EP0349606B1 - Procede d'obtention d'acide oleique de grande purete par hydrolyse d'huile de graines de tournesol - Google Patents

Procede d'obtention d'acide oleique de grande purete par hydrolyse d'huile de graines de tournesol Download PDF

Info

Publication number
EP0349606B1
EP0349606B1 EP88909701A EP88909701A EP0349606B1 EP 0349606 B1 EP0349606 B1 EP 0349606B1 EP 88909701 A EP88909701 A EP 88909701A EP 88909701 A EP88909701 A EP 88909701A EP 0349606 B1 EP0349606 B1 EP 0349606B1
Authority
EP
European Patent Office
Prior art keywords
oleic acid
oil
range
oleic
hydrolysis
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP88909701A
Other languages
German (de)
English (en)
Other versions
EP0349606A1 (fr
Inventor
Melody A. Wilk
Richard Yodice
Eileen T. Boone
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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 Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP0349606A1 publication Critical patent/EP0349606A1/fr
Application granted granted Critical
Publication of EP0349606B1 publication Critical patent/EP0349606B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • This invention relates to the field of methods for producing cis-9 octadecenoic acid, i.e. oleic acid. More particularly, the invention relates to the enzymatic hydrolysis of high oleic sunflower seed oil to produce a highly pure form of oleic acid as well as highly pure oleic acid compositions derived from such hydrolysis.
  • the main advantages of using enzymes as compared to conventional high-pressure steam for fat splitting are (1) a cleaner purer product due to a more specific reaction; (2) a lower energy requirement; and (3) the resulting sweet water is clearer, i.e. the glycerin water mixture resulting from the hydrolysis is clearer.
  • Oleic acid is a monounsaturated fatty acid of the formula CH3(CH2)7(CH:CH)(CH2)7COOH present within natural fats and oils or biological lipids. Oleic acid is a very important substance in both industry and biology. Cleaner, purer products are inherently safer when used in connection with products such as pharmaceuticals; and purer starting materials allow for the production of purer fine chemical derivatives.
  • Oleic acid is most generally obtained from high-pressure steam fat splitting processes using tallow as the starting material. When produced by such fat splitting processes, oleic acid is not generally obtained in a pure form. Highly purified oleic acid is both colorless and odorless and has excellent stability with respect to oxidative degradation. These properties make it extremely useful in connection with a large number of food and pharmaceutical products. Pure oleic acid can be used safely due to its excellent physical, chemical and physiological properties. Due to such properties oleic acid is actively and widely utilized in the fine chemical or specialty chemical fields. For example, oleic acid is extensively used in pharmaceuticals, cosmetics and foods and has found application in biochemical areas in connection with biosensors and biosurfactants. Oleic acid has also found application in connection with electronics for the stimulation of biological function as well as a number of other quickly developing high technology fields.
  • oleic acid Many uses for oleic acid require that the oleic acid be very pure, and commercially available oleic acid generally includes fatty acid homologs having different carbon numbers and double bond numbers. In addition, commercially available oleic acid often contains various minor impurities. Oleic acid compositions which are impure have properties and characteristics which make them unsatisfactory with respect to color, odor, stability, safety and the like making such compositions incapable of performing adequately in a number of high technology applications.
  • EP-A-0 232 933 describes the hydrolysis of fats in an aqueous medium using lipase immobilized on certain porous polymeric supports in order to prevent inactivation of the lipase.
  • the only lipase used as described in the examples is Candida rugosa (Candida cylindracea) which hydrolyzes olive oil in a yield of only 10-20% (Example 5, page 14, line 37). Lipase from Candida rugosa shows no substrate specificity; see page 2, lines 44 - 48.
  • GB-A-2 176 480 also describes the hydrolysis of fat or oil in an aqueous medium using a lipase.
  • the particular technical problem to be solved seems to be to prevent inactivation of the lipase in the reaction system by maintaining the glycerol concentration in the aqueous phase in the reaction system constant within a range of 10 to 40% by weight; see abstract.
  • the lipase derived from Candida rugosa (Candida cylindracea) is used for the hydrolysis of soybean oil (Ex. 1), beef tallow (Ex. 8) and olive oil (Ex. 9).
  • the two conventional oils comprise fatty acids of different types in different amounts.
  • sunflower seed oil which has a high content of oleic acid moieties and a low content of linoleic acid moieties; see column 8, Table 3.
  • the sunflower seed oils were hydrolyzed with aqueous sodium hydroxide solution; see column 8, lines 3-7.
