WO1992008363A1 - Fractionnement de lipides et produits ainsi obtenus - Google Patents

Fractionnement de lipides et produits ainsi obtenus Download PDF

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Publication number
WO1992008363A1
WO1992008363A1 PCT/AU1991/000105 AU9100105W WO9208363A1 WO 1992008363 A1 WO1992008363 A1 WO 1992008363A1 AU 9100105 W AU9100105 W AU 9100105W WO 9208363 A1 WO9208363 A1 WO 9208363A1
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WO
WIPO (PCT)
Prior art keywords
lipid
fluid
process according
mixture
water
Prior art date
Application number
PCT/AU1991/000105
Other languages
English (en)
Inventor
Corran Norman Stuart Mclachlan
Gary Norris Kerkin
Peter Vines
Christopher John Malcolm
Original Assignee
Portwall Pty. Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Portwall Pty. Limited filed Critical Portwall Pty. Limited
Publication of WO1992008363A1 publication Critical patent/WO1992008363A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C7/00—Other dairy technology
    • A23C7/04—Removing unwanted substances other than lactose or milk proteins from milk
    • A23C7/043—Removing unwanted substances other than lactose or milk proteins from milk using chemicals in liquid or solid state, e.g. flocculating, adsorbing or extracting agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C15/00—Butter; Butter preparations; Making thereof
    • A23C15/12—Butter preparations
    • A23C15/14—Butter powder; Butter oil, i.e. melted butter, e.g. ghee ; Anhydrous butter
    • A23C15/145—Removal of steroids, e.g. cholesterol or free acids; Fractionation of anhydrous milkfat by extraction with solvents other than solvent crystallisation or with supercritical gases or by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
    • B01D11/0407—Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solute
    • 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
    • C11B3/006—Refining fats or fatty oils by extraction

