WO1996037587A1 - Production de matieres a teneur elevee en acides gras polyinsatures a longue chaine - Google Patents

Production de matieres a teneur elevee en acides gras polyinsatures a longue chaine Download PDF

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Publication number
WO1996037587A1
WO1996037587A1 PCT/EP1996/002131 EP9602131W WO9637587A1 WO 1996037587 A1 WO1996037587 A1 WO 1996037587A1 EP 9602131 W EP9602131 W EP 9602131W WO 9637587 A1 WO9637587 A1 WO 9637587A1
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Prior art keywords
lcpufa
fatty acids
free fatty
product
process according
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PCT/EP1996/002131
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English (en)
Inventor
Frederick William Cain
John Bernard Harris
Stephen Raymond Moore
Gerald Patrick Mcneill
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Loders Croklaan B.V.
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Priority to AU66109/96A priority Critical patent/AU6610996A/en
Publication of WO1996037587A1 publication Critical patent/WO1996037587A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/32—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by the composition containing organic or inorganic compounds
    • A23G9/327—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor characterised by the composition containing organic or inorganic compounds characterised by the fatty product used, e.g. fat, fatty acid, fatty alcohol, their esters, lecithin, glycerides
    • 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
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G9/00—Frozen sweets, e.g. ice confectionery, ice-cream; Mixtures therefor
    • A23G9/52—Liquid products; Solid products in the form of powders, flakes or granules for making liquid products ; Finished or semi-finished solid products, frozen granules
    • 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
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/60—Salad dressings; Mayonnaise; Ketchup
    • 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
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A23L33/12—Fatty acids or derivatives thereof
    • 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
    • C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • C11B7/0008—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents
    • C11B7/0025—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents in solvents containing oxygen in their molecule
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
    • C11C1/045—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis using enzymes or microorganisms, living or dead
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6409—Fatty acids
    • C12P7/6427—Polyunsaturated fatty acids [PUFA], i.e. having two or more double bonds in their backbone
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
    • A23G2200/08—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing cocoa fat if specifically mentioned or containing products of cocoa fat or containing other fats, e.g. fatty acid, fatty alcohol, their esters, lecithin, paraffins