  • the patent discloses a composition useful for hydrolysis in an aqueous medium comprising a mixture of from 15 to 95 units of Rhizopus arrhizus lipase and from 5 to 85 units of Candida cylindracea lipase per 100 units of total lipase present.
  • U.S. Patent 4,259,440 A specific method and composition for the hydrolysis of triglycerides is described in U.S. Patent 4,259,440.
  • the method includes the steps of adding lipase and cholesterol esterase to a triglyceride in combination with a glycerol assay system and determining the amount of triglycerides present based on the amount of glycerol produced.
  • Other patents which refer generally to the enzymatic hydrolysis of triglycerides are referred to within U.S. patent 4,259,440.
  • U.S. Patent 4,275,011 describes a process for the interesterification of oils and fats comprising treating such oils and fats with a water-soluble microbial enzyme.
  • the microbial enzyme is adsorbed on an inert, powdered, water insoluble dispersing agent. Thereafter, the enzyme which is adsorbed onto the inert substrate is recovered from the reaction medium.
  • the technical problem underlying the present invention is to provide an efficient and low energy process for producing highly pure oleic acid. This problem is solved by a process comprising
  • the high oleic sunflower seed oils such as used in connection with the present invention have an oleic content of, preferably 88% or more, and most preferably about 95%.
  • Such high oleic oils are subjected to enzymatic hydrolysis by contacting the triglycerides with a combination of hydrolase enzymes to provide a reaction product which includes a high purity oleic acid.
  • the reaction medium resulting from the enzymatic hydrolysis contains the oleic acid, glycerol, and a number of contaminant acids. By carrying out the reaction in an aqueous medium the glycerol and other water soluble compounds can be easily separated from the water insoluble oleic acid.
  • high oleic sunflower seed oil "high oleic sunflower oil” and “high oleic oil” will be used synonymously to mean an oil extracted from the seed of a sunflower plant which oil contains triglycerides which have fatty acid moieties and wherein 80% or more of such moieties are oleic acid moieties (preferably 88% or more, most preferably about 95%) and further wherein the ratio of oleic acid moieties : linoleic moieties is 1:(less than 0.09), preferably in the range of from about 1:0.09 to about 1:0.01 and most preferably in the range from about 1:0.09 to about 1:0.01.
  • high purity oleic acid refers to oleic acid compositions obtained by using a “high oleic sunflower oil” starting material and carrying out the process of the present invention.
  • a typical high purity oleic acid obtained according to the present invention would have approximately the following physical characteristics: Typical Sample Specific Gravity (at 15.6°C) 0.899 Color (ASTM) L2.0 Color (Gardner) 5-6 % H20 0.13 Acid value 201 Iodine Value 87.8 Titer 18°C
  • An advantage of the process of the present invention is that the hydrolysis of the triglycerides within the sunflower oils can be carried out in an energy efficient manner.
  • a feature of the process of the present invention is that the reaction product resulting from the hydrolysis of the high oleic sunflower seed oil is a high purity oleic acid having a variety of uses within high technology fields.
  • Another feature of the process of the present invention is that it combines technological advancements from the unrelated fields of (1) agricultural plant development; (2) biochemical enzymatic hydrolysis and (3) chemical engineering purification procedures respectively.
  • the sunflower (genus Helianthus) is second only to the soybean as a source worldwide for vegetable oil. In the United States alone, there are approximately four million acres planted annually in sunflower, primarily in the Dakotas and in Minnesota. Average sunflower yields in the United States range from about 1200 to about 1400 kilograms per hectare, with the oil content from harvested seed averaging about 40 to 45% on a dry weight basis. Increasing both the oil content (as a percentage of total plant weight) and the yield of these sunflower plants are major objectives of plant breeding projects which the present invention utilizes as source material.
  • Sunflower seed oil is comprised primarily of palmitic, stearic, oleic and linoleic acids, with oleic acid and linoleic acid accounting for about 90% of the total fatty acid content of the conventional sunflower seed oils.
  • sunflower seed oil is known to contain 13 varieties of fatty acids including linoleic, oleic, palmitic, stearic, linolenic, palmitoleic, arachidic, margaric and behenic acid; see T.
  • a high linoleic acid concentration is desirable in sunflower oil used in soft margarines and salad dressings, high oleic acid content is preferred for many other applications.
  • a high oleic sunflower seed oil is desirable with respect to the present invention which involves the production of a high purity oleic acid.
  • the purity of the oleic acid with respect to its lack of linoleic acid, increases the oxidative stability of the product obtained.
  • the oxidative stability of conventional crude sunflower oil derived from seed grown in southern climates is nearly twice that of the crude oil extracted from northern-grown sunflower seeds.
