grade marine oils deodorizing and that be stabilized.
16. a reinforcement/functional food, its comprise in the claim 9 to 13 any one described by food-grade marine oils deodorizing and that be stabilized.
17. cosmetics, its comprise in the claim 9 to 13 any one described by food-grade marine oils deodorizing and that be stabilized.
18. a pharmaceutical preparation, its comprise in the claim 9 to 13 any one described by food-grade marine oils deodorizing and that be stabilized.
19. the wiped film distillation column of interstitital texture filler in making claim 9-13 any one described by the purposes in food-grade marine oils deodorizing and that be stabilized.
20. one kind is used for by intermediate food or its component production claim 15 or meals, health or the nutritious supplementary pharmaceutical of the 16 described n-3PUFA of being rich in or the method for reinforcement/functional food, described method has following feature: add the marine oils of certain quantity of fluid form, former state, emulsion or gel form or dried forms in described intermediate food or its component, wherein contain the n-3 aliphatic acid of aequum; Make its dispersion by violent mixing; If desired, the blend that obtains thus further is processed into required product after the processing also.
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| CN201510386282.8A CN105029138A (en) | 2007-05-11 | 2008-05-09 | Deodorization and stabilization of marine oils |
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|---|---|---|---|
| EP07009539.3 | 2007-05-11 | ||
| EP07009539A EP1992233A1 (en) | 2007-05-11 | 2007-05-11 | Stabilized marine oils and process of making them |
| US79849607A | 2007-05-14 | 2007-05-14 | |
| US11/798,496 | 2007-05-14 | ||
| PCT/EP2008/003782 WO2008138575A2 (en) | 2007-05-11 | 2008-05-09 | Deodorization and stabilization of marine oils |
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| EP (1) | EP2152094A2 (en) |
| JP (2) | JP5550147B2 (en) |
| KR (1) | KR101586502B1 (en) |
| CN (2) | CN101677600A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102461677A (en) * | 2010-11-19 | 2012-05-23 | 嘉里特种油脂（上海）有限公司 | Composite improving stability of long-chained polyunsaturated fatty acid and application thereof |
| CN104507324A (en) * | 2012-07-31 | 2015-04-08 | 帝斯曼营养产品股份公司 | Refinement of oils using green tea extract antioxidants |
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| KR101586502B1 (en) * | 2007-05-11 | 2016-01-18 | 디에스엠 아이피 어셋츠 비.브이. | Deodorization and stabilization of marine oils |
| JP5606430B2 (en) | 2008-03-17 | 2014-10-15 | リピッド ニュートリション ベー．フェー． | Method for purifying triglyceride oil |
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| BR112014010347A2 (en) * | 2011-11-01 | 2017-04-18 | Dsm Ip Assets Bv | oil containing oxidatively stable polyunsaturated fatty acid |
| JP6166983B2 (en) * | 2013-08-23 | 2017-07-19 | 花王株式会社 | Method for producing refined fats and oils |
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| JP6226089B2 (en) * | 2015-04-27 | 2017-11-08 | 不二製油株式会社 | Method for producing long-chain polyunsaturated fatty acid-containing oil |
| CN113528235A (en) * | 2020-04-22 | 2021-10-22 | 华中农业大学 | Deodorization process for steam distillation of ethanol of edible oil |
| EP4183462A1 (en) | 2021-11-23 | 2023-05-24 | TotalEnergies OneTech | Method for deodorizing regenerated lubricating oils using supercritical co2 |
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| US3506696A (en) * | 1968-04-22 | 1970-04-14 | Procter & Gamble | Continuous high temperature steam deodorization of edible oils |