Definitions

  • Tanaka in J Am Oil Chem. Soc. 71 (1994) 331-334 discloses a process, wherein a fish oil is subjected to enzymic
  • a hydrolysis of a fish oil is performed, using e.g. Pseudomonas lipase.
  • the resulting product is concentrated in highly unsaturated fatty acids, e.g. by low temperature fractionation, urea adduction or absorption methods.
  • the concentrate obtained is reconverted into triglycerides by reaction with
  • JP 90/071781 a process is disclosed, wherein a fish oil is split by treatment with Cand. rugosa. The resulting product is separated in free fatty acids and in glycerides. The free fatty acids are converted to esters by reaction with an alcohol, while the esters formed are subjected to urea adduction. The glycerides obtained by the separation on converted into esters by reaction with alcohol, where upon the esters formed are subjected to urea adduction.
  • our invention concerns a novel process for the production of materials, enriched in long chain
  • LCPUFA polyunsaturated fatty acids
  • component B is optionally converted by esterification to triglycerides B 1 or optionally hydrolysed to a product B 11 , rich in free fatty acids; component B or component B 1 or component B 11 is then split into at least two parts D and E; D having a total LCPUFA-content that is at least 1.2 preferably at least 1.25 times, more preferably at least 1.3 times the total LCPUFA-content of B or B 1 or B 11 ; and/or component C is split into at least two further parts F and G, from which F has a LCPUFA-content that is at least 1.2 times that of C.
  • Material A thus contains at least 5 wt% of LCPUFA's, however higher levels of LCPUFA's in the end-product are obtained, when material A contains at least 10 wt%,
  • LCPUFA's preferably at least 15 wt%, more preferably at least 20 wt% and most preferably 25-50 wt% of LCPUFA's.
  • Material A further comprises at least two different
  • L 1 and L 2 are selected from linolenic acid (C 18:3 ) ; arachidonic acid
  • C 20:4 eicosapentaenoic acid
  • C 20:5 docosapentaenoic acid
  • C 22:5 docosahexaenoic acid
  • C 22:6 docosahexaenoic acid
  • Very suitable materials A are selected from the group, consisting of at least one of the following oils:
  • liver oil tuna oil; sardine oil; anchovy oil; herring oil; sand eel oil or salmon oil.
  • oils from microbial fermentation in particular from a mortierella species; Penicillium; Phytium; Chlorella; Euglena; Porphyridium; Monodus or Nitzchia.
  • the fish oils are suitable sources, as a number of fish oils are cheap, while they still contain relatively high levels of LCPUFA's, which LCPUFA's consist in general of different LCPUFA's, such as DHA (docosahexa enoic acid: C 22:6 ) and eicosapentaenoic acid (or EPA: C 20:5 ) .
  • LCPUFA's consist in general of different LCPUFA's, such as DHA (docosahexa enoic acid: C 22:6 ) and eicosapentaenoic acid (or EPA: C 20:5 ) .
  • the split of material A into parts B and C is performed by an enzymatic hydrolysis.
  • an enzyme is applied, that can distinguish LCPUFA's of different chain length.
  • a preferred enzyme is Candida rugosa.
  • Product B formed comprises partial glycerides and triglycerides, while product C formed, comprises free fatty acids. However it is also possible that product B comprises free fatty acids and product C comprises the partial glycerides and triglycerides. Products B and C however always will have a different composition.
  • B and C can be separated by a physical separation method. Physical separation methods that can be applied are:
  • absorbent preferably basic alumina
  • the invention furhter concerns, a process wherein product B or its converted triglyceride-product B 1 or its hydrolysed product B 11 are split in other products, that have an increased level of total LCPUFA's, compared to the starting products B, B 1 or B 11 .
  • our invention also concerns a process, wherein product B is optionally esterified to a triglyceride product B 1 , or optionally randomly hydrolysed to free fatty acids B 11 or a product B 11 rich in free fatty acids, using a non-specific lipase or a base, while product B or product B 1 or product B 11 is split into products D and E by one of the following processes:
  • interesterification is followed by removal of precipitated triglycerides rich in saturated fatty acids by filtration, either dry or in solvent.
  • the solvent fractionation preferably is a low temperature fractionation (i), performed at temperatures between 0 and -70°C, in particular between -25 and -60°C. Although a dry- fractionation is possible, we found that better results are obtained, if a wet-fractionation is performed. Solvents that can be applied for such a wet-fractionation are e.g. hexane, petroleum ether and acetone. However other solvents known for the wet-fractionation of fats can also be used. Suitable weight-ratios fats: solvent are 1:4 to 4:1, preferable: 1:3 to 3:1.
  • the oleine-fraction is normally The directed interesterification (ii) can be performed by adding a base, such as Na-methylate to the mixture. The temperature applied will range from -10 to 50°C, in
  • glycerides including glycerides rich in saturated fatty acids (such as trisaturated triglycerides).
  • This separation can be performed by any known suitable separation-technique for separating a liquid and a solid phase.
  • the liquid phase is the product, enriched in LCPUFA's.
  • the interesterification can also be performed as an enzymic interesterification.
  • a lipase selected from Chromobacterium; Pseudomonas;
  • Rhizomucor Rhizomucor
  • Humicola Rhizopus or Candida.
  • the enzymic interesterification (ii) is performed in the presence of a limited amount of water (i.e. up to 2 wt%)).
  • the conditions that can be applied are set our in e.g. GB 1,577,933.