Definitions

  • This invention relates to the processing of lipids and more particularly the processing of lipids to produce a mixture of lipid fractions.
  • Milk-fat is a complex mixture of fatty acids and triglycerides with a range of molecular weights and degree of unsaturation and exhibiting a broad and variable melting range. In additio it contains many minor components- the major of which are cholesterol, mono- and di-glycerides and phospholipids. Their relative composition varies from animal to animal, seasonally, and on nutrient quality and type. In addition milk-fat contains vitamins A,D and carotene.
  • a convenient measure of the distribution of triglycerides is by reference to the carbon number distribution. Short chain triglycerides are recognised as having carbon numbers ranging from 28 to 40; and the longer chain triglycerides having carbon numbers 42 and up to 54.
  • R Norris [United States Patent No. 4,005,228, (1977)] describes a solvent extraction/crystallisation process in which milk-fat is either partially crystalised and slurried with an organic solvent, or heated and mixed with cold organic solvent to form a slurry of partially crystalised milk-fat, or is completely dissolved in a solvent and then fractionally crystalised out of the solution by cooling it.
  • the solid component of the slurry is separated mechanically.
  • the preferred solvents are propan- 2-ol, acetone, ethyl acetate, hexane or other petroleum derivatives, or mixtures thereof.
  • the milk-fat is fractionally dissolved in supercritical carbon dioxide at pressures typically ranging from 100-400 bar and at temperatures between 33-80 ⁇ C.
  • the triglycerides so dissolved are subsequently recovered by reducing the temperature and pressure to subcritical conditions under which they are no longer soluble, generally with the carbon dioxide in a gaseous state.
  • One of the disadvantages of this procedure is all the triglyceride fractions produced, including the undissolved residue, contain significant quantities of cholesterol. For example in a typical case Kankare et al reported 3.22 mg/g cholesterol in their lightest fractions through to 1.61 mg/g in the undissolved residue.
  • a process for separating at least part of the lipids from a lipid/water mixture comprising bringing a subcritical fluid at a suitable temperature and pressure and of a type such that at least part of the lipid is more soluble therein than water, into contact with the lipid-water mixture, in an extractor under conditions so that at least a part of the lipid component in the mixture is taken up by the fluid and then recovering the lipid from that fluid.
  • the mixture containing lipids may be essentially anhydrous being comprised of a range of lipid materials with minor concentrations of other dairy materials and water.
  • the mixture containing lipids may be essentially comprised of oils derived from vegetable matter, other plant matter, or other animal matter with minor concentrations of other materials and water.
  • the fluid is preferably carbon dioxide but 2 0, SF g , CFgCl, CF 2 C1, CH 2 CF 2 , C,F Rule, CHF.-, ethane, propane, butane, ethylene or acetone, which are considered unobjectionable from a health point of view can also be used. Mixtures of these fluids can also be used. This invention will be further described with reference to the use of carbon dioxide alone.
  • the amount of the lipid fraction that is extracted into the carbon dioxide fluid varies with the temperature of the extraction.
  • the temperature is below the critical temperature, it is found that the solubility of high molecular weight lipids, such as those above carbc number 40 in the lipi_ ⁇ fraction is low while the relative / low molecular weight lipids, namely those below about carbon number 40 are dissolved into the high pressure fluid.
  • the high molecular weight lipids will remain in the water phase if present, namely those lipids having a carbon number greater than about 40.
  • the fraction is itself a product of ttie invention.
  • butter-fat which has been extracted into the carbon dioxide stream.
  • Butter produced from butter-fat with a carbon number below 40 has a low softening point which is a desirable property in certain situations.
  • the softening point of that butter can be raised by adding the lipids of carbon number greater than 40. By varying the amount of added high molecular weight lipids, the softening point can be tailored to suit any desired situation.
  • a further surprising property of the high molecular weight fraction is that it is cholesterol free. This is contrary to the results of Bradley et al, for example, who found that when supercritical carbon dioxide is used to fractionate, substantial quantities of cholesterol were present in all fractions of the lipid.
  • the conditions of temperature and pressure under which the extraction is effected may vary for reasons mentioned above depending upon the desired product.
  • the temperature at a minimum will be sufficient under the conditions of pressure employed to achieve sufficient dissolution of a desired fraction of the lipids. This will normally be above -10°C.
  • the maximum temperatures will be mainly determined by cost constraints and the desire to avoid damage to heat sensitive ingredients in the butter-fat or other desired product.
  • the temperature will thus be between -10 ⁇ C and 80°C.
  • the temperature will preferably be between 0°C and 31°C.
  • the pressure is generally between 75 and 350 bar and more preferably between 150 and 280 bar.
  • the minimum pressure will be again dictated by the need to achieve a satisfactory dissolution of the desired lipid fraction(s) in the carbon dioxide stream.
  • Water has a relatively limited solubility in sub- or supercritical carbon dioxide which increases with temperature at constant pressure whereas carbon dioxide solubility for lipids decreases with temperature at constant pressure.
  • the carbon dioxide must intimately contact the surface of a thin film of the fat-in-water emulsion in a continuous co- current or counter-current manner.