  • the various fatty acids are characteristic of the oil of a given variety of seed. Such acid contents may be expressed as a percentage of the total fatty acid content of the trigylceride making up the oil.
  • This method of describing the oils obtained from sunflower seeds used in connection with the present invention is utilized herein.
  • the dimensionless ratios of oleic acid to linoleic acid mentioned below are calculated by dividing the linoleic acid percentage of total fatty acid moieties on the triglyceride by the like percentage of oleic acid moieties. Thus, smaller numbers represent a larger percentage of oleic acid relative to linoleic acid.
  • the selectivity of the enzyme is often not sufficiently specific to differentiate between linoleic and oleic acids containing the same number of carbons and an overlapping unsaturated position. Accordingly, it is particularly important to use a sunflower seed oil which has a dramatically lower linoleic content coupled with a high oleic content of 80% or greater by weight, and more preferably 88% oleic or greater and most preferably about 95% oleic content.
  • the sunflower seed oil is obtained from a substantially homogeneous assemblage of sunflower seeds.
  • any particular sunflower seed within the assemblage may well contain higher or lower amounts of oleic acid and different ratios of linoleic to oleic acid.
  • the resulting statistical mixture of triglycerides obtained from the substantially homogeneous assemblage of sunflower seeds provides an oil which on average contains 80% or more, more preferably 88% or more oleic most preferably 95% or more oleic with the ratio of the oleic to linoleic of 1:(less than 0.09).
  • a typical sunflower seed oil used in connection with the present invention would include the following acid moieties in the given percent amounts: Acid Moiety % present Oleic (18 carbons, one double bond) 80.0 Linoleic (18 carbons, 2 double bonds) 8.1 Stearic (18 carbons, no double bond) 5.5 Palmitic (16 carbons, no double bond) 4.2 Behenic (22 carbons, no double bond) 0.7 Linolenic (18 carbons, 3 double bonds) 0.2
  • the distillation steps required vary depending on the chain length of the fatty acid being isolated. As the chain length increases, the amount of temperature and vacuum required to carry out distillation also increases which further increases the expense due to the additional energy requirements. Further, as the temperature of distillation is increased, reactions can occur among the fatty acids themselves resulting in polymerization and the oxidative degradation. This decreases the yield of the fatty acid obtained from such techniques. In addition to the occurrence of polymerization reactions, some fatty acids isomerize at their double bonds creating large amounts of isomerized fatty acids which decrease the yield of the fatty acid product obtained.
  • the process of the present invention does not make use of any high pressure, high temperature techniques in order to separate the fatty acids from the trigylcerides within the sunflower seed oil.
  • the process of the present invention utilizes enzymatic hydrolysis to carry out decomposition of the sunflower seed oil.
  • the enzymatic hydrolysis reactions carried out in accordance with the present invention are very selective and have a very low energy requirement.
  • the selectivity of the reaction increases the amount of a particular fatty acid removed from the triglyceride, thus, increasing the purity of the resulting oleic acid.
  • high temperatures are not required during the hydrolysis and are actually undesirable, fatty acids are not lost by polymerization or isomerization reactions which occur under high temperature.
  • the ability of enzymes derived from specific microbes to hydrolyze a material is often specific to the material. Accordingly, the enzymatic hydrolysis reaction used in connection with the present invention are carried out only on high oleic sunflower seed oils which have been described above. To develop the process of the present invention, particular reaction conditions necessary to enzymatically hydrolyze such high oleic sunflower seed oil have been carefully studied with regard to the type and amount of enzyme, the pH of the reaction mixture, the type and amount of additives, the temperature and the amount of water necessary to obtain both a high purity oleic acid and a high yield. Adjustment of these parameters can increase the percent of hydrolysis and/or selectivity of the reaction.
  • the enzymes used in connection with the present invention can be divided into different categories as follows:
  • High oleic sunflower seed oil used in connection with the present invention is comprised of trigylcerides having the following general structural formula (I): wherein R, R' and R'' are hydrocarbon moieties of the acid moieties, 80% or more of which are oleic acid moieties. As indicated above, preferably 88% or more of the acid moieties are oleic and most preferably about 95% are oleic moieties.