  • reaction can be directed by precipitation of the glycerides, rich in saturated fatty acid moieties.
  • the glycerolysis (iii) also can be performed by using a base (e.g. Na-methylate) or by using an enzyme.
  • a base e.g. Na-methylate
  • Enzymes, that are known for glycerolysis-purposes, are disclosed in our earlier patent-application EP 94302325.9
  • the crude reaction product is a mixture of triglycerides and partial glycerides (most diglycerides), with a whole spectrum of fatty acid moieties in it. However the triglycerides and partial glycerides rich in saturated fatty acid moieties will precipitate in the crude reaction-mixture.
  • the hydrolysis (iv) is performed by using a lipase, that is selective against LCPUFA's over other fatty acids.
  • a lipase that is selective against LCPUFA's over other fatty acids.
  • Example of such lipase are: Geotrichum candidum, Lipase G and Mucor Miehei.
  • the techniques to separate D and E in this instance are well-known physical separation techniques.
  • the products D and E which are formed by our process can either be both triglycerides and/or partial glycerides, or product D can be a mixture of partial glycerides and triglycerides, while product E is a mixture of free fatty acids or D and E are both free fatty acids, however having a different composition.
  • a very beneficial process is obtained if part of product D or E is hydrolysed, resulting in a mixture comprising free fatty acids and glycerol; removing the glycerol from this mixture and reconverting the remaining free fatty acids with another part of D or E, or the original non-hydrolysed material, preferably using stoichiometric amounts of reactants.
  • the results of this process are triglycerides with an increased total level of LCPUFA's, wherein L 1 and L 2 are present in a ratio, different from its ratio in starting material A.
  • Component C or a conversion product of component C, can be split into parts F and G by physical separation methods.
  • physical separation methods are:
  • the solvent fractionation (ii) is carried out, using hexane, petroleum either or acetone as solvent.
  • the solvent/oil-ratio is 4:1 to 1:4, preferably 3:1 to 1:3.
  • the temperature applied is -20 to -60 C°, preferably -25 to -35 C°.
  • the free fatty acid products obtained by our novel process can be used for the esterification of glycerol or partial glycerides, preferably in stoichiometric amounts for the production of triglycerides.
  • Component C comprising free fatty acids can also be split into two parts by reaction with alcohols, using a lipase selective against LCPUFA.
  • the reaction forms esters depleted in LCPUFA, leaving free fatty acid, enriched in
  • the triglycerides, partial glycerides, or free fatty acids, as obtainable by the process according to the invention or its blends with anti-oxidants can also be mixed with other lipid materials that have a solid fat index at 5°C (N 5 :
  • Part of our invention are also consumer products, such as food products, in particular spreads, cream alternatives, infant food, ice cream, mayonnaise, dressings, toppings etcetera, pharmaceutical products, skin-care products, such as lotions or skin-creams comprising a fatty component or a free fatty acid, wherein the fatty component or the free fatty acid comprises a product as obtainable by the process according to claims 1-16, or wherein the fatty component or free fatty acid comprises a blend according to claims 17- 18.
  • food products in particular spreads, cream alternatives, infant food, ice cream, mayonnaise, dressings, toppings etcetera
  • pharmaceutical products skin-care products, such as lotions or skin-creams comprising a fatty component or a free fatty acid, wherein the fatty component or the free fatty acid comprises a product as obtainable by the process according to claims 1-16, or wherein the fatty component or free fatty acid comprises a blend according to claims 17- 18.
  • our invention also concerns the use of materials, enriched in LCPUFA's, wherein the products, as obtainable by the process of claims 1-16 or wherein the blends according to claims 17-18 are used to improve the health benefits of consumer goods, such as food products or personal products.
  • EXAMPLES EXAMPLES 1
  • a triglyceride/ partial glyceride mixture was thus obtained with a composition as given in table 1.
  • Fatty acid compositions were determined by fatty acid methyl ester gas chromatography (FAME GC) using the method given in AOCS Ce 1b-89, free fatty acid (FFA) contents were determined by titration against standard sodium hydroxide solution and are expressed as % oleic acid.
  • Partial glyceride contents were determined by silica gel high performance liquid chomatography (HPLC ) using an
  • LCPUFA long chain polyunsaturated
  • a SPREAD was prepared using the LCPUFA enriched oleine fraction which was compared to a reference spread made with sunflower oil.
  • the spreads were made with the following formulation:
  • the fat blend for the reference was 13% InEs, 87% SF.
  • the fat blend used was:- InEs 13%
  • Es Interesterified mix of fully hardened palm oil and fully hardened palmkernel olein.
  • a micro-votator processing lines was set up as follows:-
  • the aqueous phase was prepared by heating the required amount of water to approximately 80°C and then, using a silverson mixer, slowly mixing in the ingredients.
  • the pH of the system was adjusted to 5.1 by adding 20% Lactic acid solution as required.
  • a premix was prepared by stirring the fat phase in the premix tank and then slowly adding in the aqueous phase. When addition was complete, the mix was stirred for a further 5 minutes before pumping through the line. When the process had stabilised (around 20 minutes), product was collected for storage and evaluation.