  • the emulsion may be converted into the form of a thin film in any known manner as, for example, by passing the fat-in-water emulsion over a surface in the form of a thin film covering the same; by passing the emulsion through a cascade or packed bed, containing rings or other distribution systems known to the art, or a device which corresponds to a thin film surface evaporator or the like, or by spray nozzle or other droplet generating device.
  • the extraction may take place in a liquid-fluid extraction involving plate mixer-settler units. It is not intended that the separation process be limited but is to follow process steps well recognised in the art of chemical engineers.
  • the amount of carbon dioxide will be sufficient to dissolve the milk-fat and hence will be preferably 30-150 times the weight of milk-fat to be dissolved.
  • An important feature of the invention is to then reduce the cholesterol content in the lipid fraction in the high pressure fluid stream to produce a low cholesterol product, preferably a cholesterol free product.
  • the cholesterol can be removed by methods known in the art, such as using an adsorbent.
  • the adsorbent can be an inorganic compound or organic compound, which preferentially adsorbs cholesterol. There are many such adsorbents described in the literature. It is preferred within the scope of this invention, to use an adsorbent which selectively removes cholesterol and at the same time removes only a small amount, if any, of the lipid.
  • the preferred materials are those described in our New Zealand Patent Application No. 221,503. The methods described in that specification may be incorporated in the processes of this invention.
  • the cholesterol-free or low-cholesterol product can be then recovered by changing the fluid to the supercritical state through an increase in temperature at constant pressure or by lowering the pressure at constant temperature.
  • the product can be recovered by reducing the pressure and/or increasing the temperature.
  • This procedure therefore offers a process for making cholesterol-free lipid fractions, in which the melting point is varied to suit any desired conditions by first dissolving the milk-fat in high pressure carbon dioxide at a temperature belo its critical temperature so that high molecular weight lipids remain; passing lipid-laden carbon dioxide fluid to an adsorbent which is designed to remove substantially all the cholesterol; recovering the lipid from the carbon dioxide stream; and if desired, adding to that lipid fraction, high molecular weight lipid from the dissolution step.
  • Lipid fractions so obtained may be blended in suitable quantities with or without additional moisture and salt to produce cholesterol free butter as described in our New Zealand Patent Specification No. 233031 (1990).
  • the invention therefore provides a process for fractionating a lipid containing material into a high-molecular weight fraction and a low-molecular weight fraction, comprising treating the lipid containing material with a high pressure fluid at a temperature below its critical temperature, the temperature being chosen so that lipids of a molecular weight below a desired level are dissolved in the high pressure fluid, while the higher molecular weight lipids remain, and then recovering the low-molecular weight lipids from the high-pressure fluid stream and, if desired, recovering any high-molecular weight lipids from the residue.
  • a process for modifying the sterol and lipid content in a lipid material containing sterols comprising a subjecting the lipid material to a high-pressure fluid at a temperature below its critical temperature, so that low-molecular weight lipids containing substantially all the sterols are dissolved in the fluid and the high-molecular weight lipids substantially free of the sterols remain; contacting the sterol/lipid laden fluid with an adsorbent which is designed to selectively adsorb substantially all the sterols from the lipids, while leaving all the lipids substantially in the fluid; recovering the lipid from the high-pressure fluid and if desired recovering the high-molecular weight lipid from the dissolution step; and further, if desired, modifying the properties of the low- molecular weight lipid fraction by adding at least a part of the high-molecular weight fraction to the low-molecular weight material; and still further, if desired, recovering the steadsorbent
  • the invention also includes a process in which the fluid is in a supercritical state and hence substantially all the lipids will be extracted into the fluid.
  • the temperature of the fluid is then lowered to a subcritical temperature at which 'time those high molecular weight lipids which are insoluble will precipitate and can be recovered whilst the lipid and cholesterol laden fluid can be further processed as described above.
  • the two fluids were contacted at a temperature of 15°C, and a pressure of 250 bar. After contact the fat-rich carbon dioxide was passed to a separator in which the dissolved fat was recovered. The C0 2 was recirculated.
  • the triglyceride profile in Figure 1 shows that this residue was essentially comprised of carbon number C40 and above. This residue was free of cholesterol.
  • Figure 2 indicates the variation of softening point of the extracted fraction with extraction temperature.
  • the attached drawing shows in schematic form the process of the inventio .
  • Lipid containing material is fed into the extractor and subcritical carbon dioxide contacts that material.
  • the heavy fractions of the lipid are not solubilised in the carbon dioxide stream and hence are recovered from the extractor.
  • the remaining lipid rich stream then is fed to the adsorber where cholesterol is removed and then to a separator where the light lipid fractions are recovered.
  • the carbon dioxide is then recycled back to the extractor.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Microbiology (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dairy Products (AREA)
  • Fats And Perfumes (AREA)