  • a non-site-specific enzyme When a non-site-specific enzyme is brought into contact with a triglyceride of general structural formula (I), the enzyme will separate all of the fatty acid moieties at all three positions and leave a mixture of glycerol and the separated fatty acids.
  • the site-specific enzyme When a site-specific enzyme is utilized in connection with the triglyceride, the site-specific enzyme generally removes the fatty acid moiety from the two primary positions of the triglyceride. Thus, a 100% efficient reaction of such a site-specific enzyme with such a triglyceride would remove two-thirds of the fatty acid moieties.
  • the enzyme When a fatty acid selective enzyme is reacted with the triglyceride, the enzyme will react with fatty acid positions wherein particular fatty acids are located (the acid generally being recognized by a particular unsaturated position). For example, the enzyme could react with only oleic fatty acid moieties which have an unsaturated position at the delta nine carbon. However, such fatty acid selective enzymes might also react with other non-oleic moieties which also have an unsaturated position at the ninth carbon.
  • one embodiment of the invention involves the use of the high oleic sunflower seed oil starting material in combination with enzymatic hydrolysis techniques to obtain a high yield of oleic acid in a relatively high purity.
  • the resulting hydrolyzed product is comprised of fatty acids and glycerol with the glycerol being soluble within the aqueous phase.
  • the aqueous phase is then separated away, leaving a relatively high yield of a high purity oleic acid composition.
  • the present invention involves the use of a combination of hydrolase enzymes, and more specifically water soluble lipases.
  • microbes from which are derived non site-specific lipases used in connection with the present invention Candida rugosa (cylindracea) Chromobacterium viscosum Humicola lanuginosa Candida lipolytica
  • Aspergillus niger Mucor miehei
  • Mucor pusillus Rhizopus sp.
  • Rhizopus sp. Rhizopus sp.
  • Pseudomonas sp. Penicillium cyclopium.
  • Geotrichum candidum microbes are the source of enzymes which are selective for fatty acids with a delta nine carbon atom.
  • Some particular combinations of enzymes are found to be particularly useful in connection with the present invention are derived from the following combinations of microbes.
  • the amount of the hydrolase enzymes utilized depends on the amount of the triglyceride to be hydrolyzed.
  • the amount of the enzymes is expressed in units (U) of activity in connection with the hydrolytic decomposition of the triglyceride.
  • the amount of enzymes utilized varies depending on the particular enzyme used. Since the present invention only applies enzymes to high oleic sunflower seed oils, the amount and type of enzymes does not vary substantially depending upon the oil being hydrolyzed. However, other parameters do affect the amount of the enzymes utilized such as the reaction time, temperature and pH of the reaction medium. In connection with the present invention, it is useful to utilize 10 to 5,000 preferably 10 to 100 more preferably 20 to 40 units per gram of high oleic sunflower seed oil.
  • the enzymatic hydrolysis reaction carried out in accordance with the process of the present invention is preferably carried out in the presence of water in an amount in the range of about 0.5 to 1.5 times the amount of the high oleic sunflower seed oil.
  • the water must be present in a sufficient amount to allow for the hydrolysis to efficiently proceed.
  • the inclusion of too much water can also decrease the efficiency of hydrolysis and make it difficult to effectively remove and dispose of the aqueous phase of the reaction medium.
  • the enzymatic hydrolysis reactions of the present invention take place at the sunflower seed oil/water interface.
  • sunflower seed oil (oil) and water vary with each system and must be adjusted in order to obtain the best results.
  • the oil/water ratio is (1-1 ⁇ 2):(1-11 ⁇ 2) preferably 1:(1-11 ⁇ 2) at a temperature which is most preferably about 35°C ⁇ 2°C.
  • the temperature is generally about 38°-40°C with a combination of hydrolase enzymes specific for the 1,3 position of the triglyceride. more generally the temperature can range from 20°C to 60°C.
  • the pH of the enzymatic reaction mixture affects the hydrolysis.
  • the hydrolytic reaction yields a carboxylic acid which is not water soluble.
  • the reaction can be carried out in the presence of other additives although other additives are not generally useful in connection with the present invention.
  • the enzymatic hydrolysis of the present invention is preferably carried out in a temperature range of about 20°C to 60°C, more preferably, about 30°C to 50°C.
  • the temperature must generally be kept above 20°C in order to allow for the reaction to proceed quickly enough to economically carry out the procedure and must be carried out below 60°C in order to avoid deactivation of the enzyme prior to its interaction with the trigylceride. It is also desirable to continually agitate the reaction mixture in order to promote the enzymatic hydrolysis of the triglycerides.
  • the relative amounts of oil/water vary with other factors such as the amount of agitation, temperature and the enzyme source. Clearly, the amount of oil/water interface is affected by agitation and to some extent by temperature.