  • a "RANCH STYLE” DRESSING was prepared using the LCPUFA enriched oleine which was compared to a reference dressing made with sunflower oil.
  • the formulation for the dressing is given in table 1.4
  • a "RANCH STYLE” DRESSING was prepared using the LCPUFA enriched oleine which was compared to a reference dressing made with sunflower oil.
  • the formulation for the dressing is given in table 1.4
  • the liquid oil for the reference was sunflower and for the LCPUFA containing product was 90/10 sunflower oil /
  • liquid oils were slowly added to the aqueous phase whilst homogenising. Mixing was continued until all the oil appeared to have been dispersed. The dressings were then transferred to sterile bottles.
  • the dressings were evaluated after 24 hours storage at ambient temperature.
  • the viscosities of the samples were determined using a Brookfield Viscometer fitted with a number 4 spindle rotating at 10 rpm.
  • the samples were contained in identical 200ml plastic bottles hence the viscosities are directly comparable with each other.
  • For each sample the average of three measurements was taken with the sample being allowed to relax for 1 minute between each 1 minute of shear.
  • the oil droplet size distribution was determined using a Malvern Mastersizer fitted with a a 45mm lens.
  • a Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a triglyceride/ partial glyceride mixture was thus obtained with a composition as given in table 2.1. Analytical procedures were as described in example 1. To 5g of the triglyceride/ partial glyceride mixture were added 0.2g of Geotrichum Candida lipase dissolved in 5g of pH6.5 phosphate buffer. The mixture was stirred with a
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a triglyceride/ partial glyceride mixture was thus obtained with a
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a triglyceride/ partial glyceride mixture was thus obtained with a
  • composition as given in table 4.
  • Analytical procedures were as described in example 1. 100g of the partial glyceride fraction were hydrolysed to free fatty acids by refluxing with 23g of potassium hydroxide in 130mls of ethanol and 44mls of water for 1 hour. The potassium salts were converted to free fatty acids by addition of hydrochloric acid and then extracted into hexane.
  • 35g of the fatty acids were added to 200g of urea mixed with 600mls of ethanol at 65°C in a jacketed vessel fitted with a scape surface stirrer. The mixture was stirred for 1 hour at 65°C then cooled at 1°C/min to 4°C at which
  • the fatty acids were esterified with glycerol to form a triglyceride rich fat.
  • 1.6 g of the fatty acids were mixed with 0.2g of glycerol and 0.1g of Rhizomucor miehei
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a triglyceride/ partial glyceride mixture was thus obtained with a
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a free fatty acid fraction was thus obtained with a composition as given in table 6.
  • Analytical procedures were as described in example 1.
  • the fatty acids were esterified with glycerol to form a triglyceride rich fat.
  • 5.1 g of the fatty acids were mixed with 0.6g of glycerol and 0.3g of Rhizomucor miehei immobilised onto Duolite. The mixture was stirred in an open glass vial at 55°C for 144 hours with nitrogen blowing across the surface.
  • the composition of the triglyceride rich fat is given in table 6
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a free fatty acid fraction was thus obtained with a composition as given in table 7.
  • Analytical procedures were as described in example 1.
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a free fatty acid fraction was thus obtained with a composition as given in table 8.1.
  • Analytical procedures were as described in example 1. 400g of the fatty acids were dissolved in 1600g of acetone and cooled to -60°C. A stearine fraction was removed by filtration and washed with another 1600g of acetone. The oleine fraction fatty acids were esterified with glycerol to form a triglyceride rich fat. 166g of the fatty acids were mixed with 14.9g of glycerol and 7.9g of
  • Rhizomucor miehei immobilised onto Duolite.
  • the mixture was stirred in a round bottom flask at 55°C for 144 hours under vacuum.
  • the enzyme was removed by filtration.
  • the remaining free fatty acid was removed by treatment with basic alumina in hexane.
  • the composition of the triglyceride rich fat is given in table 8.1.
  • a SPREAD was prepared using the LCPUFA enriched
  • a "RANCH STYLE" DRESSING was prepared using the LCPUFA enriched triglyceride fraction which was compared to a reference dressing made with sunflower oil.
  • the formulation and method of production was as described in example 1.
  • AN ICE-CREAM was prepared using the LCPUFA enriched
  • Ice-creams were made according to the following recipe:
  • Sherex IC 9330 ® is a product from Quest International and comprises mono- and diglycerides admixed with different stabilizers.
  • the fat blend for the reference was PO / Sunflower oil 90/10 and the fat blend according to the invention was:
  • Hardness was measured by using a Stevens texture analyser with a 45° cone at a speed of 0.5 mm/second till a deepness of 2 mm.
  • Chilean fish oil was hydrolysed using Candida rugosa lipase to a free fatty acid content of 60% and the acids removed by evaporation as described in example 1.
  • a free fatty acid fraction was thus obtained with a composition as given in table 9.
  • Analytical procedures were as described in example 1. 356g of the fatty acids were cooled to 30°C and held for 24 hours at which time 10% of the mixture had solidified. This solid fraction was removed by filtration under a pressure of 0-24 bar for 2 hours then 24 bar for a further 2 hours.