| US5436018A (en) * | 1986-10-21 | 1995-07-25 | Source Food Technology, Inc. | Preparation of low cholesterol oil |
| US4996072A (en) * | 1987-03-02 | 1991-02-26 | General Mills, Inc. | Physical process for the deodorization and/or cholesterol reduction of fats and oils |
| JPS63145845U (en) * | 1987-03-17 | 1988-09-27 | ||
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| NZ500703A (en) * | 1998-11-04 | 2001-06-29 | F | Preparation of food-grade marine edible oils by treatment with silica, vacuum steam deodorisation and addition of a herb extract |
| DE60119932T2 (en) * | 2000-07-19 | 2007-01-18 | Lysi Hf | METHOD FOR PRODUCING OILS MARINE ORIGIN WITH REDUCED CONTAMINATION |
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| US20040229233A1 (en) * | 2002-10-16 | 2004-11-18 | Ngk Insulators, Ltd. | Human housekeeping genes and human-tissue specific genes |
| DK1673423T3 (en) * | 2003-10-21 | 2009-03-30 | Dsm Ip Assets Bv | Stabilization of polyunsaturated fatty acid (PUFA) ester concentrates |
| JP4459781B2 (en) * | 2004-10-29 | 2010-04-28 | 株式会社カネカ | Oils and fats containing phospholipids and processed oils and fats using phospholipids and oils |
| JP4280234B2 (en) * | 2004-12-24 | 2009-06-17 | 花王株式会社 | Production method of fats and oils high in diglycerides |
| JP4516897B2 (en) * | 2005-07-07 | 2010-08-04 | 日清オイリオグループ株式会社 | Edible oil and fat manufacturing method and edible oil and fat |
| CN101228257A (en) * | 2005-07-18 | 2008-07-23 | 帝斯曼知识产权资产管理有限公司 | Method for rejuvenating aged food oils |
| KR101586502B1 (en) * | 2007-05-11 | 2016-01-18 | 디에스엠 아이피 어셋츠 비.브이. | Deodorization and stabilization of marine oils |
-
2008
- 2008-05-09 KR KR1020097023423A patent/KR101586502B1/en not_active IP Right Cessation
- 2008-05-09 WO PCT/EP2008/003782 patent/WO2008138575A2/en active Application Filing
- 2008-05-09 CN CN200880015614A patent/CN101677600A/en active Pending
- 2008-05-09 CN CN201510386282.8A patent/CN105029138A/en active Pending
- 2008-05-09 JP JP2010506862A patent/JP5550147B2/en not_active Expired - Fee Related
- 2008-05-09 EP EP08758456A patent/EP2152094A2/en not_active Withdrawn
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2014
- 2014-02-07 JP JP2014022494A patent/JP2014128273A/en active Pending
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2016
- 2016-05-03 HK HK16105007.2A patent/HK1216977A1/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102461677A (en) * | 2010-11-19 | 2012-05-23 | 嘉里特种油脂（上海）有限公司 | Composite improving stability of long-chained polyunsaturated fatty acid and application thereof |
| CN102461677B (en) * | 2010-11-19 | 2014-06-18 | 嘉里特种油脂（上海）有限公司 | Composite improving stability of long-chained polyunsaturated fatty acid and application thereof |
| CN104507324A (en) * | 2012-07-31 | 2015-04-08 | 帝斯曼营养产品股份公司 | Refinement of oils using green tea extract antioxidants |
| CN112662469A (en) * | 2012-07-31 | 2021-04-16 | 帝斯曼营养产品股份公司 | Antioxidant refined oil using green tea extract |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5550147B2 (en) | 2014-07-16 |
| WO2008138575A2 (en) | 2008-11-20 |
| CN105029138A (en) | 2015-11-11 |
| KR20100016389A (en) | 2010-02-12 |
| EP2152094A2 (en) | 2010-02-17 |
| KR101586502B1 (en) | 2016-01-18 |
| WO2008138575A3 (en) | 2009-01-22 |
| JP2010526896A (en) | 2010-08-05 |
| JP2014128273A (en) | 2014-07-10 |
| HK1216977A1 (en) | 2016-12-16 |
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