  • the oil to water ratio is preferably 1:(11 ⁇ 2), (more preferably 1: 1.2) the temperature is preferably 30°C to 50°C and agitation is generally carried out at sufficient speed in order to keep the oil and water phases in a homogeneous dispersion.
  • the specific purity of the oleic acid varies somewhat depending on the starting high oleic sunflower oil used.
  • the oleic acid obtained from utilizing the high oleic sunflower seed oil and subjecting the oil to hydrolysis in accordance with the process of the present invention is considered to be the broadest aspect of the present invention.
  • this oleic acid obtained from the high oleic sunflower seed oil can be further purified by physical and chemical procedures which will now be described in detail.
  • the reaction product separates into two phases with the upper phase being comprised of the fatty acids and the lower aqueous phase being comprised largely of water having dissolved therein glycerol and certain contaminants from the high oleic sunflower seed oil. Accordingly, the first step in purification of the enzymatic hydrolysis product is to separate away the lower aqueous phase containing the water soluble compounds. The remaining upper phase will contain oleic acid in a very high concentration.
  • the characteristics of the oleic acid will vary depending on the starting sunflower seeds used. The following is typical of such a high oleic acid:
  • the oil might also include some metals such as Ca, Zn, and Fe in small amounts, e.g. 1-100 ppm.
  • metals such as Ca, Zn, and Fe in small amounts, e.g. 1-100 ppm.
  • Each of the above physical and chemical characteristics might vary to different degrees, but in general might vary ⁇ 10%.
  • the upper phase will include contaminant fatty acids such as linoleic acid as well as other fatty acids which having longer and/or shorter chains than oleic acid as well as greater and lesser degrees of unsaturation.
  • contaminant fatty acids can then be separated away by utilizing one or more chemical or physical separation techniques.
  • chemical separation techniques such as those described in U.S. Patent 4,601,856.
  • the highly pure oleic acid obtained in the process of the invention is obtained as the upper phase resulting from the enzymatic hydrolysis process described above.
  • This highly pure oleic acid includes several different types of fatty acids and other contaminants as indicated above. It is possible to separate away fatty acids having different chain lengths and fatty acids having different degrees of unsaturation in order to further purify the oleic acid composition. More specifically, those fatty acids having more or less than 18 carbon atoms or more or less than one unsaturated bond can be separated away from the oleic acid which contains 18 carbon atoms and a single unsaturated bond.
  • a highly pure oleic acid obtained in the process of the invention can be winterized by subjecting the oleic acid containing reaction mixture to a low temperature treatment. By reducing the temperature gradually until crystallization begins, it is possible to separate away those fatty acids which contain higher degrees of saturation than oleic acid. Accordingly, by reducing the temperature gradually a point will be reached wherein fatty acids such as stearic and palmitic acid will crystallize and precipitate within the composition. These fatty acids can then be removed to provide a further purified high oleic acid composition.
  • Polar solvents such as acetone and methanol allow saturated acids such as stearic acid and palmitic acid to crystallize almost quantitatively while the unsaturated acids such as oleic acid remain dissolved within a solvent. Accordingly, separation can be accomplished by including acetone and/or methanol in the oleic acid containing reaction mixture in an amount sufficient to bring about crystallization of the contaminant palmitic and stearic acids. After the crystallization occurs filtration can be carried out in order to remove the crystallized contaminant palmitic and stearic acids. In general the acetone or methanol solvents are added to the reaction mixture in a ratio of 3-4 liters of solvent per liter of fatty acid.
  • the temperature is reduced to bring about crystallization.
  • the temperature is reduced to -10 to -15°C and filtration is carried out utilizing a vacuum rotary filter after crystallization occurs.
  • the filter can then be sprayed with cold acetone to remove any free oleic acid.
  • Solvents are removed from the oleic acid by flash evaporation and steam stripping.
  • the enzymatic hydrolysis procedure is carried out. Thereafter the lower aqueous phase is separated.
  • the upper phase includes the oleic acid.
  • Approximately 1 liter of the oleic acid containing phase is mixed with 3 liters of methanol and the temperature is reduced to a range between -10 and -15°C. The mixture is kept at the reduced temperature until crystallization appears to be complete.
  • the crystallized material is filtered off and a highly purified oleic acid is obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Claims (19)