Abstract

Matières enrichies en acides gras polyinsaturés à chaîne longue (LCPUFA) qui sont obtenues à partir d'une matière A contenant au total ≥5 % de LCPUFA et comprenant ≥2 LCPUFA (L1 et L2) dans une proportion XA par séparation de A en parties B et C, de manière à ce que B présente une proportion L1:L2=XB qui est au moins 1,5 fois XA, tandis que C présente une proportion L1:L2=XC qui est ≤0,7 fois XA. Le constituant B est ensuite séparé en constituants D et E, D ayant une teneur totale en LCPUFA qui est > 1,2 fois sa teneur en B et/ou le constituant C est séparé en constituants F et G, F ayant une teneur en LCFUPA qui est » 1,2 fois sa teneur en C.
PCT/EP1996/002131 1995-05-24 1996-05-13 Production de matieres a teneur elevee en acides gras polyinsatures a longue chaine WO1996037587A1 (fr)

Priority Applications (1)

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AU66109/96A AU6610996A (en) 1995-05-24 1996-05-13 Production of materials high in long chain polyunsaturated f atty acids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95303534 1995-05-24
EP95303534.2 1995-05-24

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WO1996037587A1 true WO1996037587A1 (fr) 1996-11-28

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019601A1 (fr) * 1995-11-24 1997-06-05 Loders Croklaan B.V. Composition a base d'huiles de poisson
EP0964058A1 (fr) * 1998-05-12 1999-12-15 Loders Croklaan B.V. Procédé d'enrichissement de trans-10 isomères
US6127562A (en) * 1998-05-12 2000-10-03 Loders Croklaan B.V. Process for the enrichment of compounds in trans-10 isomers
JP2002537442A (ja) * 1999-02-17 2002-11-05 ノルスク ハイドロ アーエスアー 海産油のリパーゼ触媒したエステル化
EP1582594A2 (fr) * 2004-03-31 2005-10-05 Cognis IP Management GmbH Procédé enzymatique amélioré de préparation de triglycérides d'acides gras polyinsaturés
EP1978102A1 (fr) 2007-04-02 2008-10-08 Cognis IP Management GmbH Un mélange comprenant des glycérides d'acides gras
EP1978101A1 (fr) 2007-04-02 2008-10-08 Cognis IP Management GmbH Procédé d'enrichissement en acides gras polyinsaturés
EP2602308A2 (fr) 2002-11-14 2013-06-12 Pronova BioPharma Norge AS Estérification catalysée par lipase d'huile marine
EP3847895A1 (fr) * 2020-01-07 2021-07-14 Bunge Loders Croklaan B.V. Procédé de préparation d'un produit de graisse interestérifié de manière aléatoire
WO2022238489A1 (fr) 2021-05-12 2022-11-17 Ab Enzymes Gmbh Préparations d'huile fermentées
US11872201B2 (en) 2018-06-21 2024-01-16 Nuseed Nutritional Us Inc. DHA enriched polyunsaturated fatty acid compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0225447A (ja) * 1988-07-13 1990-01-26 Nippon Oil & Fats Co Ltd 高度不飽和脂肪酸類の製造方法
JPH0319693A (ja) * 1989-06-16 1991-01-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸高濃度含有油脂の製造方法
JPH0319694A (ja) * 1989-06-16 1991-01-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸グリセリドの濃縮法
JPH0595792A (ja) * 1991-10-03 1993-04-20 Agency Of Ind Science & Technol 濃縮された高度不飽和脂肪酸含有油脂の製造方法
JPH0751075A (ja) * 1993-08-18 1995-02-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸含有物質の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0225447A (ja) * 1988-07-13 1990-01-26 Nippon Oil & Fats Co Ltd 高度不飽和脂肪酸類の製造方法
JPH0319693A (ja) * 1989-06-16 1991-01-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸高濃度含有油脂の製造方法
JPH0319694A (ja) * 1989-06-16 1991-01-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸グリセリドの濃縮法
JPH0595792A (ja) * 1991-10-03 1993-04-20 Agency Of Ind Science & Technol 濃縮された高度不飽和脂肪酸含有油脂の製造方法
JPH0751075A (ja) * 1993-08-18 1995-02-28 Nippon Oil & Fats Co Ltd ドコサヘキサエン酸含有物質の製造方法