Abstract

On décrit un procédé d'extraction d'une partie des lipides à partir d'un lipide ou d'un mélange contenant les lipides et qui consiste à mettre en contact le lipide ou le mélange, à une pression et à une température appropriées, avec un fluide sous-critique d'un type tel qu'une partie du lipide y est plus soluble que le reste du lipide ou les autres constituants du mélange, et dans des conditions telles qu'une partie d'un constituant lipidique est absorbée par le fluide, puis à récupérer le lipide à partir de ce fluide et à récupérer éventuellement le reste du lipide n'ayant pas été absorbé par le fluide. Le procédé peut être utilisé notamment pour fractionner les triglycérides dans le beurre ou les graisses du lait à l'aide d'un dioxyde de carbone sous-critique.
PCT/AU1991/000105 1990-11-13 1991-03-21 Fractionnement de lipides et produits ainsi obtenus WO1992008363A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NZ23606490 1990-11-13
NZ236064 1990-11-13
NZ236285 1990-11-29
NZ23628590 1990-11-29

Publications (1)

Publication Number Publication Date
WO1992008363A1 true WO1992008363A1 (fr) 1992-05-29

Family

ID=26650934

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1991/000105 WO1992008363A1 (fr) 1990-11-13 1991-03-21 Fractionnement de lipides et produits ainsi obtenus

Country Status (3)

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AU (1) AU7468291A (fr)
CS (1) CS81091A3 (fr)
WO (1) WO1992008363A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016712A1 (fr) * 1994-11-25 1996-06-06 Helsinki University Licensing Ltd. Oy Procede de separation de lipides
WO1996019922A1 (fr) * 1994-12-23 1996-07-04 Tetra Laval Holdings & Finance Procede et dispositif de refroidissement d'un liquide pouvant etre pompe, charge ou non de particules
WO2004103093A1 (fr) * 2003-05-20 2004-12-02 Degussa Ag Procede de separation selective de matieres
US7919131B2 (en) 2003-01-31 2011-04-05 Fonterra Co-Operative Group Limited Extraction of compounds from dairy products
US10144904B2 (en) 2015-12-04 2018-12-04 Evonik Degussa Gmbh Process for extraction of aroma chemicals from fat-containing and/or aqueous liquid phases

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5104587A (en) * 1990-05-16 1992-04-14 The Procter & Gamble Company Countercurrent liquid/liquid extraction to fractionate complex mixtures containing medium and long chain fatty acid triglycerides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1132836A (fr) * 1978-02-13 1982-10-05 Kurt Zosel Methode de decafeinisation directe des extraits aqueux de cafe
US4504503A (en) * 1981-09-09 1985-03-12 Lever Brothers Company Fractionation of butterfat using a liquefied gas or a gas in the supercritical state
US4692280A (en) * 1986-12-01 1987-09-08 The United States Of America As Represented By The Secretary Of Commerce Purification of fish oils
EP0321055A1 (fr) * 1987-12-16 1989-06-21 Unilever N.V. Procédé d'extraction de lactones de matière lipide et utilisation de l'extrait ainsi obtenu pour aromatiser des produits alimentaires

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1132836A (fr) * 1978-02-13 1982-10-05 Kurt Zosel Methode de decafeinisation directe des extraits aqueux de cafe
US4504503A (en) * 1981-09-09 1985-03-12 Lever Brothers Company Fractionation of butterfat using a liquefied gas or a gas in the supercritical state
US4692280A (en) * 1986-12-01 1987-09-08 The United States Of America As Represented By The Secretary Of Commerce Purification of fish oils
EP0321055A1 (fr) * 1987-12-16 1989-06-21 Unilever N.V. Procédé d'extraction de lactones de matière lipide et utilisation de l'extrait ainsi obtenu pour aromatiser des produits alimentaires

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016712A1 (fr) * 1994-11-25 1996-06-06 Helsinki University Licensing Ltd. Oy Procede de separation de lipides
US5759549A (en) * 1994-11-25 1998-06-02 Helsinki University Licensing, Ltd. Processes for the separatin of lipids
WO1996019922A1 (fr) * 1994-12-23 1996-07-04 Tetra Laval Holdings & Finance Procede et dispositif de refroidissement d'un liquide pouvant etre pompe, charge ou non de particules
US7919131B2 (en) 2003-01-31 2011-04-05 Fonterra Co-Operative Group Limited Extraction of compounds from dairy products
WO2004103093A1 (fr) * 2003-05-20 2004-12-02 Degussa Ag Procede de separation selective de matieres
US10144904B2 (en) 2015-12-04 2018-12-04 Evonik Degussa Gmbh Process for extraction of aroma chemicals from fat-containing and/or aqueous liquid phases

Also Published As

Publication number Publication date
CS81091A3 (en) 1992-06-17
AU7468291A (en) 1992-06-11

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