  1. Procédé de préparation d'acide oléique très pur par hydrolyse d'une huile de graines de tournesol, dans lequel:
    a) on soumet de l'huile de graines de tournesol dans laquelle les triglycérides qui contiennent des parties d'acides oléiques en une quantité d'environ 80% ou plus et les triglycérides ont un rapport des parties à l'acide oléique aux parties acide linoléique de 1: (moins de 0,09) à une hydrolyse enzymatique dans un milieu aqueux en présence d'une combinaison d'enzymes hydrolase dans des conditions permettant l'hydrolyse des triglycérides d'huile de graines de tournesol,
    b) on laisse se former une couche d'une composition contenant de l'acide oléique et on la laisse séparer du milieu aqueux contenant du glycérol obtenu et,
    c) on sépare la composition contenant l'acide oléique d'avec la couche aqueuse contenant du glycérol.
  2. Procédé selon la revendication 1, dans lequel les parties acide oléique sont présentes sur les triglycérides en une quantité d'environ 88% ou plus.
  3. Procédé tel que revendiqué dans la revendication 1 ou 2, dans lequel les triglycérides ont un rapport des parties acide oléique aux parties acide linoléique compris entre environ 1:0,09 à environ 1:0,01.
  4. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 3, dans lequel les parties acide oléique sont présentes en une quantité d'environ 95% et les triglycérides ont un rapport des parties acide oléique aux parties acide linoléique compris dans un intervalle d'environ 1:0,09 à environ 1:0,01.
  5. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel les enzymes hydrolase sont choisies dans le groupe constitué par une enzyme dérivée de Candida rugosa, Chromobacterium viscosum, Humicola languinose, Candida lipolytica, Aspergillus niger, Mucor miehei, Mucor pusillus, Geotrichum candidum, Rhizopus sp., Pseudomonas sp. et Penicillum cyclopium.
  6. Procéde tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Candida rugosa et Penicillium cyclopium.
  7. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Aspergillus niger et Penicillium cyclopium.
  8. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Mucor miehei, Candida rugosa et Penicillium cyclopium.
  9. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Mucor pusillus et Penicillium cyclopium.
  10. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Chromobacterium viscosum et Penicillium cyclopium.
  11. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Mucor miehei et Penicillium cyclopium.
  12. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 4, dans lequel l'enzyme hydrolase est dérivée d'une combinaison de Pseudomonas sp. et Penicillium cyclopium.
  13. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 12, dans lequel le milieu aqueux contient un tampon choisi dans le groupe constitué par les tampons d'acétate et de phosphate capables de maintenir le pH dans un intervalle de 4,5 à environ 10 au cours de l'hydrolyse enzymatique.
  14. Procéde tel que revendiqué dans l'une quelconque des revendications 1 à 13, dans lequel l'hydrolyse enzymatique est réalisée à une température comprise entre environ 20°C et environ 60°C à un pH compris entre environ 4,5 et environ 10,0.
  15. Procédé tel que revendiqué dans l'une quelconque des revendications 1 à 14, dans lequel le rapport de l'huile de graines de tournesol à l'eau est de 1:0,5 à 1:1,5, la température est comprise entre 30°C et 50°C et le pH est compris entre environ 5,5 et environ 9,0, et le mélange d'huile de graines de tournesol et le milieu aqueux est agité à une vitesse suffisante pour maintenir les phases huile et aqueuse en une dispersion homogène.
  16. Procédé tel que revendiqué dans la revendication 15, dans lequel le milieu aqueux contient un tampon capable de maintenir le pH dans un intervalle de 5,5 à 9,0 au cours de l'hydrolyse enzymatique.
  17. Procédé tel que revendiqué dans la revendication 1(c), dans lequel en outre:
       on ajoute un solvant polaire à la composition contenant de l'acide oléique obtenu dans l'étape 1(c);
       on réduite graduellement la température du mélange liquide à environ 0°C à -20°C;
       on maintient la température dans un intervalle de 0°C à -20°C jusqu'à ce que se produise une saturation des acides gras saturés, et
       on enlève les acides gras saturés cristallisés de l'acide oléique.
  18. Procédé tel que revendiqué dans la revendication 17, dans lequel on utilise de l'acétone ou du méthanol comme solvant polaire.
  19. Procédé tel que revendiqué dans la revendication 17, comprenant les étapes de :
       addition d'acétone ou de méthanol à la composition contenant de l'acide oléique dans un rapport de 3 à 4 litres par litre de composition contenant de l'acide oléique;
       réduction de la température du mélange liquide à une température comprise entre -10°C et -15°C;
       maintien de la température dans un intervalle de - 10°C à -15°C jusqu'à ce que se produise une cristallisation des acides gras saturés; et
       enlèvement des acides gras saturés cristallisés de l'acide oléique.
EP88909701A 1987-10-13 1988-10-07 Procede d'obtention d'acide oleique de grande purete par hydrolyse d'huile de graines de tournesol Expired - Lifetime EP0349606B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10824187A 1987-10-13 1987-10-13
US108241 1987-10-13
PCT/US1988/003480 WO1989003419A1 (fr) 1987-10-13 1988-10-07 Procede de production de preparations a base d'acide cis-9-octadecenoique