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9010, Derwent World Patents Index; AN 90-071781, XP002013470 *
DATABASE WPI Week 9110, Derwent World Patents Index; AN 91-070269, XP002013471 *
DATABASE WPI Week 9110, Derwent World Patents Index; AN 91-070270, XP002013472 *
DATABASE WPI Week 9320, Derwent World Patents Index; AN 93-163591 *
DATABASE WPI Week 9517, Derwent World Patents Index; AN 95-127359, XP002013469 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 176 (C - 0707) 9 April 1990 (1990-04-09) *
PATENT ABSTRACTS OF JAPAN vol. 15, no. 137 (C - 0821) *
PATENT ABSTRACTS OF JAPAN vol. 15, no. 137 (C - 0821) 5 April 1991 (1991-04-05) *
PATENT ABSTRACTS OF JAPAN vol. 17, no. 429 (C - 1095) *
PATENT ABSTRACTS OF JAPAN vol. 950, no. 2 *
YUJI SHIMADA ET AL.: "Enrichment of polyunsaturated fatty acids with Geotrichum candidum lipase", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 71, no. 9, 1994, CHAMPAIGN US, pages 951 - 954, XP002013466 *
YUKIHISA TANAKA ET AL.: "Concentration of docosahexaenoic acid in glyceride by hydrolysis of fish oil with Candida cylindracea lipase", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 69, no. 12, 1992, CHAMPAIGN US, pages 1210 - 1214, XP002013468 *
YUKIHISA TANAKA ET AL.: "Synthesis of DHA-enriched triacylglycerol", JOURNAL OF THE JAPAN OIL CHEMISTS' SOCIETY, vol. 43, no. 1, 1994, JP, pages 39 - 43, XP002013467 *
YUKIHISA TANAKA ET AL.: "Synthesis of docosahexaenoic acid-rich triglyceride with immobilized Chromobacterium viscosum lipase", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 71, no. 3, 1994, CHAMPAIGN US, pages 331 - 334, XP002010220 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019601A1 (fr) * 1995-11-24 1997-06-05 Loders Croklaan B.V. Composition a base d'huiles de poisson
EP0964058A1 (fr) * 1998-05-12 1999-12-15 Loders Croklaan B.V. Procédé d'enrichissement de trans-10 isomères
US6127562A (en) * 1998-05-12 2000-10-03 Loders Croklaan B.V. Process for the enrichment of compounds in trans-10 isomers
JP2002537442A (ja) * 1999-02-17 2002-11-05 ノルスク ハイドロ アーエスアー 海産油のリパーゼ触媒したエステル化
EP2602308A2 (fr) 2002-11-14 2013-06-12 Pronova BioPharma Norge AS Estérification catalysée par lipase d'huile marine
US7981641B2 (en) 2004-03-31 2011-07-19 Cognis Ip Management Gmbh Processes for the production of triglycerides of unsaturated fatty acids in the presence of enzymes
EP1582594A3 (fr) * 2004-03-31 2005-10-12 Cognis IP Management GmbH Procédé enzymatique amélioré de préparation de triglycérides d'acides gras polyinsaturés
EP1582594A2 (fr) * 2004-03-31 2005-10-05 Cognis IP Management GmbH Procédé enzymatique amélioré de préparation de triglycérides d'acides gras polyinsaturés
EP1978102A1 (fr) 2007-04-02 2008-10-08 Cognis IP Management GmbH Un mélange comprenant des glycérides d'acides gras
EP1978101A1 (fr) 2007-04-02 2008-10-08 Cognis IP Management GmbH Procédé d'enrichissement en acides gras polyinsaturés
US7737289B2 (en) 2007-04-02 2010-06-15 Cognis Ip Management Gmbh Process for enriching polyunsaturated fatty acids
US11872201B2 (en) 2018-06-21 2024-01-16 Nuseed Nutritional Us Inc. DHA enriched polyunsaturated fatty acid compositions
EP3847895A1 (fr) * 2020-01-07 2021-07-14 Bunge Loders Croklaan B.V. Procédé de préparation d'un produit de graisse interestérifié de manière aléatoire
WO2021140109A1 (fr) * 2020-01-07 2021-07-15 Bunge Loders Croklaan B.V. Procédé de préparation d'un produit du type matière grasse à interestérification aléatoire
WO2022238489A1 (fr) 2021-05-12 2022-11-17 Ab Enzymes Gmbh Préparations d'huile fermentées

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