Publications (2)

Publication Number Publication Date
EP0349606A1 EP0349606A1 (fr) 1990-01-10
EP0349606B1 true EP0349606B1 (fr) 1995-12-06

Family

ID=22321071

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88909701A Expired - Lifetime EP0349606B1 (fr) 1987-10-13 1988-10-07 Procede d'obtention d'acide oleique de grande purete par hydrolyse d'huile de graines de tournesol

Country Status (6)

Country Link
EP (1) EP0349606B1 (fr)
JP (1) JPH02501622A (fr)
AT (1) ATE131206T1 (fr)
AU (1) AU615969B2 (fr)
DE (1) DE3854761T2 (fr)
WO (1) WO1989003419A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8729890D0 (en) * 1987-12-22 1988-02-03 Unilever Plc Improvements in & relating to fat processes
DE4124248A1 (de) * 1991-07-22 1993-01-28 Henkel Kgaa Verfahren zur selektiven fettspaltung, dazu geeignete lipasemischung und mikroorganismus
US5470741A (en) * 1992-07-22 1995-11-28 Henkel Corporation Mutant of Geotrichum candidum which produces novel enzyme system to selectively hydrolyze triglycerides
FR2772374B1 (fr) * 1998-04-20 2001-01-26 Toulousaine De Rech Et De Dev Composition lubrifiante tensioactive
US6388113B1 (en) 1999-06-04 2002-05-14 Consejo Superior De Investigaciones Cientificas ( Csic) High oleic/high stearic sunflower oils
US7592015B2 (en) 1999-06-04 2009-09-22 Consejo Superior De Investigaciones Cientificas Use of high oleic high stearic oils
HU228892B1 (en) 1999-06-04 2013-06-28 Consejo Superior Investigacion High oleic high stearic plants, seeds and oils
US11858872B2 (en) * 2021-03-30 2024-01-02 ExxonMobil Technology and Engineering Company High yield jet fuel from mixed fatty acids

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61297A (ja) * 1984-06-12 1986-01-06 日本油脂株式会社 オレイン酸の製造法
US4627192B1 (en) * 1984-11-16 1995-10-17 Sigco Res Inc Sunflower products and methods for their production
JPS61287989A (ja) * 1985-06-14 1986-12-18 花王株式会社 油脂の加水分解方法
US4629742A (en) * 1986-01-27 1986-12-16 Akzo America Inc. Hydrolysis of fats
GB2188057B (en) * 1986-02-04 1990-03-07 Inst Penyelidikan Minyak Kelap Transesterification of fats and oils
FR2596415B1 (fr) * 1986-03-26 1988-07-01 Elf Aquitaine Procede pour l'execution de reactions enzymatiques au sein d'un solvant organique
GB2190394A (en) * 1986-05-06 1987-11-18 Unilever Plc Edible fats by rearrangement of sunflower oil

Also Published As

Publication number Publication date
DE3854761D1 (de) 1996-01-18
ATE131206T1 (de) 1995-12-15
EP0349606A1 (fr) 1990-01-10
DE3854761T2 (de) 1996-04-25
JPH02501622A (ja) 1990-06-07
AU2612988A (en) 1989-05-02
WO1989003419A1 (fr) 1989-04-20
AU615969B2 (en) 1991-10-17

Similar Documents

Publication Publication Date Title
EP0191217B2 (fr) Procédé de préparation de glycérides en présence de lipases
JP4236128B2 (ja) 精油組成物
EP2175032B1 (fr) Procédé de production d'huile et graisse riche en diacylglycérol
EP1582594B1 (fr) Procédé enzymatique accéléré de synthèse de triglycérides comprenant des acides gras polyinsaturés
EP0307154B1 (fr) Préparation de diglycérides
WO2000003031A1 (fr) Procede de production d'un glyceride partiel
AU2021201921B2 (en) Polyunsaturated fatty acid triglyceride and preparation and uses thereof
AU673538B2 (en) Enzymes produced by mutants of geotrichum candidia
JP4043605B2 (ja) カプサイシン類縁体の製造法
CA2145814C (fr) Huiles a faible teneur en safa
EP0349606B1 (fr) Procede d'obtention d'acide oleique de grande purete par hydrolyse d'huile de graines de tournesol
JPH01312995A (ja) 酵素による油脂の改質方法
JP6715586B2 (ja) 高度不飽和脂肪酸の製造方法
JP2749587B2 (ja) 固定化酵素の製造方法
JP2000004894A (ja) トリグリセリドの製造方法
JPH0730352B2 (ja) 酵素による油脂の精製法
JP6645804B2 (ja) 構造油脂の製造方法
JPS62228290A (ja) カカオバタ−代用脂の製造方法
JP2545480B2 (ja) 機能性食品素材
JP3510422B2 (ja) グリセリン脂肪酸エステルの製造法
JP2570774B2 (ja) 油脂の改質法
EP1978101A1 (fr) Procédé d'enrichissement en acides gras polyinsaturés
JP2011078328A (ja) 不飽和脂肪酸類の製造方法
KR100385625B1 (ko) 고순도 디글리세리드의 분리 및 정제방법
JP2630770B2 (ja) リン脂質の改質法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890810

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19920619

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19951206

Ref country code: CH

Effective date: 19951206

Ref country code: AT

Effective date: 19951206

REF Corresponds to:

Ref document number: 131206

Country of ref document: AT

Date of ref document: 19951215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3854761

Country of ref document: DE

Date of ref document: 19960118

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO ROMA S.P.A.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961031

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970918

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970919

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970925

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970926

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19971010

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980921

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

BERE Be: lapsed

Owner name: THE LUBRIZOL CORP.

Effective date: 19981031

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981007

EUG Se: european patent has lapsed

Ref document number: 88909701.0

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051007